WO2017047703A1 - Adhesive composition, adhesive layer, optical film having attached adhesive layer, optical member, and image display device - Google Patents

Adhesive composition, adhesive layer, optical film having attached adhesive layer, optical member, and image display device Download PDF

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Publication number
WO2017047703A1
WO2017047703A1 PCT/JP2016/077289 JP2016077289W WO2017047703A1 WO 2017047703 A1 WO2017047703 A1 WO 2017047703A1 JP 2016077289 W JP2016077289 W JP 2016077289W WO 2017047703 A1 WO2017047703 A1 WO 2017047703A1
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WO
WIPO (PCT)
Prior art keywords
tackifier
pressure
sensitive adhesive
adhesive layer
film
Prior art date
Application number
PCT/JP2016/077289
Other languages
French (fr)
Japanese (ja)
Inventor
良平 澤▲崎▼
淳 保井
章典 伊▲崎▼
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 JP2016177677A external-priority patent/JP6725373B2/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020187005240A priority Critical patent/KR102315599B1/en
Priority to CN201680052402.3A priority patent/CN108026423B/en
Publication of WO2017047703A1 publication Critical patent/WO2017047703A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • 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
    • C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. Moreover, this invention relates to the optical member containing the said optical film with an adhesive layer which provided the said adhesive layer in the optical film, and the said optical film with an adhesive layer. Furthermore, this invention relates to the image display apparatus containing the said optical film with an adhesive layer and / or an optical member.
  • a single-sided protective polarizing film having a transparent protective film only on one side of a polarizer is known as a polarizing film.
  • a single-sided protective polarizing film can be reduced in thickness and weight, there is a problem that the single-sided polarizer is not easily protected by the protective film, and thus is easily deteriorated by moisture or the like.
  • the polarizer may be similarly deteriorated by moisture or the like.
  • an organic EL panel mounted on an organic EL (Electro Luminescence) display device is very vulnerable to moisture and oxygen in the atmosphere, an optical film having a barrier layer and a barrier function is usually provided on the surface of the organic EL panel.
  • the adhesive layer for bonding them is required not to transmit moisture or the like (low moisture permeability).
  • a low moisture-permeable pressure-sensitive adhesive layer for example, two types of isobutylene resins having different weight average molecular weights and a pressure-sensitive adhesive composition containing a hydrogenated petroleum resin having a specific softening point are included at a specific blending ratio.
  • An adhesive composition is known (see, for example, Patent Document 1).
  • the adhesive sealing composition which has the hydrogenated cyclic olefin type polymer and the polyisobutylene resin which has a specific weight average molecular weight is disclosed (for example, refer patent document 2).
  • the present invention provides a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer having low moisture permeability and having high durability that can suppress the occurrence of problems such as floating and peeling even in a high-temperature environment.
  • this invention provides the optical member containing the adhesive layer formed from the said adhesive composition, the optical film with an adhesive layer provided with the said adhesive layer, and the said optical film with an adhesive layer.
  • Objective. It is another object of the present invention to provide an image display device including at least one selected from the group consisting of the optical film with an adhesive layer and the optical member.
  • the present invention is a pressure-sensitive adhesive composition containing a rubber-based polymer (A) and a tackifier (B),
  • the rubber polymer (A) includes at least one rubber polymer selected from the group consisting of a styrene thermoplastic elastomer (A1) and an isobutylene polymer (A2) having a weight average molecular weight of 500,000 or more.
  • the tackifier (B) is a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2).
  • the tackifier (B) is selected from the group consisting of a natural product-based tackifier (B1) and hydrogenated products thereof. It is related with the adhesive composition characterized by including the at least 1 sort (s) of tackifier selected.
  • the tackifier (B) contains a natural product tackifier (B1).
  • a natural product tackifier (B1) at least one selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof can be used.
  • the tackifier (B) is a hydrogenated product.
  • the softening point of the tackifier (B) is 100 ° C. or higher.
  • the natural product-based tackifier (B1) includes a cyclohexanol skeleton.
  • the content of the tackifier (B) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A).
  • the pressure-sensitive adhesive composition is further selected from the group consisting of a polyisobutylene compound (C1) having a weight average molecular weight of 50,000 or less and a polyisoprene compound (C2) having a weight average molecular weight of 50,000 or less. It is preferable to include at least one softener (C).
  • the content of the softening agent (C) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A).
  • the present invention also relates to a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • the present invention also relates to an optical film with an adhesive layer, characterized by comprising an optical film and the adhesive layer provided on the optical film.
  • the optical film is preferably a polarizing film having a transparent protective film on at least one surface of the polarizer.
  • the polarizing film is preferably a single-sided protective polarizing film having a transparent protective film only on one side of the polarizer, and the pressure-sensitive adhesive layer is preferably laminated on the side of the polarizer that does not have a transparent protective film.
  • the optical film may be a brightness enhancement film.
  • the present invention also provides an optical member comprising the optical film with the pressure-sensitive adhesive layer and a brightness enhancement film, the pressure-sensitive adhesive layer, 40 ° C., 92% R.D. H.
  • the present invention relates to an optical member including a film having a moisture permeability of 1 g / (m 2 ⁇ day) or less.
  • the present invention relates to an image display device comprising at least one selected from the group consisting of the optical film with an adhesive layer and the optical member.
  • the pressure-sensitive adhesive composition of the present invention has a problem (floating or peeling) even in a high temperature environment while maintaining low moisture permeability by adding a specific tackifier (B) to a specific rubber polymer (A). Etc.) can be suppressed (high durability).
  • the present invention can provide an optical film with an adhesive layer, an optical member, and an image display device excellent in optical reliability, which are excellent in durability under a high temperature environment and excellent in low moisture permeability.
  • the pressure-sensitive adhesive composition of the present invention contains a rubber-based polymer (A) and a tackifier (B),
  • the rubber polymer (A) includes at least one rubber polymer selected from the group consisting of a styrene thermoplastic elastomer (A1) and an isobutylene polymer (A2) having a weight average molecular weight of 500,000 or more.
  • the tackifier (B) is a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2).
  • the tackifier (B) is selected from the group consisting of a natural product-based tackifier (B1) and hydrogenated products thereof. It contains at least one selected tackifier.
  • the rubber-based polymer (A) used in the present invention is a polymer that exhibits rubber elasticity in a temperature range near room temperature.
  • the styrene-based thermoplastic elastomer (A1) and the isobutylene-based polymer (A2) having a weight average molecular weight (Mw) of 500,000 or more (hereinafter sometimes simply referred to as “isobutylene-based polymer (A2)”)
  • styrenic thermoplastic elastomer (A1) examples include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene-styrene block copolymer.
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • styrene-butadiene-styrene block copolymer examples include styrene-butadiene-styrene block copolymer.
  • SBS Styrene-ethylene-propylene-styrene block copolymer
  • SIS Styrene-ethylene-propylene block copolymer
  • SEP styrene-isoprene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • SBR styrene-butadiene rubber
  • SEPS styrene-ethylene-propylene-styrene block copolymers
  • SIBS styrene-isobutylene-styrene block copolymer
  • thermoplastic elastomer (A1) for example, commercially available products such as SEPTON and HYBRAR manufactured by Kuraray Co., Ltd., Tuftec manufactured by Asahi Kasei Chemicals Co., Ltd., and SIBSTAR manufactured by Kaneka Co., Ltd. can be used.
  • the weight average molecular weight of the styrenic thermoplastic elastomer (A1) is not particularly limited, but is preferably about 50,000 to 500,000, more preferably about 50,000 to 300,000. More preferably, it is about 50,000 to 250,000. It is preferable that the weight average molecular weight of the styrene-based thermoplastic elastomer (A1) is in the above range because both the cohesive force and viscoelasticity of the polymer can be achieved.
  • the styrene content in the styrenic thermoplastic elastomer (A1) is not particularly limited, but is preferably about 5 to 70% by weight, for example, and more preferably about 5 to 40% by weight. Preferably, it is about 10 to 20% by weight.
  • the styrene content in the styrene-based thermoplastic elastomer (A1) is in the above range, it is preferable because viscoelasticity by the soft segment can be secured while maintaining the cohesive force by the styrene site.
  • Examples of the isobutylene polymer (A2) include those containing isobutylene as a constituent monomer and having a weight average molecular weight of 500,000 or more.
  • the isobutylene polymer (A2) may be a homopolymer of isobutylene (polyisobutylene, PIB), and a copolymer having isobutylene as a main monomer (that is, a copolymer in which isobutylene is copolymerized in a proportion exceeding 50 mol%).
  • Examples of such a copolymer include a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber), These vulcanizates and modified products (for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group) can be used.
  • polyisobutylene (PIB) is preferable because it does not contain a double bond in the main chain and is excellent in weather resistance.
  • isobutylene polymer (A2) for example, commercially available products such as OPPANOL manufactured by BASF can be used.
  • the weight average molecular weight of the isobutylene polymer (A2) is 500,000 or more, preferably 600,000 or more, and more preferably 700,000 or more.
  • the upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million or less, more preferably 3 million or less, and even more preferably 2 million or less.
  • content of the said rubber-type polymer (A) is not specifically limited, It is preferable that it is 30 weight% or more in the total solid of an adhesive composition, and it is more preferable that it is 40 weight% or more. Preferably, it is more preferably 50% by weight or more, and particularly preferably 60% by weight or more.
  • the upper limit of the content of the rubber-based polymer (A) is not particularly limited, and is preferably 95% by weight or less, and more preferably 90% by weight or less.
  • the content thereof is preferably 30% by weight or more in the total solid content of the pressure-sensitive adhesive composition, 35 More preferably, it is more than 40% by weight.
  • the upper limit is not particularly limited, but is preferably about 90% by weight or less, and more preferably about 70% by weight or less.
  • the content thereof is preferably 60% by weight or more in the total solid content of the pressure-sensitive adhesive composition, 70% by weight. % Or more, more preferably 80% by weight or more.
  • the upper limit value is not particularly limited, but is preferably about 98% by weight or less, and more preferably about 90% by weight or less.
  • the pressure-sensitive adhesive composition of the present invention can also contain a rubber polymer other than the rubber polymer (A).
  • a rubber polymer other than the rubber polymer (A) Specifically, butyl rubber (IIR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (ternary ethylene-propylene rubber), acrylic rubber, urethane
  • examples thereof include rubber, polyurethane-based thermoplastic elastomers; polyester-based thermoplastic elastomers; blend-based thermoplastic elastomers such as polymer blends of polypropylene and EPT (ternary ethylene-propylene rubber).
  • Tackifier (B) examples include a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2), and hydrogenated products thereof. These tackifiers (B) are selected according to the rubber polymer (A). That is, when the styrene thermoplastic elastomer (A1) is used, as the tackifier (B), a natural product tackifier (B1), a petroleum resin tackifier (B2), and hydrogenation thereof. At least one selected from the group consisting of things is used.
  • the tackifier (B) is at least one selected from the group consisting of a natural product tackifier (B1) and hydrogenated products thereof. Is used.
  • the pressure-sensitive adhesive composition of the present invention has a pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high-temperature environment. Can be formed.
  • the rubber-based polymer (A) is used, as the tackifier (B), a natural product-based tackifier (B1) containing a hydroxyl group and having high moisture permeability, such as terpene phenol. ) Can be used. That is, in the present invention, by using a specific rubber-based polymer (A) and a specific tackifier (B), durability in a high temperature environment can be improved while maintaining low moisture permeability. It is.
  • Examples of the natural product-based tackifier (B1) include tackifiers containing a terpene skeleton, tackifiers containing a rosin skeleton, and hydrogenated products thereof.
  • the description relating to the natural product-based tackifier (B1) is a concept including the hydrogenated product.
  • tackifiers containing a terpene skeleton include terpene polymers such as ⁇ -pinene polymers, ⁇ -pinene polymers, and dipentene polymers, and modified terpene polymers (phenol-modified, styrene-modified, aromatic-modified). Modified terpene resin, etc.).
  • modified terpene resin include terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin (hydrogenated terpene resin) and the like.
  • Examples of the hydrogenated terpene resin herein include hydrogenated products of terpene polymers and other modified terpene resins and hydrogenated products of terpene phenol resins. Among these, from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive and pressure-sensitive adhesive properties, hydrogenated products of terpene phenol resins are preferable.
  • tackifier containing the rosin skeleton examples include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like.
  • rosin resin polymerized rosin resin
  • hydrogenated rosin resin rosin ester resin
  • hydrogenated rosin ester resin rosin phenol resin
  • gum rosin, wood rosin Unmodified rosin such as tall oil rosin (raw rosin), hydrogenated, disproportionated, polymerized, other chemically modified modified rosin, and derivatives thereof can be used.
  • Examples of the petroleum resin tackifier (B2) include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, Aliphatic / alicyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins and the like can be mentioned.
  • aromatic petroleum resin examples include vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, ⁇ -methylstyrene, ⁇ -methylstyrene, indene, methylindene, etc.) are used alone or in combination of two or more.
  • aromatic petroleum resins (so-called “C9 petroleum resins”) obtained from fractions such as vinyl toluene and indene (so-called “C9 petroleum fractions”) are preferable.
  • aliphatic petroleum resin examples include olefins having 4 to 5 carbon atoms and dienes (olefins such as butene-1, isobutylene and pentene-1; butadiene, piperylene (1,3-pentadiene), isoprene and the like. Examples thereof include polymers in which only one type or two or more types of diene are used.
  • aliphatic petroleum resins so-called “C4 petroleum resins” and “C5 series” obtained from fractions such as butadiene, piperylene and isoprene (so-called “C4 petroleum fraction”, “C5 petroleum fraction”, etc.) Petroleum resin "etc. are preferred.
  • alicyclic petroleum resin for example, an alicyclic polymer obtained after cyclizing and dimerizing an aliphatic petroleum resin (so-called “C4 petroleum resin”, “C5 petroleum resin” or the like).
  • a hydrocarbon polymer a polymer of a cyclic diene compound (cyclopentadiene, dicyclopentadiene, ethylidene norbornene, dipentene, ethylidenebicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, limonene, or the like)
  • aromatic hydrocarbon resins and alicyclic hydrocarbon resins obtained by hydrogenating the aromatic rings of the following aliphatic / aromatic petroleum resins.
  • examples of the aliphatic / aromatic petroleum resin include styrene-olefin copolymers.
  • examples of the aliphatic / aromatic petroleum resin include so-called “C5 / C9 copolymer petroleum resin”.
  • the description relating to the petroleum resin-based tackifier (B2) is a concept including the hydrogenated product.
  • examples of the natural product-based tackifier (B1) include: Clearon series, Polystar series, Yashara Chemical Co., Ltd., Superester series, Arakawa Chemical Co., Ltd. Cell series, pine crystal series, etc. are mentioned, and as the petroleum resin-based tackifier (B2), for example, commercially available products such as Alcon series manufactured by Arakawa Chemical Industries, Ltd. can be used.
  • the hydrogenation may be a partially hydrogenated product that is partially hydrogenated, and all double bonds in the compound are hydrogenated. It may be a complete hydrogenation product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
  • a natural product tackifier (B1) can be suitably used as the tackifier (B).
  • the natural product-based tackifier (B1) preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is considered that the cyclohexanol skeleton is more compatible with the rubber polymer as the base polymer than the phenol skeleton.
  • a tackifier containing a cyclohexanol skeleton for example, hydrogenated products such as terpene phenol resin and rosin phenol resin are preferable, and complete hydrogenated products such as terpene phenol resin and rosin phenol resin are more preferable.
  • the softening point (softening temperature) of the tackifier (B) is not particularly limited, but is preferably about 80 ° C. or higher, and more preferably about 100 ° C. or higher. It is preferable that the softening point of the tackifier (B) is 80 ° C. or higher because the tackifier can be maintained without being softened even at high temperatures.
  • the upper limit value of the softening point of the tackifier (B) is not particularly limited, but if the softening point becomes too high, the molecular weight becomes higher, the compatibility deteriorates, and problems such as whitening may occur. Therefore, for example, it is preferably about 200 ° C. or lower, and preferably about 180 ° C. or lower.
  • the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in either JIS K5902 or JIS K2207.
  • the weight average molecular weight of the tackifier (B) is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less, It is more preferably 8000 or less, and particularly preferably 5000 or less.
  • the lower limit of the weight average molecular weight of the tackifier (B) is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. preferable. It is preferable that the weight-average molecular weight of the tackifier (B) is in the above range since compatibility with the rubber polymer is good and problems such as whitening do not occur.
  • the amount of the tackifier (B) added is preferably 250 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the rubber-based polymer (A). It is preferably 150 parts by weight or less.
  • the amount of the natural product-based tackifier (B1) added is 100 parts by weight of the rubber-based polymer (A).
  • the amount is preferably 100 parts by weight or less, more preferably 85 parts by weight or less, further preferably 50 parts by weight or less, and particularly preferably 45 parts by weight or less.
  • the lower limit of the addition amount of the tackifier (B) is not particularly limited, but is preferably 1 part by weight or more, and more preferably 5 parts by weight or more.
  • the rubber-based polymer (A) contains a styrene-based thermoplastic elastomer (A1)
  • a natural product-based tackifier (B1) and / or a petroleum resin-based tackifier (B2) is used as the tackifier (B).
  • the amount of the natural product-based tackifier (B1) added is preferably 100 parts by weight or less and more preferably 85 parts by weight or less with respect to 100 parts by weight of the styrene-based thermoplastic elastomer (A1).
  • the amount is preferably 70 parts by weight or less, and more preferably 45 parts by weight or less.
  • the lower limit of the amount of the natural product-based tackifier (B1) added is not particularly limited, but is preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more. The amount is more preferably 10 parts by weight or more, and particularly preferably 20 parts by weight or more.
  • the added amount of the natural product-based tackifier (B1) may be 0 parts by weight. .
  • the addition amount of the petroleum resin-based tackifier (B2) is preferably 150 parts by weight or less and 100 parts by weight or less with respect to 100 parts by weight of the styrene-based thermoplastic elastomer (A1). More preferably, it is 70 parts by weight or less, further preferably 50 parts by weight, and further preferably 30 parts by weight.
  • the lower limit value of the addition amount of the petroleum resin tackifier (B2) is not particularly limited, but is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, The amount is more preferably 5 parts by weight or more, and further preferably 10 parts by weight or more.
  • the natural product type tackifier (B1) is contained as the tackifier (B)
  • the petroleum resin type tackifier (B2) may be added in an amount of 0 part by weight.
  • the rubber polymer (A) contains a styrenic thermoplastic elastomer (A1), a natural product tackifier (B1) and a petroleum resin tackifier (B2) are used as the tackifier (B).
  • a natural product tackifier (B1) it is preferable to use a petroleum resin-based tackifier (B2) in view of compatibility with the styrene moiety.
  • the addition amount of the natural product tackifier (B1) is preferably 0.5 to 150 parts by weight, more preferably 0.5 to 150 parts by weight with respect to 100 parts by weight of the styrenic thermoplastic elastomer (A1). 100 parts by weight is preferable, and the amount of petroleum resin tackifier (B2) added is preferably 0.5 to 150 parts by weight, and more preferably 0.5 to 100 parts by weight.
  • a natural product tackifier (B1) is used as the tackifier (B).
  • the amount of the natural product-based tackifier (B1) added is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the isobutylene polymer (A2). More preferably, it is 20 parts by weight or less.
  • the lower limit of the addition amount of the tackifier (B) is not particularly limited, but is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight. More preferably, it is the above.
  • the addition of the said petroleum resin-type tackifier (B2) to an adhesive composition is arbitrary, but the addition The amount is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and may be 0 part by weight with respect to 100 parts by weight of the isobutylene polymer (A2).
  • tackifiers other than the natural product-based tackifier (B1) and petroleum resin-based tackifier (B2) can be added to the pressure-sensitive adhesive composition of the present invention.
  • the addition amount of the other tackifier is preferably 100 parts by weight or less with respect to 100 parts by weight of the rubber-based polymer (A).
  • Additives other than those described above may be added to the pressure-sensitive adhesive composition of the present invention as long as the effects of the present invention are not impaired. Although it does not specifically limit as an additive, It is preferable from a viewpoint of an adhesive characteristic to add a softener (C).
  • the elastic modulus in the low temperature region of the pressure-sensitive adhesive layer may increase, and for example, certain characteristics such as impact resistance may deteriorate.
  • the softener (C) in the pressure-sensitive adhesive composition the elastic modulus of the rubber-based polymer (A) can be lowered due to its plastic effect, and as a result, the tackifier (B ) Is preferable because the occurrence of the above-described problems can be suppressed.
  • the softener (C) is selected from the group consisting of a polyisobutylene compound (C1) having a weight average molecular weight of 50,000 or less and a polyisoprene compound (C2) having a weight average molecular weight of 50,000 or less. There may be mentioned at least one softener.
  • the weight average molecular weight of the softener (C) is 50,000 or less, and more preferably 40,000 or less.
  • the lower limit of the weight average molecular weight of the softening agent (C) is not particularly limited, but is preferably 500 or more, and more preferably 1000 or more.
  • the polyisobutylene compound (C1) may be a compound composed of only isobutylene (polyisobutylene), and a copolymer containing isobutylene as a main monomer (that is, a copolymer containing isobutylene in a proportion exceeding 50 mol%). Thing).
  • copolymers include copolymers of isobutylene and normal butylene, copolymers of isobutylene and isoprene (for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber).
  • Vulcanizates and modified products thereof for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.
  • polyisobutylene is preferable because it does not contain a double bond in the main chain and has excellent weather resistance.
  • the polyisoprene compound (C2) may be a compound consisting of isoprene alone (polyisoprene), and a copolymer having isoprene as a main monomer (that is, a copolymer having a proportion of isoprene exceeding 50 mol%).
  • a copolymer include butadiene-isoprene-styrene random copolymer, isoprene-styrene random copolymer, and hydrogenated polyisoprene.
  • hydrogenated polyisoprene is preferable from the viewpoint of the plasticizing effect on the rubber-based polymer.
  • softener (C) for example, commercially available products such as HV-300 manufactured by JX Nippon Mining & Energy, Kuraprene LIR-200 manufactured by Kuraray Co., Ltd. can be used.
  • the amount of the softening agent (C) added is not particularly limited, but is preferably 50 parts by weight or less, and 30 parts by weight or less with respect to 100 parts by weight of the rubber-based polymer (A). More preferably, it is more preferably 25 parts by weight or less.
  • the lower limit of the addition amount of the softening agent (C) is not particularly limited, but is preferably 0 part by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably.
  • an organic solvent can be added as a diluent to the pressure-sensitive adhesive composition.
  • a diluent for example, toluene, xylene, dimethyl ether etc. can be mentioned, These can be used individually by 1 type or in mixture of 2 or more types. Among these, toluene is preferable.
  • the addition amount of the diluent is not particularly limited, but is preferably added to the pressure-sensitive adhesive composition at about 50 to 95% by weight, more preferably about 70 to 90% by weight. When the addition amount of the diluent is within the above range, it is preferable from the viewpoint of coatability to a support or the like.
  • the pressure-sensitive adhesive composition may further contain any appropriate additive.
  • the additive include a crosslinking agent (for example, polyisocyanate, epoxy compound, alkyl etherified melamine compound, etc.), filler, anti-aging agent, ultraviolet absorber and the like.
  • the kind, combination, addition amount, and the like of the additive added to the pressure-sensitive adhesive composition can be appropriately set according to the purpose.
  • the content (total amount) of the additive in the pressure-sensitive adhesive composition is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less.
  • Adhesive layer The adhesive layer of this invention was formed from the said adhesive composition.
  • An adhesive layer can be formed by apply
  • Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • the heating and drying temperature is preferably about 30 ° C to 200 ° C, more preferably 40 ° C to 180 ° C, and further preferably 80 ° C to 150 ° C. By setting the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained.
  • As the drying time an appropriate time can be adopted as appropriate. The drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
  • a peeled sheet (separator) can be used as the support.
  • constituent material of the separator examples include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although an appropriate thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • -Vinyl acetate copolymer film and the like.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • An antistatic treatment such as a mold can also be performed.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
  • the thickness of the pressure-sensitive adhesive layer of the present invention is not particularly limited, and can be appropriately set depending on the application, but is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and 20 ⁇ m or less. More preferably.
  • the lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 ⁇ m or more and more preferably 5 ⁇ m or more from the viewpoint of durability.
  • the moisture permeability of the pressure-sensitive adhesive layer is not particularly limited, is preferably 100g / (m 2 ⁇ 24h) or less, more preferably 60g / (m 2 ⁇ 24h) or less, 50 g / (m 2 ⁇ 24h) or less is more preferable, 30g / (m 2 ⁇ 24h) or less is more preferable, and 20g / (m 2 ⁇ 24h) or less is particularly preferable.
  • the lower limit value of the moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not transmitted at all (that is, 0 g / (m 2 ⁇ 24 h)).
  • the moisture permeability of the pressure-sensitive adhesive layer is in the above range, when the pressure-sensitive adhesive layer is applied to an optical film such as a polarizing film, it is possible to suppress moisture from being transferred to the optical film, and deterioration of the optical film due to moisture. Etc. can be suppressed.
  • the moisture permeability is 40 ° C. and 92% R.D. when the pressure-sensitive adhesive layer has a thickness of 50 ⁇ m.
  • the water vapor transmission rate (moisture permeability) under the conditions can be measured by the method described in the examples.
  • optical film with a pressure-sensitive adhesive layer of the present invention comprises an optical film and the pressure-sensitive adhesive layer provided on the optical film.
  • the pressure-sensitive adhesive layer is formed on the optical film by applying the pressure-sensitive adhesive composition on the optical film and removing the solvent by heat drying or the like. be able to.
  • an adhesive layer can be formed on a support body etc., the said adhesive layer can be transcribe
  • the release-treated sheet used in the production of the optical film with the pressure-sensitive adhesive layer can be used as it is as a separator of the optical film with the pressure-sensitive adhesive layer, and the process can be simplified.
  • optical film those used for forming various image display devices such as a liquid crystal display device are used, and the type thereof is not particularly limited.
  • a polarizing film is mentioned as an optical film.
  • a polarizing film having a transparent protective film on one side or both sides of a polarizer is generally used, but in the present invention, a single-sided protective polarizing film is preferable from the viewpoint of thinning.
  • the polarizer is not particularly limited, and various types can be used.
  • polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
  • a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • a thin polarizer having a thickness of 10 ⁇ m or less.
  • the thickness is preferably 1 to 7 ⁇ m.
  • Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
  • the thin polarizer typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917 pamphlet, Japanese Patent Application Laid-Open No. 2014-59328, and Japanese Patent Application Laid-Open No. 2014-59328 are disclosed.
  • the thin polarizing film described in 2012-73563 gazette can be mentioned.
  • These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
  • PVA-based resin polyvinyl alcohol-based resin
  • polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • acrylic polymers such as polymethyl methacrylate
  • styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin)
  • AS resin acrylonitrile / styrene copolymer
  • polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends.
  • the transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
  • thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.
  • a protective film made of the same polymer material may be used on the front and back, or a protective film made of a different polymer material or the like may be used.
  • the thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin film properties.
  • the polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like.
  • the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester.
  • examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
  • the electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films.
  • the adhesive used in the present invention can contain a metal compound filler.
  • the surface of the transparent protective film to which the polarizer is not bonded may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the pressure-sensitive adhesive layer 3 is a transparent protective film 5 of the polarizer 4.
  • the polarizer 4 and the pressure-sensitive adhesive layer 3 are not necessarily in contact with each other, but are preferably in contact with each other from the viewpoint that the effects of the present invention can be remarkably exhibited.
  • examples of the optical film other than the polarizing film include a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film.
  • a reflection plate an anti-transmission plate
  • a retardation plate including wavelength plates such as 1/2 and 1/4
  • a viewing angle compensation film and a brightness enhancement film.
  • What becomes an optical layer which may be used for formation of a liquid crystal display device etc. is mentioned.
  • a brightness enhancement film can be suitably used as an optical film. These can be used alone as an optical film, or can be laminated on the polarizing film for practical use to use one layer or two or more layers.
  • the optical film can be activated.
  • Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.
  • optical member of the present invention includes the optical film with the pressure-sensitive adhesive layer, an optical member including a brightness enhancement film (hereinafter referred to as “first optical member”), the pressure-sensitive adhesive layer, 40 ° C., and 92% R. . H.
  • first optical member an optical member including a brightness enhancement film
  • the optical member (henceforth "the 2nd optical member") containing the film whose water vapor transmission rate is 1 g / (m ⁇ 2 > * day) or less can be mentioned.
  • the first optical member is formed by further laminating a brightness enhancement film via the pressure-sensitive adhesive layer of the optical film with the pressure-sensitive adhesive layer.
  • a polarizing film with an adhesive layer As an optical film with an adhesive layer in a 1st optical member, it is preferable that it is a polarizing film with an adhesive layer.
  • the optical member 10 which has the polarizing film 2, the adhesive layer 3, and the brightness enhancement film 6 can be mentioned.
  • such an optical member 10 may have other layers.
  • FIG. 3 as shown in FIG.
  • the prism sheet 7 can be further laminated through (not shown) or the like.
  • the prism sheet 7 typically has a substrate and a prism portion.
  • a double-sided protective polarizing film may be sufficient.
  • Such an optical member is preferably used as a polarizing plate on the backlight side of the liquid crystal display device.
  • the reflective polarizing plate is a linearly polarized light separation type polarizing plate.
  • Typical examples include grid-type polarizing plates, multilayer thin film laminated polarizing plates of two or more materials having different refractive indexes, vapor-deposited multilayer thin films having different refractive indexes, and birefringent multilayer thin films of two or more materials having different refractive indexes.
  • Laminated body two or more kinds of resin laminates using two or more kinds of resins having a refractive index difference, a polarizing plate that separates by reflecting / transmitting linearly polarized light in an orthogonal axis direction (linearly polarized light separation)
  • a linearly polarized light separation type reflection polarizing plate is preferably used.
  • a reflective polarizing plate for example, those commercially available under the trade name “D-BEF” manufactured by 3M or the product name “Nipox APCF” manufactured by Nitto Denko Corporation may be used.
  • the film having a moisture permeability of 1 g / m 2 ⁇ day or less examples include a barrier layer used in an organic EL device.
  • the barrier layer used in the organic EL device include polymers such as polyethylene trifluoride, poly (ethylene trifluorochloride) (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer.
  • Examples thereof include a layer, a laminate thereof, and a polymer layer coated with an inorganic thin film such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon by using a film forming method such as sputtering.
  • An optical member having such a low moisture-permeable film can be suitably used for an organic EL device, and specifically can be used as a sealing member for an organic EL element.
  • Image display device The image display device of the present invention is characterized by including one or more kinds selected from the group consisting of the polarizing film with an adhesive layer and the optical member.
  • Examples of the image display device include a liquid crystal display device and an organic EL display device.
  • the image display device of the present invention only needs to include the optical film or optical member with the pressure-sensitive adhesive layer of the present invention, and other configurations can be the same as those of the conventional image display device.
  • the image display device of the present invention includes the optical film or optical member with the pressure-sensitive adhesive layer, it has high optical reliability.
  • the weight average molecular weight (Mw) was measured by a gel permeation chromatography method (GPC method), and an HLC-8120 (manufactured by Tosoh Corp.) column with an inner diameter of 6.0 mm and a length of 150 mm (manufactured by Tosoh Corp., TSKgel SuperHZM-).
  • H / HZ4000 / HZ3000 / HZ2000 connected in series, tetrahydrofuran is used as the eluent, concentration is 1 g / L, flow rate is 0.6 ml / min, temperature is 40 ° C., sample injection volume is 20 ⁇ l, and detection The detector was an RI detector.
  • TSK standard polystyrene manufactured by Tosoh Corporation was used to prepare a calibration curve for molecular weight.
  • Production Example 1 (Production of polarizing film)
  • a laminate in which a 9 ⁇ m-thick polyvinyl alcohol (PVA) layer is formed on an amorphous polyethylene terephthalate (PET) substrate is stretched by air-assisted stretching at a stretching temperature of 130 ° C.
  • a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio becomes 5.94 times.
  • An optical film laminate comprising a 4 ⁇ m thick PVA layer stretched together was produced.
  • the PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex.
  • an optical film laminate including a PVA layer having a thickness of 5 ⁇ m constituting a highly functional polarizing film (polarizer) was produced.
  • a polyvinyl alcohol adhesive so that the thickness of the adhesive layer is 0.1 ⁇ m on the surface of the polarizing film (polarizer, thickness: 5 ⁇ m) of the optical film laminate according to the polarizer
  • a protective film (a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 ⁇ m and subjected to corona treatment) was bonded, followed by drying at 50 ° C. for 5 minutes. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film using a thin polarizer.
  • Example 1 100 parts by weight of a styrene-ethylene-propylene-styrene block copolymer (SEPS, trade name: SEPTON 2063, styrene content: 13%, manufactured by Kuraray Co., Ltd.) as a rubber polymer (A) and a tackifier (B ) Hydrogenated terpene phenol (trade name: YS Polyster TH130, softening point: 130 ° C., hydroxyl value: 60, manufactured by Yasuhara Chemical Co., Ltd.), 40.4 parts by weight, petroleum-based tackifier (trade name: Picolastic A5, Vinyl toluene-based tackifier, softening point: 5 ° C., Eastman Kodak Co., Ltd.
  • SEPS styrene-ethylene-propylene-styrene block copolymer
  • softening agent (C) polybutene (trade name: HV-300, weight average molecular weight: 3000, JX Nippon Oil & Energy Co., Ltd.)
  • Toluene solution (adhesive solution) containing 21.3 parts was adjusted so that the solid content was 30% by weight.
  • a composition (solution) was prepared.
  • the obtained pressure-sensitive adhesive composition (solution) was applied to the release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) with one side peeled with silicone. Formed. Subsequently, the coating layer was dried at 120 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 20 ⁇ m was produced. Also, the adhesive surface of the pressure-sensitive adhesive sheet is a 38 ⁇ m thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface is in contact with the pressure-sensitive adhesive layer. Were pasted together. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
  • One release liner of the pressure-sensitive adhesive sheet was peeled off, and the pressure-sensitive adhesive layer and the polarizer were laminated on the polarizer of the polarizing film obtained in Production Example 1 to obtain a polarizing film with a pressure-sensitive adhesive layer. .
  • the release liner of the pressure-sensitive adhesive layer was left as a separator.
  • the structure of the obtained polarizing film with an adhesive layer was transparent protective film / polarizer / adhesive layer / separator.
  • Example 1 a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that each component of the pressure-sensitive adhesive composition was changed to the composition described in Tables 1 and 2.
  • Comparative Example 8 production of acrylic pressure-sensitive adhesive layer
  • a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube 99 parts by weight of butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and a polymerization initiator
  • BA butyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • a polymerization initiator After 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so as to have a solid content of 20%, nitrogen substitution was performed for about 1 hour while flowing nitrogen gas and stirring. Thereafter, the flask was heated to 60 ° C.
  • an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million.
  • solid content 100 parts by weight
  • 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent
  • silane coupling agent An acrylic pressure-sensitive adhesive composition was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • a polarizing film with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 50 ⁇ m was formed according to the method described in the examples.
  • One release liner of the pressure-sensitive adhesive sheet was peeled off to expose the pressure-sensitive adhesive surface, and the pressure-sensitive adhesive surface was bonded to a triacetylcellulose film (TAC film, thickness 25 ⁇ m, manufactured by Konica Minolta Co., Ltd.). Then, the other release liner was peeled off to obtain a measurement sample.
  • TAC film triacetylcellulose film, thickness 25 ⁇ m, manufactured by Konica Minolta Co., Ltd.
  • moisture permeability water vapor permeability
  • cup method conforming to JIS Z 0208
  • Measurement temperature 40 ° C
  • Relative humidity 92%
  • Measurement time 24 hours
  • a constant temperature and humidity chamber was used for the measurement.
  • a tape piece having a length of 100 mm and a width of 25 mm was obtained using the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples.
  • one release liner is peeled off from the tape piece to expose the adhesive surface, and the PET film (thickness: 25 ⁇ m) is bonded to the adhesive surface of the tape piece, and (release liner / adhesive layer / A single-sided adhesive tape with a substrate (length: 100 mm, width: 25 mm) laminated in the order of PET film) was produced.
  • the release liner was peeled from the single-sided adhesive tape with the substrate to obtain a measurement sample. Then 23 ° C., 50% R.D. H.
  • a glass plate (trade name: soda lime glass # 0050, manufactured by Matsunami Glass Industry Co., Ltd.) is bonded to the exposed adhesive surface (measurement surface) of the measurement sample, and the 2 kg roller is reciprocated once. Crimped. And 23 degreeC, 50% R. H. For 30 minutes.
  • a tensile tester (trade name: TCM-1kNB, manufactured by Minebea Co., Ltd.)
  • TCM-1kNB trade name: TCM-1kNB, manufactured by Minebea Co., Ltd.
  • the peel strength (N / 25 mm) was measured. Measurement was performed at 23 ° C. and 50% R.D. H. In the atmosphere, the peeling angle was 180 ° and the tensile speed was 300 mm / min.
  • ⁇ Durability> The separator of the polarizing film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, the test piece was bonded to a glass plate, and the state after being put in an environment of 85 ° C. for 300 hours was visually or magnified (20 times) ). Evaluation was performed according to the following evaluation criteria. A: Even when confirmed with a loupe, no defects (foaming, peeling, etc.) occurred. ⁇ : Although a defect could not be confirmed by visual observation, some defect occurred to the extent that there was no problem in use when confirmed with a loupe. X: Defects could be confirmed visually.
  • HYBRAR 7311 Styrene-ethylene-propylene-styrene block copolymer (SEPS, trade name: HYBRAR 7311, styrene content 12%, manufactured by Kuraray Co., Ltd.)

Abstract

The present invention pertains to an adhesive composition containing a rubber-based polymer (A) and a tackifier (B), wherein the rubber-based polymer (A) includes at least one rubber-based polymer selected from the group consisting of a styrene-based thermoplastic elastomer (A1) and an isobutylene-based polymer (A2) having a weight average molecular weight of 500,000 or greater. The rubber-based polymer includes at least one selected from the group consisting of a natural material-based tackifier (B1), a petroleum resin-based tackifier (B2) and hydrogenated products thereof, when including the styrene-based thermoplastic elastomer (A1); and includes at least one selected from the group consisting of a natural material-based tackifier (B1) and hydrogenated products thereof, when including the isobutylene-based polymer (A2). This adhesive composition has low moisture permeability, and is capable of forming an adhesive layer which, even in high-temperature environments, is durable enough not to suffer from problems such as delamination or peeling.

Description

粘着剤組成物、粘着剤層、粘着剤層付光学フィルム、光学部材、及び画像表示装置Adhesive composition, adhesive layer, optical film with adhesive layer, optical member, and image display device
　本発明は、粘着剤組成物、当該粘着剤組成物から形成された粘着剤層に関する。また、本発明は、光学フィルムに前記粘着剤層を設けた粘着剤層付光学フィルム、及び当該粘着剤層付光学フィルムを含む光学部材に関する。さらに、本発明は、前記粘着剤層付光学フィルム及び／又は光学部材を含む画像表示装置に関する。 The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. Moreover, this invention relates to the optical member containing the said optical film with an adhesive layer which provided the said adhesive layer in the optical film, and the said optical film with an adhesive layer. Furthermore, this invention relates to the image display apparatus containing the said optical film with an adhesive layer and / or an optical member.
　近年、液晶表示装置等の画像表示装置においては、軽量化、薄型化の要求が強く、画像表示装置において使用される偏光フィルム等の各種光学部材に対しても、薄型化、軽量化することが要望されている。 In recent years, there has been a strong demand for weight reduction and thinning in image display devices such as liquid crystal display devices, and various optical members such as polarizing films used in image display devices can be thinned and lightened. It is requested.
　例えば、偏光フィルムとして、偏光子の片面のみに透明保護フィルムを有する片面保護偏光フィルムが知られている。このような片面保護偏光フィルムは薄型化、軽量化することができるものの、偏光子の片面が保護フィルムにより保護されていないため、水分等により劣化しやすいといった問題があった。また、両面保護偏光フィルムであっても、透明保護フィルムが薄膜化されている場合には、同様に偏光子が水分等により劣化する場合があった。 For example, a single-sided protective polarizing film having a transparent protective film only on one side of a polarizer is known as a polarizing film. Although such a single-sided protective polarizing film can be reduced in thickness and weight, there is a problem that the single-sided polarizer is not easily protected by the protective film, and thus is easily deteriorated by moisture or the like. Moreover, even if it is a double-sided protective polarizing film, when the transparent protective film is thinned, the polarizer may be similarly deteriorated by moisture or the like.
　また、有機ＥＬ（Ｅｌｅｃｔｒｏ　Ｌｕｍｉｎｅｓｃｅｎｃｅ）表示装置に搭載された有機ＥＬパネルは、大気中の水分や酸素に非常に弱いため、通常、有機ＥＬパネル表面にはバリア層やバリア機能を持つ光学用フィルムが設けられており、これらを貼り合せるための粘着剤層にも水分等を透過させないこと（低透湿性）が求められている。 In addition, since an organic EL panel mounted on an organic EL (Electro Luminescence) display device is very vulnerable to moisture and oxygen in the atmosphere, an optical film having a barrier layer and a barrier function is usually provided on the surface of the organic EL panel. The adhesive layer for bonding them is required not to transmit moisture or the like (low moisture permeability).
　このように画像表示装置に用いられる各種光学部材は、その素材によっては水分等により劣化しやすいものであり、当該光学部材を被着体に貼り合せるための粘着剤層には、水分等を透過させないこと（低透湿性）が要求されていた。 As described above, various optical members used in the image display device are easily deteriorated by moisture depending on the material, and the adhesive layer for bonding the optical member to the adherend is permeable to moisture. It has been required not to let it (low moisture permeability).
　このような低透湿の粘着剤層としては、例えば、２種類の重量平均分子量が異なるイソブチレン樹脂、特定の軟化点を有する水素化石油樹脂を含む粘着剤組成物を、特定の配合割合で含む粘着剤組成物が知られている（例えば、特許文献１参照）。また、水素添加された環状オレフィン系重合体と、特定の重量平均分子量を有するポリイソブチレン樹脂とを有する接着性封止組成物が開示されている（例えば、特許文献２参照）。 As such a low moisture-permeable pressure-sensitive adhesive layer, for example, two types of isobutylene resins having different weight average molecular weights and a pressure-sensitive adhesive composition containing a hydrogenated petroleum resin having a specific softening point are included at a specific blending ratio. An adhesive composition is known (see, for example, Patent Document 1). Moreover, the adhesive sealing composition which has the hydrogenated cyclic olefin type polymer and the polyisobutylene resin which has a specific weight average molecular weight is disclosed (for example, refer patent document 2).
特許第５４１６３１６号明細書Japanese Patent No. 5416316 特開２００７－１９７５１７号公報JP 2007-197517 A
　特許文献１、２に記載の粘着剤組成物から形成された粘着剤層は低透湿ではあるが、高温で保管試験を行うと、浮きや剥がれといった不具合を生じてしまうという問題があった。 Although the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition described in Patent Documents 1 and 2 has low moisture permeability, there has been a problem that when a storage test is performed at a high temperature, problems such as floating and peeling occur.
　そこで、本発明は、低透湿性であって、高温環境下においても浮きや剥がれ等の不具合の発生を抑制できる高い耐久性を有する粘着剤層を形成することができる粘着剤組成物を提供することを目的とする。また、本発明は、当該粘着剤組成物から形成された粘着剤層、当該粘着剤層が設けられた粘着剤層付光学フィルム、当該粘着剤層付光学フィルムを含む光学部材を提供することを目的とする。さらに、前記粘着剤層付光学フィルム、及び前記光学部材からなる群から選択される１種以上を含む画像表示装置を提供することも目的とする。 Accordingly, the present invention provides a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer having low moisture permeability and having high durability that can suppress the occurrence of problems such as floating and peeling even in a high-temperature environment. For the purpose. Moreover, this invention provides the optical member containing the adhesive layer formed from the said adhesive composition, the optical film with an adhesive layer provided with the said adhesive layer, and the said optical film with an adhesive layer. Objective. It is another object of the present invention to provide an image display device including at least one selected from the group consisting of the optical film with an adhesive layer and the optical member.
　本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、下記粘着剤組成物を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found the following pressure-sensitive adhesive composition and have completed the present invention.
　すなわち、本発明は、ゴム系ポリマー（Ａ）、及び粘着付与剤（Ｂ）を含有する粘着剤組成物であって、
　前記ゴム系ポリマー（Ａ）が、スチレン系熱可塑性エラストマー（Ａ１）、及び重量平均分子量が５０万以上であるイソブチレン系ポリマー（Ａ２）からなる群から選択される少なくとも１種のゴム系ポリマーを含み
　前記ゴム系ポリマー（Ａ）が前記スチレン系熱可塑性エラストマー（Ａ１）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）、及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含み、
　前記ゴム系ポリマー（Ａ）が前記イソブチレン系ポリマー（Ａ２）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含むことを特徴とする粘着剤組成物に関する。 That is, the present invention is a pressure-sensitive adhesive composition containing a rubber-based polymer (A) and a tackifier (B),
The rubber polymer (A) includes at least one rubber polymer selected from the group consisting of a styrene thermoplastic elastomer (A1) and an isobutylene polymer (A2) having a weight average molecular weight of 500,000 or more. When the rubber-based polymer (A) contains the styrene-based thermoplastic elastomer (A1), the tackifier (B) is a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2). And) at least one tackifier selected from the group consisting of these hydrogenated products,
When the rubber-based polymer (A) includes the isobutylene-based polymer (A2), the tackifier (B) is selected from the group consisting of a natural product-based tackifier (B1) and hydrogenated products thereof. It is related with the adhesive composition characterized by including the at least 1 sort (s) of tackifier selected.
　前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）を含有することが好ましい。前記天然物系粘着付与剤（Ｂ１）としては、テルペン骨格を含む粘着付与剤、ロジン骨格を含む粘着付与剤及びこれらの水素添加物からなる群から選択される少なくとも１種を用いることができる。 It is preferable that the tackifier (B) contains a natural product tackifier (B1). As the natural product-based tackifier (B1), at least one selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof can be used.
　前記粘着剤組成物から形成した厚み５０μｍの粘着剤層の、４０℃、９２％Ｒ．Ｈ．における透湿度が１００ｇ／（ｍ２・ｄａｙ）以下であることが好ましい。 A pressure-sensitive adhesive layer having a thickness of 50 μm formed from the pressure-sensitive adhesive composition, 40 ° C., 92% H. It is preferable that the water vapor transmission rate is 100 g / (m 2 · day) or less.
　前記粘着付与剤（Ｂ）が、水素添加物であることが好ましい。 It is preferable that the tackifier (B) is a hydrogenated product.
　前記粘着付与剤（Ｂ）の軟化点が、１００℃以上であることが好ましい。 It is preferable that the softening point of the tackifier (B) is 100 ° C. or higher.
　前記天然物系粘着付与剤（Ｂ１）が、シクロヘキサノール骨格を含むことが好ましい。 It is preferable that the natural product-based tackifier (B1) includes a cyclohexanol skeleton.
　前記粘着付与剤（Ｂ）の含有量が、前記ゴム系ポリマー（Ａ）１００重量部に対して１重量部以上であることが好ましい。 It is preferable that the content of the tackifier (B) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A).
　前記粘着剤組成物が、さらに、重量平均分子量が５万以下であるポリイソブチレン系化合物（Ｃ１）、及び重量平均分子量が５万以下であるポリイソプレン系化合物（Ｃ２）からなる群から選択される少なくとも１種の軟化剤（Ｃ）を含むことが好ましい。 The pressure-sensitive adhesive composition is further selected from the group consisting of a polyisobutylene compound (C1) having a weight average molecular weight of 50,000 or less and a polyisoprene compound (C2) having a weight average molecular weight of 50,000 or less. It is preferable to include at least one softener (C).
　前記軟化剤（Ｃ）の含有量が、前記ゴム系ポリマー（Ａ）１００重量部に対して１重量部以上であることが好ましい。 It is preferable that the content of the softening agent (C) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A).
　また、本発明は、前記粘着剤組成物から形成されたことを特徴とする粘着剤層に関する。 The present invention also relates to a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
　また、本発明は、光学フィルムと、当該光学フィルム上に設けられた前記粘着剤層を有することを特徴とする粘着剤層付光学フィルムに関する。 The present invention also relates to an optical film with an adhesive layer, characterized by comprising an optical film and the adhesive layer provided on the optical film.
　前記光学フィルムが、偏光子の少なくとも片面に透明保護フィルムを有する偏光フィルムであることが好ましい。 The optical film is preferably a polarizing film having a transparent protective film on at least one surface of the polarizer.
　前記偏光フィルムが、偏光子の片面のみに透明保護フィルムを有する片面保護偏光フィルムであって、前記粘着剤層が、偏光子の透明保護フィルムを有さない側に積層されていることが好ましい。 The polarizing film is preferably a single-sided protective polarizing film having a transparent protective film only on one side of the polarizer, and the pressure-sensitive adhesive layer is preferably laminated on the side of the polarizer that does not have a transparent protective film.
　前記光学フィルムが、輝度向上フィルムであってもよい。 The optical film may be a brightness enhancement film.
　また、本発明は、前記粘着剤層付光学フィルムと、輝度向上フィルムを含むことを特徴とする光学部材や、前記粘着剤層と、４０℃、９２％Ｒ．Ｈ．における透湿度が１ｇ／（ｍ２・ｄａｙ）以下であるフィルムを含むことを特徴とする光学部材に関する。 The present invention also provides an optical member comprising the optical film with the pressure-sensitive adhesive layer and a brightness enhancement film, the pressure-sensitive adhesive layer, 40 ° C., 92% R.D. H. In particular, the present invention relates to an optical member including a film having a moisture permeability of 1 g / (m 2 · day) or less.
　さらに、本発明は、前記粘着剤層付光学フィルム、及び前記光学部材からなる群から選択される少なくとも１種を含むことを特徴とする画像表示装置に関する。 Furthermore, the present invention relates to an image display device comprising at least one selected from the group consisting of the optical film with an adhesive layer and the optical member.
　本発明の粘着剤組成物は、特定のゴム系ポリマー（Ａ）に、特定の粘着付与剤（Ｂ）を添加することにより、低透湿性を保ちながら、高温環境下においても不具合（浮きや剥がれ等）の発生を抑制することができる（高い耐久性）。 The pressure-sensitive adhesive composition of the present invention has a problem (floating or peeling) even in a high temperature environment while maintaining low moisture permeability by adding a specific tackifier (B) to a specific rubber polymer (A). Etc.) can be suppressed (high durability).
　また、本発明は、高温環境下の耐久性に優れ、低透湿性に優れた粘着剤層付光学フィルム、光学部材や、光学信頼に優れた画像表示装置を提供することができる。 In addition, the present invention can provide an optical film with an adhesive layer, an optical member, and an image display device excellent in optical reliability, which are excellent in durability under a high temperature environment and excellent in low moisture permeability.
本発明の一実施形態である粘着剤層付偏光フィルムを模式的に示す断面図である。It is sectional drawing which shows typically the polarizing film with an adhesive layer which is one Embodiment of this invention. 本発明の光学部材の一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the optical member of this invention. 本発明の光学部材の一実施形態を模式的に示す断面図である。It is sectional drawing which shows typically one Embodiment of the optical member of this invention.
　１．粘着剤組成物
　本発明の粘着剤組成物は、ゴム系ポリマー（Ａ）、及び粘着付与剤（Ｂ）を含有し、
　前記ゴム系ポリマー（Ａ）が、スチレン系熱可塑性エラストマー（Ａ１）、及び重量平均分子量が５０万以上であるイソブチレン系ポリマー（Ａ２）からなる群から選択される少なくとも１種のゴム系ポリマーを含み、
　前記ゴム系ポリマー（Ａ）が前記スチレン系熱可塑性エラストマー（Ａ１）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含み、
　前記ゴム系ポリマー（Ａ）が前記イソブチレン系ポリマー（Ａ２）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含むことを特徴とする。 1. Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention contains a rubber-based polymer (A) and a tackifier (B),
The rubber polymer (A) includes at least one rubber polymer selected from the group consisting of a styrene thermoplastic elastomer (A1) and an isobutylene polymer (A2) having a weight average molecular weight of 500,000 or more. ,
When the rubber-based polymer (A) contains the styrene-based thermoplastic elastomer (A1), the tackifier (B) is a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2). And at least one tackifier selected from the group consisting of these hydrogenated products,
When the rubber-based polymer (A) includes the isobutylene-based polymer (A2), the tackifier (B) is selected from the group consisting of a natural product-based tackifier (B1) and hydrogenated products thereof. It contains at least one selected tackifier.
　（１）ゴム系ポリマー（Ａ）
　本発明で用いるゴム系ポリマー（Ａ）は、室温付近の温度域においてゴム弾性を示すポリマーである。具体的には、スチレン系熱可塑性エラストマー（Ａ１）、及び重量平均分子量（Ｍｗ）が５０万以上であるイソブチレン系ポリマー（Ａ２）（以下、単に「イソブチレン系ポリマー（Ａ２）」ということもある）からなる群から選択される１種以上のゴム系ポリマーのことをいう。 (1) Rubber polymer (A)
The rubber-based polymer (A) used in the present invention is a polymer that exhibits rubber elasticity in a temperature range near room temperature. Specifically, the styrene-based thermoplastic elastomer (A1) and the isobutylene-based polymer (A2) having a weight average molecular weight (Mw) of 500,000 or more (hereinafter sometimes simply referred to as “isobutylene-based polymer (A2)”) One or more rubber-based polymers selected from the group consisting of:
　前記スチレン系熱可塑性エラストマー（Ａ１）としては、例えば、スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、ＳＩＳの水素添加物）、スチレン－エチレン－プロピレンブロック共重合体（ＳＥＰ、スチレン－イソプレンブロック共重合体の水素添加物）、スチレン－イソブチレン－スチレンブロック共重合体（ＳＩＢＳ）、スチレン－ブタジエンゴム（ＳＢＲ）等のスチレン系ブロックコポリマーを挙げることができる。これらの中でも、分子の両末端にポリスチレンブロックを有し、ポリマーとして高い凝集力を有する点から、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、ＳＩＳの水素添加物）、スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－イソブチレン－スチレンブロック共重合体（ＳＩＢＳ）が好ましい。 Examples of the styrenic thermoplastic elastomer (A1) include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene-styrene block copolymer. Copolymer (SBS), Styrene-ethylene-propylene-styrene block copolymer (hydrogenated product of SEPS, SIS), Styrene-ethylene-propylene block copolymer (hydrogenated product of SEP, styrene-isoprene block copolymer) And styrene block copolymers such as styrene-isobutylene-styrene block copolymer (SIBS) and styrene-butadiene rubber (SBR). Among these, styrene-ethylene-propylene-styrene block copolymers (SEPS, SIS hydrogenated product), styrene-ethylene-, because of having polystyrene blocks at both ends of the molecule and high cohesion as a polymer. Butylene-styrene block copolymer (SEBS) and styrene-isobutylene-styrene block copolymer (SIBS) are preferred.
　前記スチレン系熱可塑性エラストマー（Ａ１）としては、例えば、（株）クラレ製のＳＥＰＴＯＮ、ＨＹＢＲＡＲ、旭化成ケミカルズ（株）製のタフテック、（株）カネカ製のＳＩＢＳＴＡＲ等の市販品を用いることができる。 As the styrenic thermoplastic elastomer (A1), for example, commercially available products such as SEPTON and HYBRAR manufactured by Kuraray Co., Ltd., Tuftec manufactured by Asahi Kasei Chemicals Co., Ltd., and SIBSTAR manufactured by Kaneka Co., Ltd. can be used.
　前記スチレン系熱可塑性エラストマー（Ａ１）の重量平均分子量としては、特に限定されるものではないが、５万～５０万程度であることが好ましく、５万～３０万程度であることがより好ましく、５万～２５万程度であることがより好ましい。スチレン系熱可塑性エラストマー（Ａ１）の重量平均分子量が前記範囲にあることで、ポリマーの凝集力と粘弾性を両立できるため好ましい。 The weight average molecular weight of the styrenic thermoplastic elastomer (A1) is not particularly limited, but is preferably about 50,000 to 500,000, more preferably about 50,000 to 300,000. More preferably, it is about 50,000 to 250,000. It is preferable that the weight average molecular weight of the styrene-based thermoplastic elastomer (A1) is in the above range because both the cohesive force and viscoelasticity of the polymer can be achieved.
　前記スチレン系熱可塑性エラストマー（Ａ１）中のスチレン含有量は、特に限定されるものではないが、例えば、５～７０重量％程度であることが好ましく、５～４０重量％程度であることがより好ましく、１０～２０重量％程度であることがさらに好ましい。スチレン系熱可塑性エラストマー（Ａ１）中のスチレン含有量が前記範囲であることにより、スチレン部位による凝集力を保ちながら、ソフトセグメントによる粘弾性を確保できるため好ましい。 The styrene content in the styrenic thermoplastic elastomer (A1) is not particularly limited, but is preferably about 5 to 70% by weight, for example, and more preferably about 5 to 40% by weight. Preferably, it is about 10 to 20% by weight. When the styrene content in the styrene-based thermoplastic elastomer (A1) is in the above range, it is preferable because viscoelasticity by the soft segment can be secured while maintaining the cohesive force by the styrene site.
　前記イソブチレン系ポリマー（Ａ２）としては、イソブチレンを構成単量体として含み、重量平均分子量が５０万以上であるものを挙げることができる。前記イソブチレン系ポリマー（Ａ２）としては、イソブチレンのホモポリマー（ポリイソブチレン、ＰＩＢ）であってもよく、イソブチレンを主モノマーとするコポリマー（すなわち、イソブチレンが５０モル％を超える割合で共重合されたコポリマー）であってもよい。このようなコポリマーとしては、例えば、イソブチレンとノルマルブチレンとの共重合体、イソブチレンとイソプレンとの共重合体（例えば、レギュラーブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、部分架橋ブチルゴム等のブチルゴム類）、これらの加硫物や変性物（例えば、水酸基、カルボキシル基、アミノ基、エポキシ基等の官能基で変性したもの）等を挙げることができる。これらの中でも、主鎖の中に二重結合を含まず耐候性に優れる点から、ポリイソブチレン（ＰＩＢ）が好ましい。 Examples of the isobutylene polymer (A2) include those containing isobutylene as a constituent monomer and having a weight average molecular weight of 500,000 or more. The isobutylene polymer (A2) may be a homopolymer of isobutylene (polyisobutylene, PIB), and a copolymer having isobutylene as a main monomer (that is, a copolymer in which isobutylene is copolymerized in a proportion exceeding 50 mol%). ). Examples of such a copolymer include a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber), These vulcanizates and modified products (for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group) can be used. Among these, polyisobutylene (PIB) is preferable because it does not contain a double bond in the main chain and is excellent in weather resistance.
　前記イソブチレン系ポリマー（Ａ２）としては、例えば、ＢＡＳＦ社製のＯＰＰＡＮＯＬ等の市販品を用いることができる。 As the isobutylene polymer (A2), for example, commercially available products such as OPPANOL manufactured by BASF can be used.
　前記イソブチレン系ポリマー（Ａ２）の重量平均分子量は、５０万以上であり、６０万以上であることが好ましく、７０万以上であることがより好ましい。また、重量平均分子量の上限値は特に限定されるものではないが、５００万以下が好ましく、３００万以下がより好ましく、２００万以下がさらに好ましい。イソブチレン系ポリマー（Ａ２）の重量平均分子量を５０万以上とすることで高温保管時の耐久性がより優れる粘着剤組成物とすることができる。 The weight average molecular weight of the isobutylene polymer (A2) is 500,000 or more, preferably 600,000 or more, and more preferably 700,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 5 million or less, more preferably 3 million or less, and even more preferably 2 million or less. By setting the weight average molecular weight of the isobutylene-based polymer (A2) to 500,000 or more, a pressure-sensitive adhesive composition with more excellent durability during high-temperature storage can be obtained.
　前記ゴム系ポリマー（Ａ）の含有量は、特に限定されるものではないが、粘着剤組成物の全固形分中、３０重量％以上であることが好ましく、４０重量％以上であることがより好ましく、５０重量％以上であることがさらに好ましく、６０重量％以上であることが特に好ましい。ゴム系ポリマー（Ａ）の含有量の上限は特に限定されるものではなく、９５重量％以下であることが好ましく、９０重量％以下であることがより好ましい。 Although content of the said rubber-type polymer (A) is not specifically limited, It is preferable that it is 30 weight% or more in the total solid of an adhesive composition, and it is more preferable that it is 40 weight% or more. Preferably, it is more preferably 50% by weight or more, and particularly preferably 60% by weight or more. The upper limit of the content of the rubber-based polymer (A) is not particularly limited, and is preferably 95% by weight or less, and more preferably 90% by weight or less.
　また、前記ゴム系ポリマー（Ａ）がスチレン系熱可塑性エラストマー（Ａ１）を含有する場合、その含有量としては、粘着剤組成物の全固形分中、３０重量％以上であることが好ましく、３５重量％以上であることがより好ましく、４０重量％以上であることがさらに好ましい。また、上限値としては特に限定されるものではないが、例えば、９０重量％以下程度であることが好ましく、７０重量％以下程度であることがより好ましい。 When the rubber polymer (A) contains the styrene thermoplastic elastomer (A1), the content thereof is preferably 30% by weight or more in the total solid content of the pressure-sensitive adhesive composition, 35 More preferably, it is more than 40% by weight. The upper limit is not particularly limited, but is preferably about 90% by weight or less, and more preferably about 70% by weight or less.
　また、前記ゴム系ポリマー（Ａ）が、イソブチレン系ポリマー（Ａ２）を含有する場合、その含有量としては、粘着剤組成物の全固形分中、６０重量％以上であることが好ましく、７０重量％以上であることがより好ましく、８０重量％以上であることがさらに好ましい。また、上限値としては特に限定されるものではないが、例えば、９８重量％以下程度であることが好ましく、９０重量％以下程度であることがより好ましい。 When the rubber polymer (A) contains the isobutylene polymer (A2), the content thereof is preferably 60% by weight or more in the total solid content of the pressure-sensitive adhesive composition, 70% by weight. % Or more, more preferably 80% by weight or more. The upper limit value is not particularly limited, but is preferably about 98% by weight or less, and more preferably about 90% by weight or less.
　また、本発明の粘着剤組成物においては、前記ゴム系ポリマー（Ａ）以外のゴム系ポリマーを含むこともできる。具体的には、ブチルゴム（ＩＩＲ）、ブタジエンゴム（ＢＲ）、アクリロニトリル－ブタジエンゴム（ＮＢＲ）、ＥＰＲ（二元系エチレン－プロピレンゴム）、ＥＰＴ（三元系エチレン－プロピレンゴム）、アクリルゴム、ウレタンゴム、ポリウレタン系熱可塑性エラストマー；ポリエステル系熱可塑性エラストマー；ポリプロピレンとＥＰＴ（三元系エチレン－プロピレンゴム）とのポリマーブレンド等のブレンド系熱可塑性エラストマー等が挙げられる。これらは、本発明の効果を損なわない範囲で添加することができるが、前記ゴム系ポリマー（Ａ）１００重量部に対して１０重量部程度以下であることが好ましい。 Further, the pressure-sensitive adhesive composition of the present invention can also contain a rubber polymer other than the rubber polymer (A). Specifically, butyl rubber (IIR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (ternary ethylene-propylene rubber), acrylic rubber, urethane Examples thereof include rubber, polyurethane-based thermoplastic elastomers; polyester-based thermoplastic elastomers; blend-based thermoplastic elastomers such as polymer blends of polypropylene and EPT (ternary ethylene-propylene rubber). These can be added as long as the effects of the present invention are not impaired, but it is preferably about 10 parts by weight or less with respect to 100 parts by weight of the rubber-based polymer (A).
　（２）粘着付与剤（Ｂ）
　本発明で用いる粘着付与剤（Ｂ）としては、天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）及びこれらの水素添加物が挙げられる。これら粘着付与剤（Ｂ）は、前記ゴム系ポリマー（Ａ）に応じて選択される。すなわち、前記スチレン系熱可塑性エラストマー（Ａ１）を用いる場合には、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）及びこれらの水素添加物からなる群から選択される少なくとも１種が用いられる。一方、前記イソブチレン系ポリマー（Ａ２）を用いる場合には、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）、及びこれらの水素添加物からなる群から選択される少なくとも１種が用いられる。本発明の粘着剤組成物は、粘着付与剤（Ｂ）を含むことで、各種被着体に対して高い接着性を有し、かつ、高温環境下においても高い耐久性を有する粘着剤層を形成することができる。 (2) Tackifier (B)
Examples of the tackifier (B) used in the present invention include a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2), and hydrogenated products thereof. These tackifiers (B) are selected according to the rubber polymer (A). That is, when the styrene thermoplastic elastomer (A1) is used, as the tackifier (B), a natural product tackifier (B1), a petroleum resin tackifier (B2), and hydrogenation thereof. At least one selected from the group consisting of things is used. On the other hand, when the isobutylene polymer (A2) is used, the tackifier (B) is at least one selected from the group consisting of a natural product tackifier (B1) and hydrogenated products thereof. Is used. By including the tackifier (B), the pressure-sensitive adhesive composition of the present invention has a pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high-temperature environment. Can be formed.
　本発明においては、前記ゴム系ポリマー（Ａ）を用いているため、粘着付与剤（Ｂ）として、テルペンフェノール等のように水酸基を含み透湿度が高くなるような天然物系粘着付与剤（Ｂ１）であっても使用できるものである。すなわち、本発明においては、特定のゴム系ポリマー（Ａ）と特定の粘着付与剤（Ｂ）を用いることにより、低透湿特性を保ちながら、高温環境下における耐久性を向上することができるものである。 In the present invention, since the rubber-based polymer (A) is used, as the tackifier (B), a natural product-based tackifier (B1) containing a hydroxyl group and having high moisture permeability, such as terpene phenol. ) Can be used. That is, in the present invention, by using a specific rubber-based polymer (A) and a specific tackifier (B), durability in a high temperature environment can be improved while maintaining low moisture permeability. It is.
　前記天然物系粘着付与剤（Ｂ１）としては、例えば、テルペン骨格を含む粘着付与剤、ロジン骨格を含む粘着付与剤及びこれらの水素添加物が挙げられる。なお、以降の説明では、天然物系粘着付与剤（Ｂ１）に関する記載はその水素添加物を含む概念である。 Examples of the natural product-based tackifier (B1) include tackifiers containing a terpene skeleton, tackifiers containing a rosin skeleton, and hydrogenated products thereof. In the following description, the description relating to the natural product-based tackifier (B1) is a concept including the hydrogenated product.
　テルペン骨格を含む粘着付与剤としては、例えば、α－ピネン重合体、β－ピネン重合体、ジペンテン重合体等のテルペン重合体や、前記テルペン重合体を変性（フェノール変性、スチレン変性、芳香族変性、水素添加変性、炭化水素変性等）した変性テルペン樹脂等が挙げられる。上記変性テルペン樹脂の例には、テルペンフェノール樹脂、スチレン変性テルペン樹脂、芳香族変性テルペン樹脂、水素添加テルペン樹脂（水素化テルペン樹脂）等が含まれる。ここでいう水素添加テルペン樹脂の例には、テルペン重合体の水素添加物及び他の変性テルペン樹脂、テルペンフェノール樹脂の水素添加物が含まれる。これらの中でも、ゴム系粘着剤への相溶性や粘着特性の観点から、テルペンフェノール樹脂の水素添加物が好ましい。 Examples of tackifiers containing a terpene skeleton include terpene polymers such as α-pinene polymers, β-pinene polymers, and dipentene polymers, and modified terpene polymers (phenol-modified, styrene-modified, aromatic-modified). Modified terpene resin, etc.). Examples of the modified terpene resin include terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin, hydrogenated terpene resin (hydrogenated terpene resin) and the like. Examples of the hydrogenated terpene resin herein include hydrogenated products of terpene polymers and other modified terpene resins and hydrogenated products of terpene phenol resins. Among these, from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive and pressure-sensitive adhesive properties, hydrogenated products of terpene phenol resins are preferable.
　前記ロジン骨格を含む粘着付与剤としては、ロジン樹脂、重合ロジン樹脂、水添ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂、ロジンフェノール樹脂等が挙げられ、具体的には、ガムロジン、ウッドロジン、トール油ロジン等の未変性ロジン（生ロジン）や、これらを水添化、不均化、重合、その他の化学的に修飾された変性ロジン、これらの誘導体を使用することができる。 Examples of the tackifier containing the rosin skeleton include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like. Specifically, gum rosin, wood rosin, Unmodified rosin such as tall oil rosin (raw rosin), hydrogenated, disproportionated, polymerized, other chemically modified modified rosin, and derivatives thereof can be used.
　前記石油樹脂系粘着付与剤（Ｂ２）としては、例えば、芳香族系石油樹脂、脂肪族系石油樹脂、脂環族系石油樹脂（脂肪族環状石油樹脂）、脂肪族・芳香族系石油樹脂、脂肪族・脂環族系石油樹脂、水素添加石油樹脂、クマロン系樹脂、クマロンインデン系樹脂等が挙げられる。上記芳香族系石油樹脂としては、例えば、炭素数が８～１０であるビニル基含有芳香族系炭化水素（スチレン、ｏ－ビニルトルエン、ｍ－ビニルトルエン、ｐ－ビニルトルエン、α－メチルスチレン、β－メチルスチレン、インデン、メチルインデン等）が１種のみ又は２種以上用いられた重合体等が挙げられる。これらの中でも、ビニルトルエンやインデン等の留分（いわゆる「Ｃ９石油留分」）から得られる芳香族系石油樹脂（いわゆる「Ｃ９系石油樹脂」）が好ましい。また、上記脂肪族系石油樹脂としては、例えば、炭素数４～５のオレフィンやジエン（ブテン－１、イソブチレン、ペンテン－１等のオレフィン；ブタジエン、ピペリレン（１，３－ペンタジエン）、イソプレン等のジエン等）が１種のみ又は２種以上用いられた重合体等が挙げられる。これらの中でも、ブタジエン、ピペリレンやイソプレン等の留分（いわゆる「Ｃ４石油留分」や「Ｃ５石油留分」等）から得られる脂肪族系石油樹脂（いわゆる「Ｃ４系石油樹脂」や「Ｃ５系石油樹脂」等）が好ましい。さらに、上記脂環族系石油樹脂としては、例えば、脂肪族系石油樹脂（いわゆる「Ｃ４系石油樹脂」や「Ｃ５系石油樹脂」等）を環化二量体化した後重合させた脂環式炭化水素系樹脂、環状ジエン化合物（シクロペンタジエン、ジシクロペンタジエン、エチリデンノルボルネン、ジペンテン、エチリデンビシクロヘプテン、ビニルシクロヘプテン、テトラヒドロインデン、ビニルシクロヘキセン、リモネン等）の重合体又はその水素添加物、上記の芳香族系炭化水素樹脂や、下記の脂肪族・芳香族系石油樹脂の芳香環を水素添加した脂環式炭化水素系樹脂等が挙げられる。さらにまた、脂肪族・芳香族系石油樹脂としては、スチレン－オレフィン系共重合体等が挙げられる。脂肪族・芳香族系石油樹脂としては、いわゆる「Ｃ５／Ｃ９共重合系石油樹脂」等も挙げられる。なお、以降の説明では、石油樹脂系粘着付与剤（Ｂ２）に関する記載はその水素添加物を含む概念である。 Examples of the petroleum resin tackifier (B2) include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, Aliphatic / alicyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins and the like can be mentioned. Examples of the aromatic petroleum resin include vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene, β-methylstyrene, indene, methylindene, etc.) are used alone or in combination of two or more. Among these, aromatic petroleum resins (so-called “C9 petroleum resins”) obtained from fractions such as vinyl toluene and indene (so-called “C9 petroleum fractions”) are preferable. Examples of the aliphatic petroleum resin include olefins having 4 to 5 carbon atoms and dienes (olefins such as butene-1, isobutylene and pentene-1; butadiene, piperylene (1,3-pentadiene), isoprene and the like. Examples thereof include polymers in which only one type or two or more types of diene are used. Among these, aliphatic petroleum resins (so-called “C4 petroleum resins” and “C5 series” obtained from fractions such as butadiene, piperylene and isoprene (so-called “C4 petroleum fraction”, “C5 petroleum fraction”, etc.) Petroleum resin "etc. are preferred. Furthermore, as the alicyclic petroleum resin, for example, an alicyclic polymer obtained after cyclizing and dimerizing an aliphatic petroleum resin (so-called “C4 petroleum resin”, “C5 petroleum resin” or the like). A hydrocarbon polymer, a polymer of a cyclic diene compound (cyclopentadiene, dicyclopentadiene, ethylidene norbornene, dipentene, ethylidenebicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, limonene, or the like) Examples thereof include the above aromatic hydrocarbon resins and alicyclic hydrocarbon resins obtained by hydrogenating the aromatic rings of the following aliphatic / aromatic petroleum resins. Furthermore, examples of the aliphatic / aromatic petroleum resin include styrene-olefin copolymers. Examples of the aliphatic / aromatic petroleum resin include so-called “C5 / C9 copolymer petroleum resin”. In the following description, the description relating to the petroleum resin-based tackifier (B2) is a concept including the hydrogenated product.
　前記粘着付与剤（Ｂ）のなかで天然物系粘着付与剤（Ｂ１）としては、例えば、ヤスハラケミカル（株）製のクリアロンシリーズ、ポリスターシリーズ、荒川化学工業（株）製のスーパーエステルシリーズ、ペンセルシリーズ、パインクリスタルシリーズ等が挙げられ、石油樹脂系粘着付与剤（Ｂ２）としては、例えば、荒川化学工業（株）製のアルコンシリーズ等の市販品を使用することができる。 Among the tackifiers (B), examples of the natural product-based tackifier (B1) include: Clearon series, Polystar series, Yashara Chemical Co., Ltd., Superester series, Arakawa Chemical Co., Ltd. Cell series, pine crystal series, etc. are mentioned, and as the petroleum resin-based tackifier (B2), for example, commercially available products such as Alcon series manufactured by Arakawa Chemical Industries, Ltd. can be used.
　前記粘着付与剤（Ｂ）が水素添加物である場合、水素添加は、部分的に水素添加されている部分水素添加物であってもよく、化合物中の全ての二重結合に水素添加がされている完全水素添加物であってもよい。本発明においては、粘着特性、耐候性や色相の観点から完全水素添加物であることが好ましい。 When the tackifier (B) is a hydrogenated product, the hydrogenation may be a partially hydrogenated product that is partially hydrogenated, and all double bonds in the compound are hydrogenated. It may be a complete hydrogenation product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
　前記粘着付与剤（Ｂ）としては天然物系粘着付与剤（Ｂ１）を好適に使用することができる。天然物系粘着付与剤（Ｂ１）は、シクロヘキサノール骨格を含むことが粘着特性の観点から好ましい。これは詳細な原理は不明であるが、フェノール骨格よりシクロヘキサノール骨格の方が、ベースポリマーであるゴム系ポリマーとの相溶性のバランスがとれるためと考えられる。シクロヘキサノール骨格を含む粘着付与剤としては、例えば、テルペンフェノール樹脂、ロジンフェノール樹脂等の水素添加物が好ましく、テルペンフェノール樹脂、ロジンフェノール樹脂等の完全水素添加物がより好ましい。 As the tackifier (B), a natural product tackifier (B1) can be suitably used. The natural product-based tackifier (B1) preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is considered that the cyclohexanol skeleton is more compatible with the rubber polymer as the base polymer than the phenol skeleton. As a tackifier containing a cyclohexanol skeleton, for example, hydrogenated products such as terpene phenol resin and rosin phenol resin are preferable, and complete hydrogenated products such as terpene phenol resin and rosin phenol resin are more preferable.
　前記粘着付与剤（Ｂ）の軟化点（軟化温度）は、特に限定されないが、例えば、８０℃以上程度であることが好ましく、１００℃以上程度であることがより好ましい。粘着付与剤（Ｂ）の軟化点が８０℃以上であることで、高温においても粘着付与剤が軟化せずに粘着特性を保つことができるため好ましい。粘着付与剤（Ｂ）の軟化点の上限値は、特に限定されないが、軟化点が高くなり過ぎると、分子量がより高くなり、相溶性が悪化し、白化等の不具合を生じてしまう場合があるため、例えば、２００℃以下程度であることが好ましく、１８０℃以下程度であることが好ましい。なお、ここでいう粘着付与樹脂の軟化点は、ＪＩＳ　Ｋ５９０２及びＪＩＳ　Ｋ２２０７のいずれかに規定する軟化点試験方法（環球法）によって測定された値として定義される。 The softening point (softening temperature) of the tackifier (B) is not particularly limited, but is preferably about 80 ° C. or higher, and more preferably about 100 ° C. or higher. It is preferable that the softening point of the tackifier (B) is 80 ° C. or higher because the tackifier can be maintained without being softened even at high temperatures. The upper limit value of the softening point of the tackifier (B) is not particularly limited, but if the softening point becomes too high, the molecular weight becomes higher, the compatibility deteriorates, and problems such as whitening may occur. Therefore, for example, it is preferably about 200 ° C. or lower, and preferably about 180 ° C. or lower. In addition, the softening point of the tackifier resin here is defined as a value measured by a softening point test method (ring ball method) defined in either JIS K5902 or JIS K2207.
　前記粘着付与剤（Ｂ）の重量平均分子量は、特に限定されるものではないが、５万以下であることが好ましく、３万以下であることが好ましく、１万以下であることがより好ましく、８０００以下であることがさらに好ましく、５０００以下であることが特に好ましい。また、前記粘着付与剤（Ｂ）の重量平均分子量の下限値は特に限定されるものではないが、５００以上であることが好ましく、１０００以上であることがより好ましく、２０００以上であることがさらに好ましい。前記粘着付与剤（Ｂ）の重量平均分子量が前記範囲にあることで、ゴム系ポリマーとの相溶性が良く、白化等の不具合を生じないため好ましい。 The weight average molecular weight of the tackifier (B) is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less, It is more preferably 8000 or less, and particularly preferably 5000 or less. The lower limit of the weight average molecular weight of the tackifier (B) is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. preferable. It is preferable that the weight-average molecular weight of the tackifier (B) is in the above range since compatibility with the rubber polymer is good and problems such as whitening do not occur.
　前記粘着付与剤（Ｂ）の添加量は、前記ゴム系ポリマー（Ａ）１００重量部に対して、２５０重量部以下であることが好ましく、さらには２００重量部以下であることが好ましく、さらには１５０重量部以下であることが好ましい。前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）を含有する場合には、前記天然物系粘着付与剤（Ｂ１）の添加量は、前記ゴム系ポリマー（Ａ）１００重量部に対して、１００重量部以下であることが好ましく、８５重量部以下であることがより好ましく、５０重量部以下であることがさらに好ましく、４５重量部以下であることが特に好ましい。また、粘着付与剤（Ｂ）の添加量の下限値は特に限定されるものではないが、１重量部以上であることが好ましく、５重量部以上であることがより好ましい。粘着付与剤（Ｂ）の使用量を前記範囲にすることで、粘着特性を向上できるため好ましい。また、粘着付与剤（Ｂ）の使用料が前記範囲を超えて多量添加となると、粘着剤の凝集力が低下してしまう傾向があり、好ましくない。 The amount of the tackifier (B) added is preferably 250 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the rubber-based polymer (A). It is preferably 150 parts by weight or less. When the natural product-based tackifier (B1) is contained as the tackifier (B), the amount of the natural product-based tackifier (B1) added is 100 parts by weight of the rubber-based polymer (A). The amount is preferably 100 parts by weight or less, more preferably 85 parts by weight or less, further preferably 50 parts by weight or less, and particularly preferably 45 parts by weight or less. Moreover, the lower limit of the addition amount of the tackifier (B) is not particularly limited, but is preferably 1 part by weight or more, and more preferably 5 parts by weight or more. By making the usage-amount of a tackifier (B) into the said range, since an adhesive characteristic can be improved, it is preferable. Moreover, when the usage-amount of a tackifier (B) is added in large quantities exceeding the said range, there exists a tendency for the cohesive force of an adhesive to fall, and it is unpreferable.
　また、前記ゴム系ポリマー（Ａ）がスチレン系熱可塑性エラストマー（Ａ１）を含有する場合、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）及び／又は石油樹脂系粘着付与剤（Ｂ２）が用いられる。前記天然物系粘着付与剤（Ｂ１）の添加量は、前記スチレン系熱可塑性エラストマー（Ａ１）１００重量部に対して、１００重量部以下であることが好ましく、８５重量部以下であることがより好ましく、７０重量部以下であることがさらに好ましく、４５重量部以下であることが特に好ましい。また、前記天然物系粘着付与剤（Ｂ１）の添加量の下限値は特に限定されるものではないが、０．５重量部以上であることが好ましく、１重量部以上であることがより好ましく、１０重量部以上であることがさらに好ましく、２０重量部以上であることが特に好ましい。なお、前記粘着付与剤（Ｂ）として、前記石油樹脂系粘着付与剤（Ｂ２）を含有する場合には、前記天然物系粘着付与剤（Ｂ１）の添加量は０重量部であってもよい。 When the rubber-based polymer (A) contains a styrene-based thermoplastic elastomer (A1), as the tackifier (B), a natural product-based tackifier (B1) and / or a petroleum resin-based tackifier (B2) is used. The amount of the natural product-based tackifier (B1) added is preferably 100 parts by weight or less and more preferably 85 parts by weight or less with respect to 100 parts by weight of the styrene-based thermoplastic elastomer (A1). The amount is preferably 70 parts by weight or less, and more preferably 45 parts by weight or less. Moreover, the lower limit of the amount of the natural product-based tackifier (B1) added is not particularly limited, but is preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more. The amount is more preferably 10 parts by weight or more, and particularly preferably 20 parts by weight or more. When the petroleum resin-based tackifier (B2) is contained as the tackifier (B), the added amount of the natural product-based tackifier (B1) may be 0 parts by weight. .
　一方、前記石油樹脂系粘着付与剤（Ｂ２）の添加量は、スチレン系熱可塑性エラストマー（Ａ１）１００重量部に対して、１５０重量部以下であることが好ましく、１００重量部以下であることがより好ましく、７０重量部以下であることがさらに好ましく、５０重量部であることがさらに好ましく、３０重量部であることがさらに好ましい。また、石油樹脂系粘着付与剤（Ｂ２）の添加量の下限値は特に限定されるものではないが、０．５重量部以上であることが好ましく、１重量部以上であることがより好ましく、５重量部以上であることがより好ましく、１０重量部以上であることがさらに好ましい。なお、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）を含有する場合には、前記石油樹脂系粘着付与剤（Ｂ２）の添加量は０重量部であってもよい。 On the other hand, the addition amount of the petroleum resin-based tackifier (B2) is preferably 150 parts by weight or less and 100 parts by weight or less with respect to 100 parts by weight of the styrene-based thermoplastic elastomer (A1). More preferably, it is 70 parts by weight or less, further preferably 50 parts by weight, and further preferably 30 parts by weight. Further, the lower limit value of the addition amount of the petroleum resin tackifier (B2) is not particularly limited, but is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, The amount is more preferably 5 parts by weight or more, and further preferably 10 parts by weight or more. In addition, when the natural product type tackifier (B1) is contained as the tackifier (B), the petroleum resin type tackifier (B2) may be added in an amount of 0 part by weight.
　前記ゴム系ポリマー（Ａ）がスチレン系熱可塑性エラストマー（Ａ１）を含有する場合、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）および石油樹脂系粘着付与剤（Ｂ２）を用いる場合が好ましい。前記天然物系粘着付与剤（Ｂ１）に加えて、石油樹脂系粘着付与剤（Ｂ２）を併用することはスチレン部位との相溶性の観点から好ましい。前記併用系では、前記スチレン系熱可塑性エラストマー（Ａ１）１００重量部に対して、天然物系粘着付与剤（Ｂ１）の添加量は０．５～１５０重量部が好ましく、さらには０．５～１００重量部が好ましく、石油樹脂系粘着付与剤（Ｂ２）の添加量は０．５～１５０重量部が好ましく、さらには０．５～１００重量部が好ましい。 When the rubber polymer (A) contains a styrenic thermoplastic elastomer (A1), a natural product tackifier (B1) and a petroleum resin tackifier (B2) are used as the tackifier (B). Use is preferred. In addition to the natural product-based tackifier (B1), it is preferable to use a petroleum resin-based tackifier (B2) in view of compatibility with the styrene moiety. In the combined system, the addition amount of the natural product tackifier (B1) is preferably 0.5 to 150 parts by weight, more preferably 0.5 to 150 parts by weight with respect to 100 parts by weight of the styrenic thermoplastic elastomer (A1). 100 parts by weight is preferable, and the amount of petroleum resin tackifier (B2) added is preferably 0.5 to 150 parts by weight, and more preferably 0.5 to 100 parts by weight.
　また、前記ゴム系ポリマー（Ａ）がイソブチレン系ポリマー（Ａ２）を含有する場合、前記粘着付与剤（Ｂ）として、天然物系粘着付与剤（Ｂ１）が用いられる。前記天然物系粘着付与剤（Ｂ１）の添加量は、前記イソブチレン系ポリマー（Ａ２）１００重量部に対して、４０重量部以下であることが好ましく、３０重量部以下であることがより好ましく、２０重量部以下であることがさらに好ましい。また、粘着付与剤（Ｂ）の添加量の下限値は特に限定されるものではないが、０．５重量部以上であることが好ましく、１重量部以上であることがより好ましく、５重量部以上であることがさらに好ましい。なお、前記ゴム系ポリマー（Ａ）がイソブチレン系ポリマー（Ａ２）を含有する場合には、粘着剤組成物への、前記石油樹脂系粘着付与剤（Ｂ２）の添加は任意であるが、その添加量は、イソブチレン系ポリマー（Ａ２）１００重量部に対して４０重量部以下であるのが好ましく、さらには２０重量部以下であるのが好ましく、０重量部であってもよい。 When the rubber polymer (A) contains an isobutylene polymer (A2), a natural product tackifier (B1) is used as the tackifier (B). The amount of the natural product-based tackifier (B1) added is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, with respect to 100 parts by weight of the isobutylene polymer (A2). More preferably, it is 20 parts by weight or less. Moreover, the lower limit of the addition amount of the tackifier (B) is not particularly limited, but is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight. More preferably, it is the above. In addition, when the said rubber-type polymer (A) contains an isobutylene-type polymer (A2), the addition of the said petroleum resin-type tackifier (B2) to an adhesive composition is arbitrary, but the addition The amount is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and may be 0 part by weight with respect to 100 parts by weight of the isobutylene polymer (A2).
　また、本発明の粘着剤組成物には、前記天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）以外の粘着付与剤を添加することもできる。但し、他の粘着付与剤の添加量は、前記ゴム系ポリマー（Ａ）１００重量部に対して、１００重量部以下であるのが好ましい。 Moreover, tackifiers other than the natural product-based tackifier (B1) and petroleum resin-based tackifier (B2) can be added to the pressure-sensitive adhesive composition of the present invention. However, the addition amount of the other tackifier is preferably 100 parts by weight or less with respect to 100 parts by weight of the rubber-based polymer (A).
　（３）その他の添加剤
　本発明の粘着剤組成物には、本発明の効果を損なわない範囲で、前記以外の添加剤を添加することもできる。添加剤としては、特に限定されるものではないが、軟化剤（Ｃ）を添加することが、粘着特性の観点から好ましい。 (3) Other additives Additives other than those described above may be added to the pressure-sensitive adhesive composition of the present invention as long as the effects of the present invention are not impaired. Although it does not specifically limit as an additive, It is preferable from a viewpoint of an adhesive characteristic to add a softener (C).
　前記粘着付与剤（Ｂ）の種類によっては、粘着剤層の低温領域における弾性率が上昇し、例えば、耐衝撃性等の特定の特性が悪化する場合がある。そのような場合に、粘着剤組成物に軟化剤（Ｃ）を用いることで、その可塑効果によりゴム系ポリマー（Ａ）の弾性率を低くすることができ、その結果、前記粘着付与剤（Ｂ）を使用していても、前記不具合が発生することが抑制することができるため、好ましい。 Depending on the type of the tackifier (B), the elastic modulus in the low temperature region of the pressure-sensitive adhesive layer may increase, and for example, certain characteristics such as impact resistance may deteriorate. In such a case, by using the softener (C) in the pressure-sensitive adhesive composition, the elastic modulus of the rubber-based polymer (A) can be lowered due to its plastic effect, and as a result, the tackifier (B ) Is preferable because the occurrence of the above-described problems can be suppressed.
　前記軟化剤（Ｃ）としては、重量平均分子量が５万以下であるポリイソブチレン系化合物（Ｃ１）、及び重量平均分子量が５万以下であるポリイソプレン系化合物（Ｃ２）からなる群から選択される少なくとも１種の軟化剤を挙げることができる。 The softener (C) is selected from the group consisting of a polyisobutylene compound (C1) having a weight average molecular weight of 50,000 or less and a polyisoprene compound (C2) having a weight average molecular weight of 50,000 or less. There may be mentioned at least one softener.
　軟化剤（Ｃ）の重量平均分子量は、５万以下であり、４万以下であることがより好ましい。また、前記軟化剤（Ｃ）の重量平均分子量の下限値は特に限定されるものではないが、５００以上であることが好ましく、１０００以上であることがより好ましい。前記軟化剤（Ｃ）の重量平均分子量が前記範囲にあることで、分子量が小さくなりすぎたために起こる凝集力の低下を防ぐことができ、一方、分子量が大きくなりすぎると軟化剤として作用しなくなることを防ぐことができる。 The weight average molecular weight of the softener (C) is 50,000 or less, and more preferably 40,000 or less. Moreover, the lower limit of the weight average molecular weight of the softening agent (C) is not particularly limited, but is preferably 500 or more, and more preferably 1000 or more. When the weight average molecular weight of the softening agent (C) is in the above range, it is possible to prevent a decrease in cohesive force caused by the molecular weight being too small, while when the molecular weight is too large, the softening agent (C) does not act as a softening agent. Can be prevented.
　前記ポリイソブチレン系化合物（Ｃ１）としては、イソブチレンのみかなる化合物（ポリイソブチレン）であってもよく、イソブチレンを主モノマーとする共重合物（すなわち、イソブチレンが５０モル％を超える割合で含む共重合物）であってもよい。このような共重合物としては、例えば、イソブチレンとノルマルブチレンとの共重合体、イソブチレンとイソプレンとの共重合体（例えば、レギュラーブチルゴム、塩素化ブチルゴム、臭素化ブチルゴム、部分架橋ブチルゴム等のブチルゴム類）、これらの加硫物や変性物（例えば、水酸基、カルボキシル基、アミノ基、エポキシ基等の官能基で変性したもの）等を挙げることができる。これらの中でも、主鎖に二重結合を含まず、耐候性に優れているため、ポリイソブチレンが好ましい。 The polyisobutylene compound (C1) may be a compound composed of only isobutylene (polyisobutylene), and a copolymer containing isobutylene as a main monomer (that is, a copolymer containing isobutylene in a proportion exceeding 50 mol%). Thing). Examples of such copolymers include copolymers of isobutylene and normal butylene, copolymers of isobutylene and isoprene (for example, butyl rubbers such as regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and partially crosslinked butyl rubber). ), Vulcanizates and modified products thereof (for example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group). Among these, polyisobutylene is preferable because it does not contain a double bond in the main chain and has excellent weather resistance.
　前記ポリイソプレン系化合物（Ｃ２）としては、イソプレンのみかなる化合物（ポリイソプレン）であってもよく、イソプレンを主モノマーとする共重合物（すなわち、イソプレンが５０モル％を超える割合の共重合物）であってもよい。このような共重合物としては、具体的には、ブタジエン－イソプレン－スチレンランダム共重合体、イソプレン－スチレンランダム共重合体、水添ポリイソプレン等を挙げることができる。これらの中でも、ゴム系ポリマーへの可塑効果の点から水添ポリイソプレンが好ましい。 The polyisoprene compound (C2) may be a compound consisting of isoprene alone (polyisoprene), and a copolymer having isoprene as a main monomer (that is, a copolymer having a proportion of isoprene exceeding 50 mol%). ). Specific examples of such a copolymer include butadiene-isoprene-styrene random copolymer, isoprene-styrene random copolymer, and hydrogenated polyisoprene. Among these, hydrogenated polyisoprene is preferable from the viewpoint of the plasticizing effect on the rubber-based polymer.
　軟化剤（Ｃ）としては、例えば、ＪＸ日鉱日石エネルギー（株）製のＨＶ－３００、（株）クラレ製のクラプレンＬＩＲ－２００等の市販品を用いることができる。 As the softener (C), for example, commercially available products such as HV-300 manufactured by JX Nippon Mining & Energy, Kuraprene LIR-200 manufactured by Kuraray Co., Ltd. can be used.
　また、前記軟化剤（Ｃ）の添加量は、特に限定されるものではないが、前記ゴム系ポリマー（Ａ）１００重量部に対して、５０重量部以下であることが好ましく、３０重量部以下であることがより好ましく、２５重量部以下であることがさらに好ましい。また、軟化剤（Ｃ）の添加量の下限値は特に限定されるものではないが、０重量部以上であることが好ましく、１重量部以上であることがより好ましく、５重量部以上であることがさらに好ましい。 The amount of the softening agent (C) added is not particularly limited, but is preferably 50 parts by weight or less, and 30 parts by weight or less with respect to 100 parts by weight of the rubber-based polymer (A). More preferably, it is more preferably 25 parts by weight or less. Moreover, the lower limit of the addition amount of the softening agent (C) is not particularly limited, but is preferably 0 part by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably.
　また、前記粘着剤組成物には、希釈剤として有機溶媒を添加することができる。希釈剤としては、特に限定されるものではないが、例えば、トルエン、キシレン、ジメチルエーテル等を挙げることができ、これらを１種単独で又は２種以上を混合して使用することができる。これらの中でも、トルエンが好ましい。 Also, an organic solvent can be added as a diluent to the pressure-sensitive adhesive composition. Although it does not specifically limit as a diluent, For example, toluene, xylene, dimethyl ether etc. can be mentioned, These can be used individually by 1 type or in mixture of 2 or more types. Among these, toluene is preferable.
　希釈剤の添加量は、特に限定されるものではないが、粘着剤組成物中に５０～９５重量％程度で添加することが好ましく、７０～９０重量％程度であることがより好ましい。希釈剤の添加量が前記範囲であることにより、支持体等へ塗工性の観点から好ましい。 The addition amount of the diluent is not particularly limited, but is preferably added to the pressure-sensitive adhesive composition at about 50 to 95% by weight, more preferably about 70 to 90% by weight. When the addition amount of the diluent is within the above range, it is preferable from the viewpoint of coatability to a support or the like.
　前記粘着剤組成物には、任意の適切な添加剤をさらに含んでいてもよい。添加剤の具体例としては、架橋剤（例えば、ポリイソシアネート、エポキシ化合物、アルキルエーテル化メラミン化合物等）、充填剤、老化防止剤、紫外線吸収剤等が挙げられる。粘着剤組成物に添加される添加剤の種類、組み合わせ、添加量等は、目的に応じて適切に設定され得る。粘着剤組成物における前記添加剤の含有量（総量）は、３０重量％以下であることが好ましく、２０重量％以下であることがより好ましく、１０重量％以下であることがさらに好ましい。 The pressure-sensitive adhesive composition may further contain any appropriate additive. Specific examples of the additive include a crosslinking agent (for example, polyisocyanate, epoxy compound, alkyl etherified melamine compound, etc.), filler, anti-aging agent, ultraviolet absorber and the like. The kind, combination, addition amount, and the like of the additive added to the pressure-sensitive adhesive composition can be appropriately set according to the purpose. The content (total amount) of the additive in the pressure-sensitive adhesive composition is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less.
　２．粘着剤層
　本発明の粘着剤層は、前記粘着剤組成物から形成されたことを特徴とする。 2. Adhesive layer The adhesive layer of this invention was formed from the said adhesive composition.
　本発明の粘着剤層の製造方法は特に限定されないが、各種支持体等に前記粘着剤組成物を塗布し、加熱乾燥等により溶媒等を除去することにより、粘着剤層を形成することができる。 Although the manufacturing method of the adhesive layer of this invention is not specifically limited, An adhesive layer can be formed by apply | coating the said adhesive composition to various support bodies etc., and removing a solvent etc. by heat drying etc. .
　粘着剤組成物の塗布方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
　前記加熱乾燥温度は、３０℃～２００℃程度が好ましく、４０℃～１８０℃がより好ましく、８０℃～１５０℃がさらに好ましい。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する粘着剤層を得ることができる。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、５秒～２０分程度が好ましく、３０秒～１０分がより好ましく、１分～８分がさらに好ましい。 The heating and drying temperature is preferably about 30 ° C to 200 ° C, more preferably 40 ° C to 180 ° C, and further preferably 80 ° C to 150 ° C. By setting the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained. As the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
　前記支持体としては、例えば、剥離処理したシート（セパレーター）を用いることができる。 As the support, for example, a peeled sheet (separator) can be used.
　前記セパレーターの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、及びこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 Examples of the constituent material of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Although an appropriate thin leaf body etc. can be mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.
　前記プラスチックフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 Examples of the plastic film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -Vinyl acetate copolymer film and the like.
　前記セパレーターの厚みは、通常５～２００μｍ、好ましくは５～１００μｍ程度である。前記セパレーターには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型、及び防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレーターの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜行うことにより、前記粘着剤層からの剥離性をより高めることができる。 The thickness of the separator is usually about 5 to 200 μm, preferably about 5 to 100 μm. For the separator, silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, release by silica powder, and antifouling treatment, coating type, kneading type, vapor deposition, as required An antistatic treatment such as a mold can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
　本発明の粘着剤層の厚みは、特に限定されるものではなく、その用途に応じて適宜設定することができるが、５０μｍ以下であることが好ましく、３０μｍ以下であることがより好ましく、２０μｍ以下であることがさらに好ましい。また、粘着剤層の厚みの下限値は、特に限定されるものではないが、耐久性の観点からは、１μｍ以上であることが好ましく、５μｍ以上であることがより好ましい。 The thickness of the pressure-sensitive adhesive layer of the present invention is not particularly limited, and can be appropriately set depending on the application, but is preferably 50 μm or less, more preferably 30 μm or less, and 20 μm or less. More preferably. The lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 μm or more and more preferably 5 μm or more from the viewpoint of durability.
　前記粘着剤層の透湿度は、特に限定されるものではないが、１００ｇ／（ｍ２・２４ｈ）以下であることが好ましく、６０ｇ／（ｍ２・２４ｈ）以下がより好ましく、５０ｇ／（ｍ２・２４ｈ）以下がさらに好ましく、３０ｇ／（ｍ２・２４ｈ）以下がさらに好ましく、２０ｇ／（ｍ２・２４ｈ）以下が特に好ましい。また、透湿度の下限値は特に限定されるものではないが、理想的には、水蒸気を全く透過させないこと（すなわち、０ｇ／（ｍ２・２４ｈ））が好ましい。粘着剤層の透湿度が前記範囲であれば、当該粘着層を偏光フィルム等の光学フィルムに適用した場合に、光学フィルムに水分が移行することを抑制することができ、光学フィルムの水分による劣化等を抑制することができるため好ましい。前記透湿度は、粘着剤層の厚み５０μｍにおける４０℃、９２％Ｒ．Ｈ．条件下での水蒸気透過率（透湿度）であって、その測定方法は実施例に記載の方法により測定することができる。 The moisture permeability of the pressure-sensitive adhesive layer is not particularly limited, is preferably 100g / (m 2 · 24h) or less, more preferably 60g / (m 2 · 24h) or less, 50 g / (m 2 · 24h) or less is more preferable, 30g / (m 2 · 24h) or less is more preferable, and 20g / (m 2 · 24h) or less is particularly preferable. Further, the lower limit value of the moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not transmitted at all (that is, 0 g / (m 2 · 24 h)). If the moisture permeability of the pressure-sensitive adhesive layer is in the above range, when the pressure-sensitive adhesive layer is applied to an optical film such as a polarizing film, it is possible to suppress moisture from being transferred to the optical film, and deterioration of the optical film due to moisture. Etc. can be suppressed. The moisture permeability is 40 ° C. and 92% R.D. when the pressure-sensitive adhesive layer has a thickness of 50 μm. H. The water vapor transmission rate (moisture permeability) under the conditions can be measured by the method described in the examples.
　３．粘着剤層付光学フィルム
　本発明の粘着剤層付光学フィルムは、光学フィルムと、前記光学フィルム上に設けられた前記粘着剤層を有することを特徴とする。 3. Optical film with pressure-sensitive adhesive layer The optical film with a pressure-sensitive adhesive layer of the present invention comprises an optical film and the pressure-sensitive adhesive layer provided on the optical film.
　前記光学フィルム上に粘着剤層を形成する方法としては、光学フィルム上に前記粘着剤組成物を塗布し、加熱乾燥等により溶媒等を除去することにより、粘着剤層を光学フィルム上に形成することができる。また、前述の通り、支持体等上に粘着剤層を形成し、当該粘着剤層を光学フィルム上に転写して、粘着剤層付光学フィルムを形成することもできる。この場合、前記粘着剤層付光学フィルムの作製にあたって用いた、剥離処理したシートは、そのまま粘着剤層付光学フィルムのセパレーターとして用いることができ、工程面における簡略化ができる。 As a method for forming the pressure-sensitive adhesive layer on the optical film, the pressure-sensitive adhesive layer is formed on the optical film by applying the pressure-sensitive adhesive composition on the optical film and removing the solvent by heat drying or the like. be able to. Moreover, as above-mentioned, an adhesive layer can be formed on a support body etc., the said adhesive layer can be transcribe | transferred on an optical film, and an optical film with an adhesive layer can also be formed. In this case, the release-treated sheet used in the production of the optical film with the pressure-sensitive adhesive layer can be used as it is as a separator of the optical film with the pressure-sensitive adhesive layer, and the process can be simplified.
　前記光学フィルムとしては、液晶表示装置等の各種画像表示装置の形成に用いられるものが使用され、その種類は特に制限されない。例えば、光学フィルムとしては偏光フィルムが挙げられる。偏光フィルムは偏光子の片面又は両面には透明保護フィルムを有するものが一般に用いられるが、本発明においては、薄型化の観点から、片面保護偏光フィルムであることが好ましい。 As the optical film, those used for forming various image display devices such as a liquid crystal display device are used, and the type thereof is not particularly limited. For example, a polarizing film is mentioned as an optical film. A polarizing film having a transparent protective film on one side or both sides of a polarizer is generally used, but in the present invention, a single-sided protective polarizing film is preferable from the viewpoint of thinning.
　偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素等の二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的に５～８０μｍ程度である。 The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.
　ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の３～７倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いヨウ化カリウム等の水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラ等の不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウム等の水溶液や水浴中でも延伸することができる。 A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
　また、薄膜化の観点から、厚みが１０μｍ以下の薄型偏光子を用いることが好ましい。薄型化の観点から言えば当該厚みは、１～７μｍであるのが好ましい。このような薄型の偏光子は、厚みムラが少なく、視認性が優れており、また寸法変化が少ないため耐久性に優れ、さらには偏光フィルムとしての厚みも薄型化が図れる点が好ましい。 Further, from the viewpoint of thinning, it is preferable to use a thin polarizer having a thickness of 10 μm or less. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.
　薄型の偏光子としては、代表的には、特開昭５１－０６９６４４号公報や特開２０００－３３８３２９号公報や、国際公開第２０１０／１００９１７号パンフレット、又は特開２０１４－５９３２８号公報や特開２０１２－７３５６３号公報に記載されている薄型偏光膜を挙げることができる。これら薄型偏光膜は、ポリビニルアルコール系樹脂（以下、ＰＶＡ系樹脂ともいう）層と延伸用樹脂基材を積層体の状態で延伸する工程と染色する工程を含む製法による得ることができる。この製法であれば、ＰＶＡ系樹脂層が薄くても、延伸用樹脂基材に支持されていることにより延伸による破断等の不具合なく延伸することが可能となる。 As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917 pamphlet, Japanese Patent Application Laid-Open No. 2014-59328, and Japanese Patent Application Laid-Open No. 2014-59328 are disclosed. The thin polarizing film described in 2012-73563 gazette can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.
　前記薄型偏光膜としては、積層体の状態で延伸する工程と染色する工程を含む製法の中でも、高倍率に延伸できて偏光性能を向上させることのできる点で、国際公開第２０１０／１００９１７号パンフレット、又は特開２０１４－０５９３２８号公報や特開２０１２－０７３５６３号公報に記載のあるようなホウ酸水溶液中で延伸する工程を含む製法で得られるものが好ましく、特に特開２０１４－０５９３２８号公報や特開２０１２－０７３５６３号公報に記載のあるホウ酸水溶液中で延伸する前に補助的に空中延伸する工程を含む製法により得られるものが好ましい。 As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. Or obtained by a production method including a step of stretching in a boric acid aqueous solution as described in Japanese Patent Application Laid-Open No. 2014-059328 and Japanese Patent Application Laid-Open No. 2012-0753563. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution described in Unexamined-Japanese-Patent No. 2012-0753563 is preferable.
　前記偏光子の片面又は両面に設けられる透明保護フィルムを形成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体（ＡＳ樹脂）等のスチレン系ポリマー、ポリカーボネート系ポリマー等が挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体等のポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、又は、前記ポリマーのブレンド物等も前記透明保護フィルムを形成するポリマーの例として挙げられる。透明保護フィルムは、アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化型、紫外線硬化型の樹脂の硬化層として形成することもできる。偏光子の両側に保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いても良く、異なるポリマー材料等からなる保護フィルムを用いても良い。 As the material for forming the transparent protective film provided on one or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone. When providing a protective film on both sides of the polarizer, a protective film made of the same polymer material may be used on the front and back, or a protective film made of a different polymer material or the like may be used.
　保護フィルムの厚みは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄膜性等の点より１～５００μｍ程度である。 The thickness of the protective film can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin film properties.
　前記偏光子と保護フィルムとは通常、水系接着剤等を介して密着している。水系接着剤としては、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリウレタン、水系ポリエステル等を例示できる。上記の他、偏光子と透明保護フィルムとの接着剤としては、紫外硬化型接着剤、電子線硬化型接着剤等が挙げられる。電子線硬化型偏光フィルム用接着剤は、上記各種の透明保護フィルムに対して、好適な接着性を示す。また本発明で用いる接着剤には、金属化合物フィラーを含有させることができる。 The polarizer and the protective film are usually in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness to the various transparent protective films. The adhesive used in the present invention can contain a metal compound filler.
　前記透明保護フィルムの偏光子を接着させない面には、ハードコート層や反射防止処理、スティッキング防止や、拡散ないしアンチグレアを目的とした処理を施したものであっても良い。 The surface of the transparent protective film to which the polarizer is not bonded may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
　例えば、図１に示すように、偏光フィルム２が、偏光子４の片面のみに透明保護フィルム５を有する片面保護偏光フィルムである場合、前記粘着剤層３が、偏光子４の透明保護フィルム５を有さない側（すなわち、偏光子４側）に形成されていることが好ましい。この場合、前記偏光子４と粘着剤層３は必ずしも接触している必要はないが、本発明の効果を顕著に発現できる観点からは、これらが接触していることが好ましい。このような構成とすることで、偏光子への水分等の移行を抑制することができ、片面保護偏光フィルムの偏光子が劣化することを抑制することができる。 For example, as shown in FIG. 1, when the polarizing film 2 is a single-sided protective polarizing film having a transparent protective film 5 only on one side of the polarizer 4, the pressure-sensitive adhesive layer 3 is a transparent protective film 5 of the polarizer 4. Preferably, it is formed on the side that does not have (that is, the polarizer 4 side). In this case, the polarizer 4 and the pressure-sensitive adhesive layer 3 are not necessarily in contact with each other, but are preferably in contact with each other from the viewpoint that the effects of the present invention can be remarkably exhibited. By setting it as such a structure, transfer of the water | moisture content etc. to a polarizer can be suppressed, and it can suppress that the polarizer of a single-sided protection polarizing film deteriorates.
　また、前記偏光板フィルム以外の光学フィルムとしては、例えば、反射板や反透過板、位相差板（１／２や１／４等の波長板を含む）、視角補償フィルム、輝度向上フィルム等の液晶表示装置等の形成に用いられることのある光学層となるものが挙げられる。これらの中でも、輝度向上フィルムを光学フィルムとして好適に用いることができる。これらは単独で光学フィルムとして用いることができる他、前記偏光フィルムに、実用に際して積層して、１層又は２層以上用いることができる。 In addition, examples of the optical film other than the polarizing film include a reflection plate, an anti-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), a viewing angle compensation film, and a brightness enhancement film. What becomes an optical layer which may be used for formation of a liquid crystal display device etc. is mentioned. Among these, a brightness enhancement film can be suitably used as an optical film. These can be used alone as an optical film, or can be laminated on the polarizing film for practical use to use one layer or two or more layers.
　また、前記光学フィルムには活性化処理を施すことができる。活性化処理は各種方法を採用でき、例えばコロナ処理、低圧ＵＶ処理、プラズマ処理等を採用できる。 Also, the optical film can be activated. Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.
　４．光学部材
　本発明の光学部材は、前記粘着剤層付光学フィルムと、輝度向上フィルムを含む光学部材（以下、「第１光学部材」という）や、前記粘着剤層と、４０℃、９２％Ｒ．Ｈ．における透湿度が１ｇ／（ｍ２・ｄａｙ）以下であるフィルムを含む光学部材（以下、「第２光学部材」という）を挙げることができる。 4). Optical member The optical member of the present invention includes the optical film with the pressure-sensitive adhesive layer, an optical member including a brightness enhancement film (hereinafter referred to as “first optical member”), the pressure-sensitive adhesive layer, 40 ° C., and 92% R. . H. The optical member (henceforth "the 2nd optical member") containing the film whose water vapor transmission rate is 1 g / (m < 2 > * day) or less can be mentioned.
　第１光学部材は、前記粘着剤層付光学フィルムの粘着剤層を介して、さらに輝度向上フィルムを積層するものである。第１光学部材における粘着剤層付光学フィルムとしては、粘着剤層付偏光フィルムであることが好ましい。例えば、図２に示すように、偏光フィルム２、粘着剤層３、輝度向上フィルム６を有する光学部材１０を挙げることができる。また、このような光学部材１０は、その他の層を有していてもよく、例えば、図３に示すように、前記輝度向上フィルム６の粘着剤層３を有さない側に、粘着剤層（不図示）等を介して、プリズムシート７をさらに積層することができる。プリズムシート７は、代表的には、基板とプリズム部とを有する。また、図２、３においては、図１と同様に片面保護偏光フィルムを記載しているが、両面保護偏光フィルムであってもよい。このような光学部材は、液晶表示装置のバックライト側の偏光板として用いることが好ましい。 The first optical member is formed by further laminating a brightness enhancement film via the pressure-sensitive adhesive layer of the optical film with the pressure-sensitive adhesive layer. As an optical film with an adhesive layer in a 1st optical member, it is preferable that it is a polarizing film with an adhesive layer. For example, as shown in FIG. 2, the optical member 10 which has the polarizing film 2, the adhesive layer 3, and the brightness enhancement film 6 can be mentioned. Moreover, such an optical member 10 may have other layers. For example, as shown in FIG. 3, as shown in FIG. The prism sheet 7 can be further laminated through (not shown) or the like. The prism sheet 7 typically has a substrate and a prism portion. Moreover, in FIG. 2, 3, although the single-sided protective polarizing film is described similarly to FIG. 1, a double-sided protective polarizing film may be sufficient. Such an optical member is preferably used as a polarizing plate on the backlight side of the liquid crystal display device.
　また、前記輝度向上フィルム６としては、反射型偏光板を挙げることができる。前記反射型偏光板は、直線偏光分離型の偏光板である。その代表例としては、グリッド型偏光板、屈折率の異なる２種以上の材料の多層薄膜積層偏光板、屈折率の異なる蒸着多層薄膜、屈折率の異なる２種以上の材料の複屈折層多層薄膜積層体、屈折率差を有する２種以上の樹脂を用いた２種以上の樹脂積層体を延伸したもの、直線偏光を直交する軸方向で反射／透過することで分離する偏光板（直線偏光分離型反射偏光板）が挙げられる。これらの中でも直線偏光分離型反射偏光板が好適に用いられる。このような反射型偏光板としては、例えばスリーエム製の商品名「Ｄ－ＢＥＦ」や、日東電工（株）製の商品名「ニポックスＡＰＣＦ」として市販されているものを用いることもできる。 Moreover, as the brightness enhancement film 6, a reflective polarizing plate can be mentioned. The reflective polarizing plate is a linearly polarized light separation type polarizing plate. Typical examples include grid-type polarizing plates, multilayer thin film laminated polarizing plates of two or more materials having different refractive indexes, vapor-deposited multilayer thin films having different refractive indexes, and birefringent multilayer thin films of two or more materials having different refractive indexes. Laminated body, two or more kinds of resin laminates using two or more kinds of resins having a refractive index difference, a polarizing plate that separates by reflecting / transmitting linearly polarized light in an orthogonal axis direction (linearly polarized light separation) Type reflective polarizing plate). Among these, a linearly polarized light separation type reflection polarizing plate is preferably used. As such a reflective polarizing plate, for example, those commercially available under the trade name “D-BEF” manufactured by 3M or the product name “Nipox APCF” manufactured by Nitto Denko Corporation may be used.
　また、第２光学部材に用いる、４０℃、９２％Ｒ．Ｈ．における透湿度が１ｇ／ｍ２・ｄａｙ以下であるフィルムとしては、例えば、有機ＥＬ素子に用いられるバリア層等を挙げることできる。有機ＥＬ素子に用いられるバリア層としては、例えば、三フッ化ポリエチレン、ポリ三フッ化塩化エチレン（ＰＣＴＦＥ）、ポリイミド、ポリカーボネート、ポリエチレンテレフタレート、脂環式ポリオレフィン、エチレン－ビニルアルコール共重合体等のポリマー層、若しくはこれらの積層体、さらに前記ポリマー層にスパッタリング等の成膜法を用いて酸化ケイ素、窒化ケイ素、酸化アルミニウム、ダイヤモンドライクカーボン等の無機薄膜が被覆されたもの等を挙げることができる。このような低透湿フィルムを有する光学部材は、有機ＥＬ装置に好適に用いることができ、具体的には、有機ＥＬ素子の封止部材として用いることができる。 In addition, it is used for the second optical member at 40 ° C. and 92% R.D. H. Examples of the film having a moisture permeability of 1 g / m 2 · day or less include a barrier layer used in an organic EL device. Examples of the barrier layer used in the organic EL device include polymers such as polyethylene trifluoride, poly (ethylene trifluorochloride) (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer. Examples thereof include a layer, a laminate thereof, and a polymer layer coated with an inorganic thin film such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon by using a film forming method such as sputtering. An optical member having such a low moisture-permeable film can be suitably used for an organic EL device, and specifically can be used as a sealing member for an organic EL element.
　５．画像表示装置
　本発明の画像表示装置は、前記粘着剤層付偏光フィルム、及び前記光学部材からなる群から選択される１種以上を含むことを特徴とする。画像表示装置としては、例えば、液晶表示装置、有機ＥＬ表示装置等を挙げることができる。 5). Image display device The image display device of the present invention is characterized by including one or more kinds selected from the group consisting of the polarizing film with an adhesive layer and the optical member. Examples of the image display device include a liquid crystal display device and an organic EL display device.
　本発明の画像表示装置は、本発明の粘着剤層付光学フィルム又は光学部材を含むものであればよく、その他の構成については、従来の画像表示装置と同様のものを挙げることができる。 The image display device of the present invention only needs to include the optical film or optical member with the pressure-sensitive adhesive layer of the present invention, and other configurations can be the same as those of the conventional image display device.
　本発明の画像表示装置は、前記粘着剤層付光学フィルム又は光学部材を含むため、高い光学信頼性を有するものである。 Since the image display device of the present invention includes the optical film or optical member with the pressure-sensitive adhesive layer, it has high optical reliability.
　以下に、実施例によって本発明を具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、各例中の部及び％はいずれも重量基準である。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.
　（重量平均分子量）
　重量平均分子量（Ｍｗ）の測定は，ゲルパーミエーションクロマトグラフィ法（ＧＰＣ法）において行い、ＨＬＣ－８１２０（東ソー社製）による内径６．０ｍｍ、長さ１５０ｍｍのカラム（東ソ社製、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ／ＨＺ４０００／ＨＺ３０００／ＨＺ２０００）を直列に接続して使用し、溶離液にテトラヒドロフランを用いて濃度１ｇ／Ｌ、流量０．６ｍｌ／分、温度４０℃、サンプル注入量２０μｌの条件で行い、検出器にはＲＩ検出器を用いた。また分子量の検量線の作成には，ＴＳＫ　標準ポリスチレン（東ソー社製）を用いた。 (Weight average molecular weight)
The weight average molecular weight (Mw) was measured by a gel permeation chromatography method (GPC method), and an HLC-8120 (manufactured by Tosoh Corp.) column with an inner diameter of 6.0 mm and a length of 150 mm (manufactured by Tosoh Corp., TSKgel SuperHZM-). H / HZ4000 / HZ3000 / HZ2000) connected in series, tetrahydrofuran is used as the eluent, concentration is 1 g / L, flow rate is 0.6 ml / min, temperature is 40 ° C., sample injection volume is 20 μl, and detection The detector was an RI detector. In addition, TSK standard polystyrene (manufactured by Tosoh Corporation) was used to prepare a calibration curve for molecular weight.
　製造例１（偏光フィルムの製造）
　薄型偏光膜を作製するため、まず、非晶性ポリエチレンテレフタレート（ＰＥＴ）基材に９μｍ厚のポリビニルアルコール（ＰＶＡ）層が製膜された積層体を延伸温度１３０℃の空中補助延伸によって延伸積層体を生成した。次に、延伸積層体を染色によって着色積層体を生成し、さらに着色積層体を延伸温度６５℃のホウ酸水中延伸によって総延伸倍率が５．９４倍になるように非晶性ＰＥＴ基材と一体に延伸された４μｍ厚のＰＶＡ層を含む光学フィルム積層体を生成した。このような２段延伸によって非晶性ＰＥＴ基材に製膜されたＰＶＡ層のＰＶＡ分子が高次に配向され、染色によって吸着されたヨウ素がポリヨウ素イオン錯体として一方向に高次に配向された高機能偏光膜（偏光子）を構成する、厚さ５μｍのＰＶＡ層を含む光学フィルム積層体を生成した。 Production Example 1 (Production of polarizing film)
In order to produce a thin polarizing film, first, a laminate in which a 9 μm-thick polyvinyl alcohol (PVA) layer is formed on an amorphous polyethylene terephthalate (PET) substrate is stretched by air-assisted stretching at a stretching temperature of 130 ° C. Was generated. Next, a colored laminate is produced by dyeing the stretched laminate, and the colored laminate is further stretched in boric acid in water at a stretching temperature of 65 ° C. so that the total stretch ratio becomes 5.94 times. An optical film laminate comprising a 4 μm thick PVA layer stretched together was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. Thus, an optical film laminate including a PVA layer having a thickness of 5 μm constituting a highly functional polarizing film (polarizer) was produced.
　上記偏光子に係る上記光学フィルム積層体の偏光膜（偏光子、厚み：５μｍ）の表面に、接着剤層の厚さが０．１μｍになるようにポリビニルアルコール系接着剤を塗布しながら、透明保護フィルム（厚さ２０μｍのラクトン環構造を有する（メタ）アクリル樹脂フィルムにコロナ処理を施したもの）を貼合せたのち、５０℃で５分間の乾燥を行った。次いで、非晶性ＰＥＴ基材を剥離して、薄型偏光子を用いた片保護偏光フィルムを作製した。 While applying a polyvinyl alcohol adhesive so that the thickness of the adhesive layer is 0.1 μm on the surface of the polarizing film (polarizer, thickness: 5 μm) of the optical film laminate according to the polarizer, A protective film (a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 μm and subjected to corona treatment) was bonded, followed by drying at 50 ° C. for 5 minutes. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film using a thin polarizer.
　実施例１
　ゴム系ポリマー（Ａ）としてスチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、商品名：ＳＥＰＴＯＮ　２０６３、スチレン含有量：１３％、（株）クラレ製）１００重量部と、粘着付与剤（Ｂ）として水添テルペンフェノール（商品名：ＹＳポリスターＴＨ１３０、軟化点：１３０℃、水酸基価：６０、ヤスハラケミカル（株）製）４０．４重量部、石油系粘着付与剤（商品名：ピコラスチックＡ５、ビニルトルエン系粘着付与剤、軟化点：５℃、イーストマンコダック社製）６１．７部、軟化剤（Ｃ）としてポリブテン（商品名：ＨＶ－３００、重量平均分子量：３０００、ＪＸ日鉱日石エネルギー（株）製）２１．３部を配合したトルエン溶液（粘着剤溶液）を固形分が３０重量％になるように調整し、粘着剤組成物（溶液）を調製した。 Example 1
100 parts by weight of a styrene-ethylene-propylene-styrene block copolymer (SEPS, trade name: SEPTON 2063, styrene content: 13%, manufactured by Kuraray Co., Ltd.) as a rubber polymer (A) and a tackifier (B ) Hydrogenated terpene phenol (trade name: YS Polyster TH130, softening point: 130 ° C., hydroxyl value: 60, manufactured by Yasuhara Chemical Co., Ltd.), 40.4 parts by weight, petroleum-based tackifier (trade name: Picolastic A5, Vinyl toluene-based tackifier, softening point: 5 ° C., Eastman Kodak Co., Ltd. 61.7 parts, softening agent (C) polybutene (trade name: HV-300, weight average molecular weight: 3000, JX Nippon Oil & Energy Co., Ltd.) Toluene solution (adhesive solution) containing 21.3 parts was adjusted so that the solid content was 30% by weight. A composition (solution) was prepared.
　得られた粘着剤組成物（溶液）を、片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）の剥離処理面に塗布して塗布層を形成した。次いで、塗布層を１２０℃で３分乾燥させて、粘着剤層を形成し、粘着剤層の厚みが２０μｍの粘着シートを作製した。また、粘着シートの粘着面には、前記片面をシリコーンで剥離処理した厚み３８μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ、三菱樹脂（株）製）を、剥離処理面と前記粘着剤層が接するように貼り合せた。粘着剤層の両面に被覆されたポリエステルフィルムは、剥離ライナー（セパレーター）として機能する。 The obtained pressure-sensitive adhesive composition (solution) was applied to the release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) with one side peeled with silicone. Formed. Subsequently, the coating layer was dried at 120 ° C. for 3 minutes to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 20 μm was produced. Also, the adhesive surface of the pressure-sensitive adhesive sheet is a 38 μm thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone, and the peel-treated surface is in contact with the pressure-sensitive adhesive layer. Were pasted together. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
　前記粘着剤シートの一方の剥離ライナーを剥離し、製造例１で得られた偏光フィルムの偏光子上に、粘着剤層と偏光子が接するように積層して粘着剤層付偏光フィルムを得た。粘着剤層の剥離ライナーはセパレーターとして残した。得られた粘着剤層付偏光フィルムの構成は、透明保護フィルム／偏光子／粘着剤層／セパレーターであった。 One release liner of the pressure-sensitive adhesive sheet was peeled off, and the pressure-sensitive adhesive layer and the polarizer were laminated on the polarizer of the polarizing film obtained in Production Example 1 to obtain a polarizing film with a pressure-sensitive adhesive layer. . The release liner of the pressure-sensitive adhesive layer was left as a separator. The structure of the obtained polarizing film with an adhesive layer was transparent protective film / polarizer / adhesive layer / separator.
　実施例２～３１、比較例１～７
　実施例１において、粘着剤組成物の各成分を表１、２に記載の組成にした以外は実施例１と同様にして、粘着剤層付偏光フィルムを作製した。 Examples 2-31 and Comparative Examples 1-7
In Example 1, a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that each component of the pressure-sensitive adhesive composition was changed to the composition described in Tables 1 and 2.
　比較例８（アクリル系粘着剤層の作製）
　温度計、攪拌機、還流冷却管及び窒素ガス導入管を備えたセパラブルフラスコに、モノマー成分として、ブチルアクリレート（ＢＡ）９９重量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）１重量部、重合開始剤としてアゾビスイソブチロニトリル０．２重量部及び重合溶媒として酢酸エチルを固形分が２０％になるように投入した後、窒素ガスを流し、攪拌しながら約１時間窒素置換を行った。その後、６０℃にフラスコを加熱し、７時間反応させて重量平均分子量（Ｍｗ）１１０万のアクリル系ポリマーを得た。上記アクリル系ポリマー溶液（固形分１００重量部）に、イソシアネート系架橋剤としてトリメチロールプロパントリレンジイソシアネート（商品名：コロネートＬ、日本ポリウレタン工業（株）製）０．８重量部、シランカップリング剤（商品名：ＫＢＭ－４０３、信越化学（株）製）０．１重量部を加えてアクリル系粘着剤組成物を調製した。 Comparative Example 8 (production of acrylic pressure-sensitive adhesive layer)
In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 99 parts by weight of butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and a polymerization initiator After 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so as to have a solid content of 20%, nitrogen substitution was performed for about 1 hour while flowing nitrogen gas and stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. To the acrylic polymer solution (solid content: 100 parts by weight), 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent, silane coupling agent An acrylic pressure-sensitive adhesive composition was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
　アクリル系粘着剤組成物を用いた以外は実施例１と同様にして粘着剤層付偏光フィルムを得た。 A polarizing film with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive composition was used.
　実施例、比較例で得られた粘着剤組成物、粘着剤層付偏光フィルムについて、以下の評価を行った。評価結果を表１、２に示す。 The following evaluation was performed about the adhesive composition and the polarizing film with an adhesive layer obtained by the Example and the comparative example. The evaluation results are shown in Tables 1 and 2.
　＜透湿度の測定方法＞
　実施例、比較例で得られた粘着剤組成物を用いて、実施例に記載の方法に準じて、粘着剤層の厚みが５０μｍである粘着シートを形成した。粘着シートの一方の剥離ライナーを剥がし、粘着面を露出させて、該粘着面により、粘着シートをトリアセチルセルロースフィルム（ＴＡＣフィルム、厚み２５μｍ、コニカミノルタ（株）製）に貼り合わせた。そして、もう一方の剥離ライナーを剥がして、測定用サンプルを得た。
　次に、この測定用サンプルを用いて、下記条件で、透湿度試験方法（カップ法、ＪＩＳ　Ｚ　０２０８に準じる）により、透湿度（水蒸気透過率）を測定した。
　　測定温度：４０℃
　　相対湿度：９２％
　　測定時間：２４時間
　　なお、測定の際には、恒温恒湿槽を使用した。 <Measurement method of moisture permeability>
Using the pressure-sensitive adhesive compositions obtained in the examples and comparative examples, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 50 μm was formed according to the method described in the examples. One release liner of the pressure-sensitive adhesive sheet was peeled off to expose the pressure-sensitive adhesive surface, and the pressure-sensitive adhesive surface was bonded to a triacetylcellulose film (TAC film, thickness 25 μm, manufactured by Konica Minolta Co., Ltd.). Then, the other release liner was peeled off to obtain a measurement sample.
Next, using this measurement sample, moisture permeability (water vapor permeability) was measured by the moisture permeability test method (cup method, conforming to JIS Z 0208) under the following conditions.
Measurement temperature: 40 ° C
Relative humidity: 92%
Measurement time: 24 hours A constant temperature and humidity chamber was used for the measurement.
　＜粘着力＞
　実施例、比較例で得られた粘着剤シートを用いて、長さ１００ｍｍ、幅２５ｍｍのテープ片を得た。次に、テープ片から一方の剥離ライナーを剥離して、粘着面を露出させて、テープ片の該粘着面に、ＰＥＴフィルム（厚さ：２５μｍ）に貼り合わせ、（剥離ライナー／粘着剤層／ＰＥＴフィルム）の順に積層している基材付き片面粘着テープ（長さ：１００ｍｍ、幅：２５ｍｍ）を作製した。この基材付き片面粘着テープから剥離ライナーを剥離して、測定用サンプルを得た。
　次いで、２３℃、５０％Ｒ．Ｈ．雰囲気下で、測定用サンプルの露出した粘着面（測定面）に、ガラス板（商品名：ソーダライムガラス　＃００５０、松浪硝子工業（株）製）を貼り合わせ、２ｋｇローラーを１往復させることにより圧着した。そして、２３℃、５０％Ｒ．Ｈ．の雰囲気中で３０分間放置した。
　放置後、引張試験機（商品名：ＴＣＭ－１ｋＮＢ、ミネベア社製）を用いて、ガラス板から測定用サンプルを引き剥がす１８０°剥離試験を行い、ガラス板に対する１８０°ピール粘着力（１８０度引き剥がし粘着力）（Ｎ／２５ｍｍ）を測定した。測定は、２３℃、５０％Ｒ．Ｈ．の雰囲気下、剥離角度１８０°、引張速度３００ｍｍ／分の条件で行った。 <Adhesive strength>
A tape piece having a length of 100 mm and a width of 25 mm was obtained using the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. Next, one release liner is peeled off from the tape piece to expose the adhesive surface, and the PET film (thickness: 25 μm) is bonded to the adhesive surface of the tape piece, and (release liner / adhesive layer / A single-sided adhesive tape with a substrate (length: 100 mm, width: 25 mm) laminated in the order of PET film) was produced. The release liner was peeled from the single-sided adhesive tape with the substrate to obtain a measurement sample.
Then 23 ° C., 50% R.D. H. In an atmosphere, a glass plate (trade name: soda lime glass # 0050, manufactured by Matsunami Glass Industry Co., Ltd.) is bonded to the exposed adhesive surface (measurement surface) of the measurement sample, and the 2 kg roller is reciprocated once. Crimped. And 23 degreeC, 50% R. H. For 30 minutes.
After leaving, using a tensile tester (trade name: TCM-1kNB, manufactured by Minebea Co., Ltd.), a 180 ° peel test is performed to peel off the measurement sample from the glass plate, and 180 ° peel adhesion (180 ° pulling) to the glass plate. The peel strength (N / 25 mm) was measured. Measurement was performed at 23 ° C. and 50% R.D. H. In the atmosphere, the peeling angle was 180 ° and the tensile speed was 300 mm / min.
　＜耐久性＞
　実施例及び比較例で得られた粘着剤層付偏光フィルムのセパレーターを剥がし、試験片をガラス板に貼り合わせ、これを８５℃の環境下に３００時間投入後の状態を目視又はルーペ（２０倍）を用いて観察した。以下の評価基準により評価した。
　◎：ルーペで確認しても、不具合（発泡、剥がれ等）の発生がなかった。
　〇：目視では不具合が確認できなかったが、ルーペで確認すると使用に問題ない程度の多少の不具合が生じていた。
　×：目視で不具合が確認できた。 <Durability>
The separator of the polarizing film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, the test piece was bonded to a glass plate, and the state after being put in an environment of 85 ° C. for 300 hours was visually or magnified (20 times) ). Evaluation was performed according to the following evaluation criteria.
A: Even when confirmed with a loupe, no defects (foaming, peeling, etc.) occurred.
◯: Although a defect could not be confirmed by visual observation, some defect occurred to the extent that there was no problem in use when confirmed with a loupe.
X: Defects could be confirmed visually.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１、２中の表記は以下の通りである。
　＜ゴム系ポリマー（Ａ１）＞
　ＳＥＰＴＯＮ　２０６３：スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、商品名：ＳＥＰＴＯＮ　２０６３、スチレン含有量：１３％、（株）クラレ製）、
　ＨＹＢＲＡＲ　７３１１：スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ、商品名：ＨＹＢＲＡＲ　７３１１、スチレン含有量１２％、(株)クラレ製）、
　＜ゴム系ポリマー（Ａ２）＞
　ＯＰＰＡＮＯＬ　Ｂ８０：ポリイソブチレン（Ｍｗ：約７５万、ＢＡＳＦ社製）、
　＜それ以外のポリマー＞
　ＯＰＰＡＮＯＬ　Ｂ５０：ポリイソブチレン（Ｍｗ：約３４万、ＢＡＳＦ社製）、
　ＯＰＰＡＮＯＬ　Ｂ３０：ポリイソブチレン（Ｍｗ：約２０万、ＢＡＳＦ社製）、
　アクリル：比較例８で得られたアクリル系粘着剤組成物
　＜天然物系粘着付与剤（Ｂ１）＞
　クリアロンＭ１２５：芳香族変性テルペン樹脂水素添加物（軟化点：１２５℃、ヤスハラケミカル（株）製）、
　クリアロンＰ１５０：テルペン系水素添加物（軟化点：１５２℃、ヤスハラケミカル（株）製）、
　ＹＳポリスターＴＨ１３０：水添テルペンフェノール（軟化点：１３０℃、水酸基価：６０、ヤスハラケミカル（株）製）、
　ＹＳポリスターＵＨ１１５：完全水添テルペンフェノール（軟化点：１１５、水酸基価：２５、ヤスハラケミカル（株）製）、
　完全水添テルペンフェノール（Ａ）：軟化点が１３５℃、水酸基価が１６０である完全水添テルペンフェノール、
　完全水添テルペンフェノール（Ｂ）：軟化点が１３５℃、水酸基価が６０である完全水添テルペンフェノール、
　完全水添テルペンフェノール（Ｃ）：軟化点が１６０℃、水酸基価が６０である完全水添テルペンフェノール、
　＜石油樹脂系粘着付与剤（Ｂ２）＞
　ピコラスチックＡ５：ビニルトルエン系粘着付与剤（軟化点：５℃、イーストマンコダック社製）、
　Ｔ－ＲＥＺ　ＨＡ１２５：水添ジシクロペンタジエン系粘着付与剤（軟化点：１２５℃、東燃ゼネラル石油(株)製）、
　ＦＭＲ－０１５０：スチレン系／芳香族系粘着付与剤（軟化点：１４５℃、三井化学(株)製）、
　アルコンＰ１１５：脂環族飽和炭化水素樹脂（軟化点：約１１５℃、荒川化学工業（株）製）、
　アルコンＰ１２５：脂環族飽和炭化水素樹脂（軟化点：約１２５℃、荒川化学工業（株）製）、
　アルコンＰ１４０：脂環族飽和炭化水素樹脂（軟化点：約１４０℃、荒川化学工業（株）製）、
　＜軟化剤（Ｃ）＞
　ＯＰＰＡＮＯＬ　Ｂ１０：ポリイソブチレン（重量平均分子量：約３万６千、ＢＡＳＦ社製）、
　ＨＶ－３００：ポリブテン（重量平均分子量：３０００、ＪＸ日鉱日石エネルギー（株）製）。 The notations in Tables 1 and 2 are as follows.
<Rubber polymer (A1)>
SEPTON 2063: Styrene-ethylene-propylene-styrene block copolymer (SEPS, trade name: SEPTON 2063, styrene content: 13%, manufactured by Kuraray Co., Ltd.)
HYBRAR 7311: Styrene-ethylene-propylene-styrene block copolymer (SEPS, trade name: HYBRAR 7311, styrene content 12%, manufactured by Kuraray Co., Ltd.)
<Rubber polymer (A2)>
OPPANOL B80: polyisobutylene (Mw: about 750,000, manufactured by BASF),
<Other polymers>
OPPANOL B50: polyisobutylene (Mw: about 340,000, manufactured by BASF),
OPPANOL B30: polyisobutylene (Mw: about 200,000, manufactured by BASF),
Acrylic: Acrylic pressure-sensitive adhesive composition obtained in Comparative Example 8 <Natural product-based tackifier (B1)>
Clearon M125: Aromatically modified terpene resin hydrogenated product (softening point: 125 ° C., manufactured by Yasuhara Chemical Co., Ltd.)
Clearon P150: Terpene-based hydrogenated product (softening point: 152 ° C., manufactured by Yasuhara Chemical Co., Ltd.)
YS polystar TH130: hydrogenated terpene phenol (softening point: 130 ° C., hydroxyl value: 60, manufactured by Yasuhara Chemical Co., Ltd.)
YS polystar UH115: fully hydrogenated terpene phenol (softening point: 115, hydroxyl value: 25, manufactured by Yasuhara Chemical Co., Ltd.)
Completely hydrogenated terpene phenol (A): fully hydrogenated terpene phenol having a softening point of 135 ° C. and a hydroxyl value of 160,
Completely hydrogenated terpene phenol (B): Completely hydrogenated terpene phenol having a softening point of 135 ° C. and a hydroxyl value of 60,
Completely hydrogenated terpene phenol (C): fully hydrogenated terpene phenol having a softening point of 160 ° C. and a hydroxyl value of 60,
<Petroleum resin-based tackifier (B2)>
Picolastic A5: Vinyltoluene-based tackifier (softening point: 5 ° C., manufactured by Eastman Kodak Company),
T-REZ HA125: hydrogenated dicyclopentadiene-based tackifier (softening point: 125 ° C., manufactured by TonenGeneral Sekiyu KK)
FMR-0150: Styrenic / aromatic tackifier (softening point: 145 ° C., manufactured by Mitsui Chemicals, Inc.)
Alcon P115: Alicyclic saturated hydrocarbon resin (softening point: about 115 ° C., manufactured by Arakawa Chemical Industries, Ltd.)
Alcon P125: Alicyclic saturated hydrocarbon resin (softening point: about 125 ° C., manufactured by Arakawa Chemical Industries, Ltd.)
Alcon P140: Alicyclic saturated hydrocarbon resin (softening point: about 140 ° C., manufactured by Arakawa Chemical Industries, Ltd.)
<Softener (C)>
OPPANOL B10: polyisobutylene (weight average molecular weight: about 36,000, manufactured by BASF),
HV-300: polybutene (weight average molecular weight: 3000, manufactured by JX Nippon Oil & Energy Corporation).
　１　粘着剤層付偏光フィルム
　２　偏光フィルム
　３　粘着剤層
　４　偏光子
　５　透明保護フィルム
　６　輝度向上フィルム
　７　プリズムシート
　１０　光学部材 DESCRIPTION OF SYMBOLS 1 Polarizing film with an adhesive layer 2 Polarizing film 3 Adhesive layer 4 Polarizer 5 Transparent protective film 6 Brightness improvement film 7 Prism sheet 10 Optical member

Claims (18)

  1. 　ゴム系ポリマー（Ａ）、及び粘着付与剤（Ｂ）を含有する粘着剤組成物であって、
    　前記ゴム系ポリマー（Ａ）が、スチレン系熱可塑性エラストマー（Ａ１）、及び重量平均分子量が５０万以上であるイソブチレン系ポリマー（Ａ２）からなる群から選択される少なくとも１種のゴム系ポリマーを含み
    　前記ゴム系ポリマー（Ａ）が前記スチレン系熱可塑性エラストマー（Ａ１）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、石油樹脂系粘着付与剤（Ｂ２）、及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含み、
    　前記ゴム系ポリマー（Ａ）が前記イソブチレン系ポリマー（Ａ２）を含む場合には、前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）、及びこれらの水素添加物からなる群から選択される少なくとも１種の粘着付与剤を含むことを特徴とする粘着剤組成物。     A pressure-sensitive adhesive composition containing a rubber-based polymer (A) and a tackifier (B),
    The rubber polymer (A) includes at least one rubber polymer selected from the group consisting of a styrene thermoplastic elastomer (A1) and an isobutylene polymer (A2) having a weight average molecular weight of 500,000 or more. When the rubber-based polymer (A) contains the styrene-based thermoplastic elastomer (A1), the tackifier (B) is a natural product-based tackifier (B1), a petroleum resin-based tackifier (B2). And) at least one tackifier selected from the group consisting of these hydrogenated products,
    When the rubber-based polymer (A) includes the isobutylene-based polymer (A2), the tackifier (B) is selected from the group consisting of a natural product-based tackifier (B1) and hydrogenated products thereof. A pressure-sensitive adhesive composition comprising at least one selected tackifier.
  2. 　前記粘着付与剤（Ｂ）が、天然物系粘着付与剤（Ｂ１）であることを特徴とする請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the tackifier (B) is a natural product-based tackifier (B1).
  3. 　前記天然物系粘着付与剤（Ｂ１）が、テルペン骨格を含む粘着付与剤、ロジン骨格を含む粘着付与剤及びこれらの水素添加物からなる群から選択される少なくとも１種であることを特徴とする請求項１又は２記載の粘着剤組成物。 The natural product-based tackifier (B1) is at least one selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof. The pressure-sensitive adhesive composition according to claim 1 or 2.
  4. 　前記粘着剤組成物から形成した厚み５０μｍの粘着剤層の、４０℃、９２％Ｒ．Ｈ．における透湿度が１００ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする請求項１～３のいずれかにに記載の粘着剤組成物。 A pressure-sensitive adhesive layer having a thickness of 50 μm formed from the pressure-sensitive adhesive composition, 40 ° C., 92% H. The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the moisture permeability is 100 g / (m 2 · day) or less.
  5. 　前記粘着付与剤（Ｂ）が、水素添加物であることを特徴とする請求項１～４のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the tackifier (B) is a hydrogenated product.
  6. 　前記粘着付与剤（Ｂ）の軟化点が、１００℃以上であることを特徴とする請求項１～５のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the tackifier (B) has a softening point of 100 ° C or higher.
  7. 　前記天然物系粘着付与剤（Ｂ１）が、シクロヘキサノール骨格を含むことを特徴とする請求項１～６いずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the natural product-based tackifier (B1) contains a cyclohexanol skeleton.
  8. 　前記粘着付与剤（Ｂ）の含有量が、前記ゴム系ポリマー（Ａ）１００重量部に対して１重量部以上であることを特徴とする請求項１～７のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the content of the tackifier (B) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A). object.
  9. 　さらに、重量平均分子量が５万以下であるポリイソブチレン系化合物（Ｃ１）、及び重量平均分子量が５万以下であるポリイソプレン系化合物（Ｃ２）からなる群から選択される少なくとも１種の軟化剤（Ｃ）を含むことを特徴とする請求項１～８のいずれかに記載の粘着剤組成物。 Furthermore, at least one softener selected from the group consisting of a polyisobutylene compound (C1) having a weight average molecular weight of 50,000 or less and a polyisoprene compound (C2) having a weight average molecular weight of 50,000 or less ( The pressure-sensitive adhesive composition according to any one of claims 1 to 8, which comprises C).
  10. 　前記軟化剤（Ｃ）の含有量が、前記ゴム系ポリマー（Ａ）１００重量部に対して１重量部以上であることを特徴とする請求項９に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 9, wherein the content of the softening agent (C) is 1 part by weight or more with respect to 100 parts by weight of the rubber-based polymer (A).
  11. 　請求項１～１０のいずれかに記載の粘着剤組成物から形成されたことを特徴とする粘着剤層。 A pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 10.
  12. 　光学フィルムと、当該光学フィルム上に設けられた請求項１１に記載の粘着剤層を有することを特徴とする粘着剤層付光学フィルム。 An optical film with an adhesive layer, comprising the optical film and the adhesive layer according to claim 11 provided on the optical film.
  13. 　前記光学フィルムが、偏光子の少なくとも片面に透明保護フィルムを有する偏光フィルムであることを特徴とする請求項１２に記載の粘着剤層付光学フィルム。 The optical film with an adhesive layer according to claim 12, wherein the optical film is a polarizing film having a transparent protective film on at least one surface of a polarizer.
  14. 　前記偏光フィルムが、偏光子の片面のみに透明保護フィルムを有する片面保護偏光フィルムであって、前記粘着剤層が、偏光子の透明保護フィルムを有さない側に積層されていることを特徴とする請求項１３に記載の粘着剤層付光学フィルム。 The polarizing film is a single-sided protective polarizing film having a transparent protective film only on one side of the polarizer, and the pressure-sensitive adhesive layer is laminated on the side of the polarizer that does not have a transparent protective film. The optical film with an adhesive layer according to claim 13.
  15. 　前記光学フィルムが、輝度向上フィルムであることを特徴とする請求項１２に記載の粘着剤層付光学フィルム。 The optical film with an adhesive layer according to claim 12, wherein the optical film is a brightness enhancement film.
  16. 　請求項１３又は１４に記載の粘着剤層付光学フィルムと、輝度向上フィルムを含むことを特徴とする光学部材。 An optical member comprising the optical film with an adhesive layer according to claim 13 or 14, and a brightness enhancement film.
  17. 　請求項１１に記載の粘着剤層と、４０℃、９２％Ｒ．Ｈ．における透湿度が１ｇ／（ｍ２・ｄａｙ）以下であるフィルムを含むことを特徴とする光学部材。 The pressure-sensitive adhesive layer according to claim 11, 40 ° C., 92% R.D. H. An optical member comprising a film having a moisture permeability of 1 g / (m 2 · day) or less.
  18. 　請求項１２～１５に記載の粘着剤層付光学フィルム、及び請求項１６～１７に記載の光学部材からなる群から選択される少なくとも１種を含むことを特徴とする画像表示装置。 An image display device comprising at least one selected from the group consisting of an optical film with an adhesive layer according to claims 12 to 15 and an optical member according to claims 16 to 17.
PCT/JP2016/077289 2015-09-16 2016-09-15 Adhesive composition, adhesive layer, optical film having attached adhesive layer, optical member, and image display device WO2017047703A1 (en)

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