WO2017110913A1 - Rubber-based adhesive composition, rubber-based adhesive layer, optical film with rubber-based adhesive layer, optical member, image display device, and method for producing rubber-based adhesive layer - Google Patents
Rubber-based adhesive composition, rubber-based adhesive layer, optical film with rubber-based adhesive layer, optical member, image display device, and method for producing rubber-based adhesive layer Download PDFInfo
- Publication number
- WO2017110913A1 WO2017110913A1 PCT/JP2016/088191 JP2016088191W WO2017110913A1 WO 2017110913 A1 WO2017110913 A1 WO 2017110913A1 JP 2016088191 W JP2016088191 W JP 2016088191W WO 2017110913 A1 WO2017110913 A1 WO 2017110913A1
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- WIPO (PCT)
- Prior art keywords
- rubber
- sensitive adhesive
- adhesive layer
- based pressure
- film
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 118
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- 239000000853 adhesive Substances 0.000 title claims abstract description 23
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- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical class [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
- 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 rubber-based pressure-sensitive adhesive composition and a rubber-based pressure-sensitive adhesive layer formed from the rubber-based pressure-sensitive adhesive composition.
- the present invention also relates to an optical film with a rubber-based adhesive layer in which the rubber-based adhesive layer is provided on an optical film, and an optical member including the optical film with a rubber-based adhesive layer.
- this invention relates to the image display apparatus containing the said optical film with an adhesive layer and / or an optical member.
- this invention relates to the manufacturing method of a rubber-type adhesive layer.
- a single-sided protective polarizing film having a 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).
- an adhesive encapsulating composition containing a hydrogenated cyclic olefin polymer and a polyisobutylene resin for example, see Patent Document 1
- an unsaturated bond Adhesive composition having a high barrier property including a conjugated diene-based uncrosslinked rubber, a crosslinked rubber composition containing a hydrogen abstraction type photopolymerization initiator (see, for example, Patent Document 2), and a butyl rubber containing a specific amount of isoprene (for example, see Patent Document 3).
- Patent Documents 1 to 3 are described as having a moisture barrier property, a gas barrier property, and the like. However, when the pressure-sensitive adhesive layer described in these documents is stored in a high temperature environment, it floats or peels off. In some cases, such a problem occurs.
- Patent Document 1 does not discuss the crosslinking of rubber-based resins, and Patent Documents 2 and 3 describe that rubber is crosslinked, but those that have unsaturated bonds are crosslinked. It is a cross-linking utilizing an unsaturated bond in rubber.
- the present invention provides a rubber-based pressure-sensitive adhesive composition that can form a rubber-based pressure-sensitive adhesive layer having low moisture permeability and having high durability capable of suppressing the occurrence of problems such as floating and peeling even in a high temperature environment.
- the purpose is to provide goods.
- the present invention also includes a rubber-based pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, an optical film with a pressure-sensitive adhesive layer provided with the rubber-based pressure-sensitive adhesive layer, and an optical including the optical film with the rubber-based pressure-sensitive adhesive layer.
- An object is to provide a member.
- Another object of the present invention is to provide an image display device including at least one selected from the group consisting of the optical film with a rubber-based pressure-sensitive adhesive layer and the optical member. It is another object of the present invention to provide a method for producing the rubber-based pressure-sensitive adhesive layer.
- the present invention relates to a rubber-based pressure-sensitive adhesive composition
- a rubber-based pressure-sensitive adhesive composition comprising polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
- the rubber-based pressure-sensitive adhesive composition of the present invention preferably contains 20 parts by weight or less of a polyfunctional radical polymerizable compound with respect to 100 parts by weight of the polyisobutylene.
- the polyfunctional radically polymerizable compound is preferably a compound having at least two (meth) acryloyl groups.
- the compound having at least two (meth) acryloyl groups is a bifunctional (meth) acrylate having two (meth) acryloyl groups and / or a trifunctional (meth) acrylate having three (meth) acryloyl groups. Is preferred.
- the hydrogen abstraction type photopolymerization initiator is preferably a benzophenone compound.
- the content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene.
- the rubber-based pressure-sensitive adhesive composition of the present invention contains at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof. It is preferable.
- the rubber-based pressure-sensitive adhesive composition of the present invention can be crosslinked by irradiation with active energy rays.
- the active energy ray is preferably ultraviolet light.
- the present invention also relates to a rubber-based pressure-sensitive adhesive layer formed from the rubber-based pressure-sensitive adhesive composition.
- the present invention also relates to an optical film and an optical film with a rubber-based pressure-sensitive adhesive layer comprising the rubber-based pressure-sensitive adhesive layer provided on the optical film.
- the optical film is preferably a polarizing film having a protective film on at least one surface of a polarizer.
- the polarizing film is a single-sided protective polarizing film having a protective film only on one side of the polarizer, and the rubber-based adhesive layer is laminated on the side not having the protective film of the polarizer.
- the optical film is preferably a brightness enhancement film.
- the present invention also relates to the rubber-based 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 also relates to an image display device comprising at least one selected from the group consisting of the optical film with a rubber adhesive layer and the optical member.
- the present invention relates to a method for producing a rubber-based pressure-sensitive adhesive layer, which is obtained by crosslinking the rubber-based pressure-sensitive adhesive composition by irradiation with active energy rays.
- the rubber-based pressure-sensitive adhesive composition of the present invention contains polyisobutylene containing no double bond in the main chain and a hydrogen abstraction type photopolymerization initiator, a crosslinked structure is introduced by irradiation with active energy rays. It is possible to provide a rubber-based pressure-sensitive adhesive layer (having high durability) that can suppress the occurrence of defects (floating, peeling, etc.) even in a high-temperature environment while maintaining low moisture permeability. Can do.
- the present invention can provide an optical film with a rubber adhesive layer, an optical member excellent in durability under a high temperature environment and excellent in low moisture permeability, and an image display device excellent in optical reliability. Furthermore, this invention can provide the manufacturing method of the rubber-type adhesive layer which has the said outstanding effect.
- Rubber-based pressure-sensitive adhesive composition comprises polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
- polyisobutylene The polyisobutylene (PIB) is a homopolymer of isobutylene, and for example, commercially available products such as OPPANOL manufactured by BASF can be used. In the present invention, since polyisobutylene containing no double bond in the main chain is used, the weather resistance is excellent.
- the weight average molecular weight (Mw) of the polyisobutylene is preferably 100,000 or more, more preferably 300,000 or more, further preferably 600,000 or more, and particularly 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.
- the content of the polyisobutylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more in the total solid content of the rubber-based pressure-sensitive adhesive composition. It is further preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 85% by weight or more, and particularly preferably 90% by weight or more.
- the upper limit of the content of polyisobutylene is not particularly limited, and is preferably 99% by weight or less, and more preferably 98% by weight or less. It is preferable that polyisobutylene is contained in the above range because it is excellent in low moisture permeability.
- the rubber-based pressure-sensitive adhesive composition of the present invention may contain a polymer, an elastomer, or the like other than the polyisobutylene.
- copolymers of isobutylene and normal butylene for example, 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), and vulcanization thereof
- 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
- SEBS styrene-ethylene-butylene-styrene block copolymer
- SIS Styrene-butadiene-styrene block copolymer
- SBS Styrene-ethylene-propylene-st
- a hydrogen abstraction type photopolymerization initiator is an active energy ray that is used to extract hydrogen from the polyisobutylene and react with polyisobutylene without cleavage of the initiator itself. It is something that can make points. By forming the reaction point, the crosslinking reaction of polyisobutylene can be started.
- the photopolymerization initiator in addition to the hydrogen abstraction type photopolymerization initiator used in the present invention, there are also cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays.
- cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays.
- the main chain of polyisobutylene is cleaved by the photopolymerization initiator in which radicals are generated, and cannot be crosslinked.
- polyisobutylene can be crosslinked as described above.
- Examples of the hydrogen abstraction type photopolymerization initiator include acetophenone, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4 '-Dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone; thioxanes such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Compounds such as 4,
- the content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene. More preferably, it is 0.01 to 10 parts by weight. It is preferable to include a hydrogen abstraction type photopolymerization initiator in the above-mentioned range since the crosslinking reaction can proceed to a target density.
- a cleavage type photopolymerization initiator may be used together with the hydrogen abstraction type photopolymerization initiator as long as the effects of the present invention are not impaired.
- the rubber-based pressure-sensitive adhesive composition of the present invention can further contain a polyfunctional radically polymerizable compound.
- the polyfunctional radically polymerizable compound functions as a crosslinking agent for polyisobutylene.
- the polyfunctional radical polymerizable compound is a compound having at least two radical polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group.
- Specific examples of the polyfunctional radical polymerizable compound include, for example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol.
- the content of the polyfunctional radically polymerizable compound is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less based on 100 parts by weight of the polyisobutylene.
- the lower limit value of the content of the polyfunctional radical polymerizable compound is not particularly limited. For example, it is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyisobutylene, More preferably, it is more than 1 part by weight, and still more preferably 1 part by weight. It is preferable from a viewpoint of durability of the obtained rubber-type adhesive layer that content of a polyfunctional radically polymerizable compound exists in the said range.
- the molecular weight of the polyfunctional radically polymerizable compound is not particularly limited, but is preferably about 1000 or less, and more preferably about 500 or less.
- the rubber-based pressure-sensitive adhesive composition of the present invention 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.
- a tackifier can be included.
- tackifier containing the terpene skeleton examples include terpene polymers such as ⁇ -pinene polymer, ⁇ -pinene polymer and dipentene polymer, and modified terpene polymers (phenol-modified, styrene-modified, aromatic). Modified terpene resin and the like).
- modified terpene resin examples 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 a hydride of a terpene polymer and other modified terpene resins and hydrogenated terpene phenol resins.
- a hydrogenated product of terpene phenol resin is preferable from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive composition and pressure-sensitive adhesive properties.
- 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.
- tackifier for example, commercially available products such as the Clearon series, Polystar series, Superester series, Pencel series, Pine Crystal series, etc. manufactured by Yashara Chemical Co., Ltd. may be used. it can.
- the hydrogenation may be a partially hydrogenated product that has been partially hydrogenated, and all the double bonds in the compound are fully hydrogenated. It may be a hydrogenated product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
- the tackifier preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is thought that the cyclohexanol skeleton is more compatible with the base polymer polyisobutylene 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 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 tackifier has a softening point of 80 ° C. or higher because the tackifier can be kept soft without being softened even at high temperatures.
- the upper limit value of the softening point of the tackifier 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.
- the temperature is preferably about 200 ° C. or less, and preferably about 180 ° C. or less.
- 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 (Mw) of the tackifier is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, and 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 is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. It is preferable that the weight average molecular weight of the tackifier is in the above range because the compatibility with polyisobutylene is good and problems such as whitening do not occur.
- the addition amount of the tackifier is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and further preferably 20 parts by weight or less with respect to 100 parts by weight of the polyisobutylene. .
- the lower limit of the addition amount of the tackifier is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably.
- a tackifier other than the tackifier containing the terpene skeleton and the tackifier containing the rosin skeleton can be added to the rubber-based pressure-sensitive adhesive composition of the present invention.
- the tackifier include petroleum resin-based tackifiers.
- the petroleum-based tackifier include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, aliphatic / aliphatic resins. Examples thereof include cyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins, and the like.
- the petroleum resin tackifier can be used within a range that does not impair the effects of the present invention.
- it can be used in an amount of about 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene.
- An organic solvent can be added as a diluent to the rubber-based pressure-sensitive adhesive composition.
- the diluent is not particularly limited, and examples thereof include toluene, xylene, n-heptane, dimethyl ether, and the like. These may be used alone or in combination of two or more. it can. Among these, toluene is preferable.
- the addition amount of the diluent is not particularly limited, but it is preferably added to the rubber-based pressure-sensitive adhesive composition at about 50 to 95% by weight, and 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.
- Additives other than those described above can be added to the rubber-based pressure-sensitive adhesive composition of the present invention as long as the effects of the present invention are not impaired.
- the additive include a softening agent, 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 rubber-based pressure-sensitive adhesive composition can be appropriately set according to the purpose.
- the content (total amount) of the additive in the rubber-based 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.
- Rubber-based pressure-sensitive adhesive layer The rubber-based pressure-sensitive adhesive layer of the present invention is formed from the rubber-based pressure-sensitive adhesive composition. The manufacturing method of the rubber-type adhesive layer of this invention is mentioned later.
- the thickness of the rubber-based pressure-sensitive adhesive layer of the present invention is not particularly limited and can be appropriately set according to the use, but is preferably 250 ⁇ m or less, more preferably 100 ⁇ m or less, More preferably, it is 50 ⁇ m or less.
- 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.
- Moisture permeability of rubber SL adhesive layer of the present invention is not particularly limited, is preferably 50g / (m 2 ⁇ day) or less, 30g / (m 2 ⁇ day ) , more preferably less 20 g / (m 2 ⁇ day) or less is more preferable, and 15 g / (m 2 ⁇ day) or less is particularly preferable.
- the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 ⁇ day)).
- the moisture permeability of the rubber-based 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, It is preferable because deterioration due to the above can be suppressed.
- the moisture permeability is 40 ° C. and 92% R.D. when the rubber 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.
- the gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably about 10 to 98%, more preferably about 25 to 98%, further preferably about 45 to 90%, and more preferably 60 to It is particularly preferably about 85%. It is preferable for the gel fraction to be in the above range since both durability and adhesive strength can be achieved.
- the measuring method of a gel fraction can be measured by the method as described in an Example.
- Method for producing rubber-based pressure-sensitive adhesive layer includes a step of crosslinking the polyisobutylene by irradiating the rubber-based pressure-sensitive adhesive composition with active energy rays.
- the irradiation with the active energy ray is usually performed by applying the rubber-based pressure-sensitive adhesive composition to various supports and irradiating the obtained coating layer.
- the active energy ray may be irradiated directly on the coating layer (without bonding other members, etc.), or after bonding various members such as an optical film such as a separator or glass to the coating layer. May be.
- active energy rays may be irradiated through the optical film or various members, and the optical film or various members are peeled off, and the peeled surface is used. You may irradiate an active energy ray.
- Various methods are used as a method for applying the rubber-based 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 coating layer of the rubber-based pressure-sensitive adhesive composition is irradiated with active energy rays, but when the rubber-based pressure-sensitive adhesive composition contains an organic solvent as a diluent, It is preferable to remove the solvent and the like by heat drying after application and before irradiation with active energy rays.
- the heating and drying temperature is not particularly limited, but is preferably about 30 ° C. to 90 ° C., more preferably about 60 ° C. to 80 ° C. from the viewpoint of reducing the residual solvent.
- 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.
- Examples of the active energy rays include visible light, ultraviolet rays, and electron beams. Among these, ultraviolet rays are preferable.
- the irradiation condition of ultraviolet rays is not particularly limited, and can be set to any appropriate condition depending on the composition of the rubber-based pressure-sensitive adhesive composition to be crosslinked.
- the integrated irradiation light amount is 100 mJ / cm 2. ⁇ 2000 mJ / cm 2 is preferred.
- 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 and moisture permeability of the rubber-based pressure-sensitive adhesive layer obtained by the production method of the present invention are as described above.
- optical film with pressure-sensitive adhesive layer The optical film with a rubber-based pressure-sensitive adhesive layer of the present invention has an optical film and the rubber-based pressure-sensitive adhesive layer provided on the optical film.
- the rubber-based pressure-sensitive adhesive layer is applied to the optical film by irradiating active energy rays. Can be formed on top.
- an optical film with a rubber-based pressure-sensitive adhesive layer can be formed by forming a rubber-based pressure-sensitive adhesive layer on a support or the like and transferring the rubber-based pressure-sensitive adhesive layer onto the optical film.
- the release-treated sheet used in the production of the optical film with a rubber-based pressure-sensitive adhesive layer can be used as it is as a separator for the optical film with a rubber-based 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 protective film on one or both sides of the polarizer is generally used.
- a single-sided protective polarizing film is preferable from the viewpoint of reducing the thickness.
- 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 and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. 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
- the material for forming the protective film provided on one or both sides of the polarizer is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like.
- 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 protective film include blends of the polymer.
- the protective film can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone, or other thermosetting or ultraviolet curable resin.
- 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 protective film include an ultraviolet curable adhesive and an electron beam curable adhesive.
- the electron beam curable polarizing film adhesive exhibits suitable adhesion to the various protective films.
- the adhesive used in the present invention can contain a metal compound filler.
- the surface of the protective film to which the polarizer is not adhered 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 has the protective film 5 of the polarizer 4. It is preferable that it is formed on the non-side (that is, the polarizer 4 side).
- 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 pressure-sensitive adhesive layer can be formed after forming an anchor layer or a transparent resin layer on the surface of the optical film or polarizer, or after performing various easy adhesion treatments such as corona treatment and plasma treatment. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
- 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.
- Production Example 1 (Production of Polarizing Film (1))
- 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.
- polarizing film thickness: 5 ⁇ m
- protection is performed.
- a film a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 ⁇ m and subjected to corona treatment
- drying was performed at 50 ° C. for 5 minutes.
- the amorphous PET base material was peeled off to produce a piece protective polarizing film (polarizing film (1)) using a thin polarizer.
- Production Example 2 (Production of Polarizing Film (2)) A 30 ⁇ m-thick polyvinyl alcohol film was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 12 ⁇ m.
- Both protective polarizing films were produced by bonding with a polyvinyl alcohol-based adhesive (adhesive layer thickness: 0.1 ⁇ m).
- the configuration of the polarizing film (2) was hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film.
- an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million.
- Mw weight average molecular weight
- An acrylic pressure-sensitive adhesive composition (A) was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
- 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. Next, the coating layer was dried at 155 ° C. for 3 minutes to form an acrylic pressure-sensitive adhesive layer (A) having a thickness of 20 ⁇ m, and a pressure-sensitive adhesive sheet composed of a polyester film / acrylic pressure-sensitive adhesive layer (A) was produced.
- a pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is applied to the protective film of the polarizing film (1) obtained in Production Example 1 (a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 ⁇ m subjected to corona treatment).
- a polarizing film (3) having a constitution of polyester film (separator) / acrylic pressure-sensitive adhesive layer (A) / protective film / adhesive layer / polarizer was obtained.
- Example 1 (Preparation of rubber composition) 100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Toluene solution containing 5 parts by weight of functional acrylate, molecular weight: 304 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.5 part of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) as a hydrogen abstraction type photopolymerization initiator (The pressure-sensitive adhesive solution was adjusted so that the solid content was 15% by weight to prepare a rubber-based pressure-sensitive adhesive composition (solution).
- polyisobutylene trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF
- NK ester A-DCP tricyclodecane dimethanol diacrylate
- the obtained rubber-based pressure-sensitive adhesive composition (solution) was applied to a release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) with one side being peel-treated with silicone. A layer was formed. Subsequently, the coating layer was dried at 80 ° C. for 3 minutes to form a rubber-based pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 ⁇ m was produced.
- a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone is used.
- the layers were bonded so that the layers were in contact.
- the polyester film coated on both surfaces of the rubber pressure-sensitive adhesive layer functions as a release liner (separator).
- One separator was peeled off, and ultraviolet rays were irradiated at room temperature from the side where the separator was peeled off to obtain a rubber-based pressure-sensitive adhesive sheet comprising a rubber-based pressure-sensitive adhesive layer / separator.
- the UV irradiation was a light amount of 1000 mJ / cm 2 .
- Examples 2 to 22, Comparative Examples 1 to 3, 5 A rubber-based pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the composition and film thickness described in Table 1 were used.
- Comparative Example 4 (Production of acrylic adhesive sheet)
- the acrylic pressure-sensitive adhesive composition (A) produced in Production Example 3 was applied to a release-treated surface of a 38 ⁇ m-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone. Thus, a coating layer was formed. Next, 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 50 ⁇ m was prepared.
- 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 and the pressure-sensitive adhesive layer are in contact with each other.
- an acrylic pressure-sensitive adhesive sheet was obtained.
- the polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
- ⁇ Durability 1 (polarizing film (1))>
- the polarizing film (1) obtained in Production Example 1 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were laminated such that the polarizer of the polarizing film (1) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet were in contact with each other.
- a polarizing film with an adhesive layer was obtained.
- 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 protective film / adhesive layer / polarizer / adhesive layer / separator.
- the separator of the obtained polarizing film with an adhesive layer is peeled off, the test piece is bonded to a glass plate, and the state after being put in an environment of 95 ° C. for 500 hours is observed visually or using a magnifying glass (20 times). did. 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.
- ⁇ Durability 2 (polarizing film (2))>
- the polarizing film (2) obtained in Production Example 2 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples are respectively in contact with the cycloolefin resin film of the polarizing film (2) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet.
- a polarizing film with a pressure-sensitive adhesive layer was obtained.
- 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 hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film / adhesive layer / separator.
- ⁇ Durability 3 (Polarizing film (3))>
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples and a 20 ⁇ m linearly polarized light separating film (trade name: D-BEF, manufactured by 3M Company) were bonded to produce a brightness enhancement film with a pressure-sensitive adhesive layer.
- the brightness-enhancing film with the pressure-sensitive adhesive layer and the polarizing film (3) obtained in Production Example 3 are the same as the pressure-sensitive adhesive layer of the brightness-enhancing film with the pressure-sensitive adhesive layer and the polarizing film (3) obtained in Production Example 3. It laminated
- the release liner of the pressure-sensitive adhesive layer was left as a separator.
- the composition of the obtained polarizing film with a pressure-sensitive adhesive layer was as follows: polyester film (separator) / acrylic pressure-sensitive adhesive layer (A) / protective film / adhesive layer / polarizer / Example, pressure-sensitive adhesive layer obtained in Comparative Example / It was a brightness enhancement film.
- the polarizing film was laminated on the adherend (glass plate) in the durability test via the pressure-sensitive adhesive layers obtained in Examples and Comparative Examples, respectively.
- the adherend (glass plate) and the polarizing film of the durability test were laminated through the acrylic pressure-sensitive adhesive layer (A) obtained in Production Example 3. .
- ⁇ Gel fraction> The total weight of the kite string and a porous membrane made of tetrafluoroethylene resin having a pore diameter of 0.2 ⁇ m (trade name: NITOFLON NTF1122, manufactured by Nitto Denko Corporation) was measured in advance (W a (mg)). About 1 g of the pressure-sensitive adhesive layer was collected from the obtained pressure-sensitive adhesive sheet, wrapped in a purse-like shape in the porous membrane, and the mouth was tied with a string, and the weight of the wrap was measured (W b (mg)). This packet was placed in a 50-mL screw bottle, and the screw bottle was filled with toluene.
- 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 sheet was bonded to a triacetyl cellulose 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 triacetyl cellulose film, thickness: 25 ⁇ m, manufactured by Konica Minolta Co., Ltd.
- A-DCP Tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.)
- DCP Tricyclodecane dimethanol dimethacrylate (trade name: NK ester DCP, bifunctional methacrylate, molecular weight: 332, manufactured by Shin-Nakamura Chemical Co., Ltd.)
- A-TMPTA trimethylolpropane triacrylate (trade name: NK ester A-TMPT, trifunctional acrylate, molecular weight: 296, manufactured by Shin-Nakamura Chemical Co., Ltd.)
- Benzophenone Hydrogen abstraction type photopolymerization initiator Irgacure 184: Cleavage type photoinitiator, 1-hydroxycyclohexyl pheny
Abstract
This rubber-based adhesive composition contains a polyisobutylene and a hydrogen abstraction type photopolymerization initiator. This rubber-based adhesive composition is able to form a highly durable rubber-based adhesive layer which is capable of suppressing the occurrence of defects such as separation and loss of adhesion in a high-temperature environment, while having low water vapor permeability.
Description
本発明は、ゴム系粘着剤組成物、当該ゴム系粘着剤組成物から形成されたゴム系粘着剤層に関する。また、本発明は、光学フィルムに前記ゴム系粘着剤層を設けたゴム系粘着剤層付光学フィルム、及び当該ゴム系粘着剤層付光学フィルムを含む光学部材に関する。また、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。さらに、本発明は、ゴム系粘着剤層の製造方法に関する。
The present invention relates to a rubber-based pressure-sensitive adhesive composition and a rubber-based pressure-sensitive adhesive layer formed from the rubber-based pressure-sensitive adhesive composition. The present invention also relates to an optical film with a rubber-based adhesive layer in which the rubber-based adhesive layer is provided on an optical film, and an optical member including the optical film with a rubber-based adhesive layer. Moreover, this invention relates to the image display apparatus containing the said optical film with an adhesive layer and / or an optical member. Furthermore, this invention relates to the manufacturing method of a rubber-type adhesive layer.
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、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 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 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を形成する材料としては、例えば、水素添加環状オレフィン系ポリマー及びポリイソブチレン樹脂を含む接着性封入用組成物（例えば、特許文献１参照）、不飽和結合を有する共役ジエン系未架橋ゴム、水素引抜型光重合開始剤を含む架橋ゴム組成物（例えば、特許文献２参照）、イソプレンを特定量含むブチル系ゴムを含む、バリア性の高い粘着剤組成物（例えば、特許文献３参照）等が知られている。
As a material for forming such a low moisture-permeable pressure-sensitive adhesive layer, for example, an adhesive encapsulating composition containing a hydrogenated cyclic olefin polymer and a polyisobutylene resin (for example, see Patent Document 1), an unsaturated bond Adhesive composition having a high barrier property, including a conjugated diene-based uncrosslinked rubber, a crosslinked rubber composition containing a hydrogen abstraction type photopolymerization initiator (see, for example, Patent Document 2), and a butyl rubber containing a specific amount of isoprene ( For example, see Patent Document 3).
特許文献１～３の粘着剤等は、水分バリア特性やガスバリア特性等を有することが記載されているが、これらの文献に記載されている粘着剤層を高温環境下で保管すると、浮きや剥がれといった不具合が生じる場合があった。これは、特許文献１ではゴム系樹脂の架橋について検討されておらず、また、特許文献２、３では、ゴムを架橋することが記載されているものの、不飽和結合を有するゴムを架橋するものであって、ゴム中の不飽和結合を利用した架橋である。このような架橋では、不飽和結合が少ないと架橋密度が低く耐久性が向上せず、また不飽和結合が多いと残存した不飽和結合が太陽光等により劣化し、黄変や主鎖切断が生じ、実用上問題になる場合があった。
The pressure-sensitive adhesives of Patent Documents 1 to 3 are described as having a moisture barrier property, a gas barrier property, and the like. However, when the pressure-sensitive adhesive layer described in these documents is stored in a high temperature environment, it floats or peels off. In some cases, such a problem occurs. Patent Document 1 does not discuss the crosslinking of rubber-based resins, and Patent Documents 2 and 3 describe that rubber is crosslinked, but those that have unsaturated bonds are crosslinked. It is a cross-linking utilizing an unsaturated bond in rubber. In such crosslinking, if there are few unsaturated bonds, the crosslinking density is low and the durability is not improved, and if there are many unsaturated bonds, the remaining unsaturated bonds deteriorate due to sunlight, etc., and yellowing and main chain breakage occur. This may cause a problem in practical use.
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ゴム系粘着剤層を形成することができるゴム系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ゴム系粘着剤層、当該ゴム系粘着剤層が設けられた粘着剤層付光学フィルム、当該ゴム系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。また、前記ゴム系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。さらに、前記ゴム系粘着剤層の製造方法を提供することも目的とする。
Therefore, the present invention provides a rubber-based pressure-sensitive adhesive composition that can form a rubber-based pressure-sensitive adhesive layer having low moisture permeability and having high durability capable of suppressing the occurrence of problems such as floating and peeling even in a high temperature environment. The purpose is to provide goods. The present invention also includes a rubber-based pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, an optical film with a pressure-sensitive adhesive layer provided with the rubber-based pressure-sensitive adhesive layer, and an optical including the optical film with the rubber-based pressure-sensitive adhesive layer. An object is to provide a member. Another object of the present invention is to provide an image display device including at least one selected from the group consisting of the optical film with a rubber-based pressure-sensitive adhesive layer and the optical member. It is another object of the present invention to provide a method for producing the rubber-based pressure-sensitive adhesive layer.
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、下記ゴム系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-mentioned problems, the present inventors have found the following rubber-based pressure-sensitive adhesive composition and have completed the present invention.
すなわち、本発明は、ポリイソブチレン、及び水素引抜型光重合開始剤を含むことを特徴とするゴム系粘着剤組成物に関する。
That is, the present invention relates to a rubber-based pressure-sensitive adhesive composition comprising polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
本発明のゴム系粘着剤組成物には、多官能ラジカル重合性化合物を、前記ポリイソブチレン１００重量部に対して２０重量部以下含むことが好ましい。
The rubber-based pressure-sensitive adhesive composition of the present invention preferably contains 20 parts by weight or less of a polyfunctional radical polymerizable compound with respect to 100 parts by weight of the polyisobutylene.
前記多官能ラジカル重合性化合物が、（メタ）アクリロイル基を少なくとも２つ有する化合物であることが好ましい。
The polyfunctional radically polymerizable compound is preferably a compound having at least two (meth) acryloyl groups.
前記（メタ）アクリロイル基を少なくとも２つ有する化合物が、（メタ）アクリロイル基を２つ有する２官能（メタ）アクリレート及び／又は（メタ）アクリロイル基を３つ有する３官能（メタ）アクリレートであることが好ましい。
The compound having at least two (meth) acryloyl groups is a bifunctional (meth) acrylate having two (meth) acryloyl groups and / or a trifunctional (meth) acrylate having three (meth) acryloyl groups. Is preferred.
前記水素引抜型光重合開始剤が、ベンゾフェノン系化合物であることが好ましい。
The hydrogen abstraction type photopolymerization initiator is preferably a benzophenone compound.
前記水素引抜型光重合開始剤の含有量が、前記ポリイソブチレン１００重量部に対して、０．００１～１０重量部であることが好ましい。
The content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene.
本発明のゴム系粘着剤組成物には、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、及びこれらの水添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が好ましい。
The rubber-based pressure-sensitive adhesive composition of the present invention contains at least one tackifier selected from the group consisting of a tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and a hydrogenated product thereof. It is preferable.
本発明のゴム系粘着剤組成物は、活性エネルギー線の照射により架橋することができる。
The rubber-based pressure-sensitive adhesive composition of the present invention can be crosslinked by irradiation with active energy rays.
前記活性エネルギー線が、紫外線であることが好ましい。
The active energy ray is preferably ultraviolet light.
前記ゴム系粘着剤組成物から形成した厚み５０μｍのゴム系粘着剤層の、４０℃、９２％Ｒ．Ｈ．における透湿度が、５０ｇ／（ｍ２・ｄａｙ）以下であることが好ましい。
A rubber-based pressure-sensitive adhesive layer having a thickness of 50 μm formed from the rubber-based pressure-sensitive adhesive composition, at 40 ° C. and 92% R.D. H. It is preferable that the moisture permeability in is 50 g / (m 2 · day) or less.
また、本発明は、前記ゴム系粘着剤組成物から形成されたことを特徴とするゴム系粘着剤層に関する。
The present invention also relates to a rubber-based pressure-sensitive adhesive layer formed from the rubber-based pressure-sensitive adhesive composition.
また、本発明は、光学フィルム、及び当該光学フィルム上に設けられた前記ゴム系粘着剤層を有することを特徴とするゴム系粘着剤層付光学フィルムに関する。
The present invention also relates to an optical film and an optical film with a rubber-based pressure-sensitive adhesive layer comprising the rubber-based pressure-sensitive 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 protective film on at least one surface of a polarizer.
前記偏光フィルムが、偏光子の片面のみに保護フィルムを有する片面保護偏光フィルムであって、前記ゴム系粘着剤層が、偏光子の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。
It is preferable that the polarizing film is a single-sided protective polarizing film having a protective film only on one side of the polarizer, and the rubber-based adhesive layer is laminated on the side not having the protective film of the polarizer.
前記光学フィルムが、輝度向上フィルムであることが好ましい。
The optical film is preferably a brightness enhancement film.
また、本発明は、前記ゴム系粘着剤層と、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 relates to the rubber-based 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.
また、本発明は、前記ゴム系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。
The present invention also relates to an image display device comprising at least one selected from the group consisting of the optical film with a rubber adhesive layer and the optical member.
さらに、本発明は、前記ゴム系粘着剤組成物に、活性エネルギー線を照射して架橋させることで得られることを特徴とするゴム系粘着剤層の製造方法に関する。
Furthermore, the present invention relates to a method for producing a rubber-based pressure-sensitive adhesive layer, which is obtained by crosslinking the rubber-based pressure-sensitive adhesive composition by irradiation with active energy rays.
本発明のゴム系粘着剤組成物は、主鎖の中に二重結合を含まないポリイソブチレン、及び水素引抜型光重合開始剤を含むため、活性エネルギー線を照射することで架橋構造を導入することができるものであり、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（高い耐久性を有する）ゴム系粘着剤層を提供することができる。
Since the rubber-based pressure-sensitive adhesive composition of the present invention contains polyisobutylene containing no double bond in the main chain and a hydrogen abstraction type photopolymerization initiator, a crosslinked structure is introduced by irradiation with active energy rays. It is possible to provide a rubber-based pressure-sensitive adhesive layer (having high durability) that can suppress the occurrence of defects (floating, peeling, etc.) even in a high-temperature environment while maintaining low moisture permeability. Can do.
また、本発明は、高温環境下の耐久性に優れ、低透湿性に優れたゴム系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。さらに、本発明は、前記優れた効果を奏するゴム系粘着剤層の製造方法を提供することができる。
In addition, the present invention can provide an optical film with a rubber adhesive layer, an optical member excellent in durability under a high temperature environment and excellent in low moisture permeability, and an image display device excellent in optical reliability. Furthermore, this invention can provide the manufacturing method of the rubber-type adhesive layer which has the said outstanding effect.
１．ゴム系粘着剤組成物
本発明のゴム系粘着剤組成物は、ポリイソブチレン、及び水素引抜型光重合開始剤を含むことを特徴とする。 1. Rubber-based pressure-sensitive adhesive composition The rubber-based pressure-sensitive adhesive composition of the present invention comprises polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
本発明のゴム系粘着剤組成物は、ポリイソブチレン、及び水素引抜型光重合開始剤を含むことを特徴とする。 1. Rubber-based pressure-sensitive adhesive composition The rubber-based pressure-sensitive adhesive composition of the present invention comprises polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
（１）ポリイソブチレン
前記ポリイソブチレン（ＰＩＢ）は、イソブチレンの単独重合体であり、例えば、ＢＡＳＦ社製のＯＰＰＡＮＯＬ等の市販品を用いることができる。本発明においては、主鎖の中に二重結合を含まないポリイソブチレンを用いるため、耐候性に優れるものである。 (1) Polyisobutylene The polyisobutylene (PIB) is a homopolymer of isobutylene, and for example, commercially available products such as OPPANOL manufactured by BASF can be used. In the present invention, since polyisobutylene containing no double bond in the main chain is used, the weather resistance is excellent.
前記ポリイソブチレン（ＰＩＢ）は、イソブチレンの単独重合体であり、例えば、ＢＡＳＦ社製のＯＰＰＡＮＯＬ等の市販品を用いることができる。本発明においては、主鎖の中に二重結合を含まないポリイソブチレンを用いるため、耐候性に優れるものである。 (1) Polyisobutylene The polyisobutylene (PIB) is a homopolymer of isobutylene, and for example, commercially available products such as OPPANOL manufactured by BASF can be used. In the present invention, since polyisobutylene containing no double bond in the main chain is used, the weather resistance is excellent.
前記ポリイソブチレンの重量平均分子量（Ｍｗ）は、１０万以上であることが好ましく、３０万以上であることがより好ましく、６０万以上であることがさらに好ましく、７０万以上であることが特に好ましい。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。前記ポリイソブチレンの重量平均分子量を１０万以上とすることで高温保管時の耐久性がより優れるゴム系粘着剤組成物とすることができる。
The weight average molecular weight (Mw) of the polyisobutylene is preferably 100,000 or more, more preferably 300,000 or more, further preferably 600,000 or more, and particularly 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 polyisobutylene to 100,000 or more, it is possible to obtain a rubber-based pressure-sensitive adhesive composition that is more excellent in durability during high-temperature storage.
前記ポリイソブチレンの含有量は、特に限定されるものではないが、ゴム系粘着剤組成物の全固形分中、５０重量％以上であることが好ましく、６０重量％以上であることがより好ましく、７０重量％以上であることがさらに好ましく、８０重量％以上であることがさらに好ましく、８５重量％以上であることがさらに好ましく、９０重量％以上であることが特に好ましい。ポリイソブチレンの含有量の上限は特に限定されるものではなく、９９重量％以下であることが好ましく、９８重量％以下であることがより好ましい。ポリイソブチレンを前記範囲で含むことで、低透湿性に優れるため好ましい。
The content of the polyisobutylene is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more in the total solid content of the rubber-based pressure-sensitive adhesive composition. It is further preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 85% by weight or more, and particularly preferably 90% by weight or more. The upper limit of the content of polyisobutylene is not particularly limited, and is preferably 99% by weight or less, and more preferably 98% by weight or less. It is preferable that polyisobutylene is contained in the above range because it is excellent in low moisture permeability.
また、本発明のゴム系粘着剤組成物においては、前記ポリイソブチレン以外のポリマーやエラストマー等を含むこともできる。具体的には、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）等のイソブチレン系ポリマー；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の水添物）、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添物）、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等のスチレン系熱可塑性エラストマー；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、前記ポリイソブチレン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く、耐久性の観点からは、含まないことが好ましい。
Further, the rubber-based pressure-sensitive adhesive composition of the present invention may contain a polymer, an elastomer, or the like other than the polyisobutylene. Specifically, 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), and vulcanization thereof 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); styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Styrene block copolymer (SIS), Styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-propylene-styrene block copolymer (SEPS, SIS hydrogenated product), Styrene-ethylene-propylene block Copolymer (SEP, styrene-a Styrene-based thermoplastic elastomers such as styrene-based block copolymers such as styrene-isobutylene-styrene block copolymer (SIBS) and styrene-butadiene rubber (SBR); butyl rubber (IIR), Butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (ternary ethylene-propylene rubber), acrylic rubber, urethane rubber, polyurethane thermoplastic elastomer; polyester Thermoplastic elastomers; blend thermoplastic elastomers such as polymer blends of polypropylene and EPT (ternary ethylene-propylene rubber). These can be added within a range that does not impair the effects of the present invention, but is preferably about 10 parts by weight or less with respect to 100 parts by weight of the polyisobutylene, and may not be included from the viewpoint of durability. preferable.
（２）水素引抜型光重合開始剤
水素引抜型光重合開始剤とは、活性エネルギー線を照射することで、開始剤自身は開裂することなく、前記ポリイソブチレンより水素を引き抜き、ポリイソブチレンに反応点を作ることができるものである。当該反応点形成により、ポリイソブチレンの架橋反応を開始することができるものである。 (2) Hydrogen abstraction type photopolymerization initiator A hydrogen abstraction type photopolymerization initiator is an active energy ray that is used to extract hydrogen from the polyisobutylene and react with polyisobutylene without cleavage of the initiator itself. It is something that can make points. By forming the reaction point, the crosslinking reaction of polyisobutylene can be started.
水素引抜型光重合開始剤とは、活性エネルギー線を照射することで、開始剤自身は開裂することなく、前記ポリイソブチレンより水素を引き抜き、ポリイソブチレンに反応点を作ることができるものである。当該反応点形成により、ポリイソブチレンの架橋反応を開始することができるものである。 (2) Hydrogen abstraction type photopolymerization initiator A hydrogen abstraction type photopolymerization initiator is an active energy ray that is used to extract hydrogen from the polyisobutylene and react with polyisobutylene without cleavage of the initiator itself. It is something that can make points. By forming the reaction point, the crosslinking reaction of polyisobutylene can be started.
光重合開始剤としては、本発明で用いる水素引抜型光重合開始剤の他に、活性エネルギー線の照射により、光重合開始剤自身が開裂分解してラジカルを発生させる開裂型光重合開始剤も知られている。しかしながら、本発明で用いるポリイソブチレンに、開裂型光重合開始剤を用いると、ラジカルが発生した光重合開始剤によりポリイソブチレンの主鎖が切断されてしまい、架橋することができないものである。本発明においては、水素引抜型光重合開始剤を用いることで、前述の通りポリイソブチレンの架橋をすることができるものである。
As the photopolymerization initiator, in addition to the hydrogen abstraction type photopolymerization initiator used in the present invention, there are also cleavage type photopolymerization initiators that generate radicals by cleavage of the photopolymerization initiator itself upon irradiation with active energy rays. Are known. However, when a cleavage type photopolymerization initiator is used for the polyisobutylene used in the present invention, the main chain of polyisobutylene is cleaved by the photopolymerization initiator in which radicals are generated, and cannot be crosslinked. In the present invention, by using a hydrogen abstraction type photopolymerization initiator, polyisobutylene can be crosslinked as described above.
水素引抜型光重合開始剤としては、例えば、アセトフェノン、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル－４－フェニルベンゾフェノン、４，４’－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジクロルベンゾフェノン、４，４’－ジメチルベンゾフェノン、４－ベンゾイル－４’－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，３’－ジメチル－４－メトキシベンゾフェノン等のベンゾフェノン系化合物；２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等のチオキサントン系化合物；４，４’－ビス(ジメチルアミノ)1481850634851_0、４，４’－ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、カンファーキノン等；アセトナフトン、１－ヒドロキシシクロヘキシルフェニルケトン等の芳香族ケトン化合物；テレフタルアルデヒド等の芳香族アルデヒド、メチルアントラキノン等のキノン系芳香族化合物が挙げられる。これらは１種単独で、又は、２種以上を混合して用いることができる。これらの中でも、反応性の点から、ベンゾフェノン系化合物が好ましく、ベンゾフェノンがより好ましい。
Examples of the hydrogen abstraction type photopolymerization initiator include acetophenone, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4,4′-dimethoxybenzophenone, 4,4 '-Dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone; thioxanes such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Compounds such as 4,4′-bis (dimethylamino) 1481850634851_0, 4,4′-diethylaminobenzophenone, etc .; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10- Examples thereof include phenanthrenequinone and camphorquinone; aromatic ketone compounds such as acetonaphthone and 1-hydroxycyclohexyl phenyl ketone; aromatic aldehydes such as terephthalaldehyde; and quinone aromatic compounds such as methylanthraquinone. These can be used individually by 1 type or in mixture of 2 or more types. Among these, from the viewpoint of reactivity, a benzophenone-based compound is preferable, and benzophenone is more preferable.
前記水素引抜型光重合開始剤の含有量は、前記ポリイソブチレン１００重量部に対して、０．００１～１０重量部であることが好ましく、０．００５～１０重量部であることがより好ましく、０．０１～１０重量部であることがさらに好ましい。水素引抜型光重合開始剤を前記範囲で含むことで、架橋反応を目的の密度まで進行させることができるため好ましい。
The content of the hydrogen abstraction type photopolymerization initiator is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene. More preferably, it is 0.01 to 10 parts by weight. It is preferable to include a hydrogen abstraction type photopolymerization initiator in the above-mentioned range since the crosslinking reaction can proceed to a target density.
また、本発明においては、本発明の効果を損なわない範囲で、開裂型光重合開始剤を前記水素引抜型光重合開始剤と伴に用いてもよいが、前述の理由により用いないことが好ましい。
In the present invention, a cleavage type photopolymerization initiator may be used together with the hydrogen abstraction type photopolymerization initiator as long as the effects of the present invention are not impaired. .
（３）多官能ラジカル重合性化合物
本発明のゴム系粘着剤組成物は、さらに多官能ラジカル重合性化合物を含むことができる。本発明において、多官能ラジカル重合性化合物はポリイソブチレンの架橋剤として機能するものである。 (3) Polyfunctional radically polymerizable compound The rubber-based pressure-sensitive adhesive composition of the present invention can further contain a polyfunctional radically polymerizable compound. In the present invention, the polyfunctional radically polymerizable compound functions as a crosslinking agent for polyisobutylene.
本発明のゴム系粘着剤組成物は、さらに多官能ラジカル重合性化合物を含むことができる。本発明において、多官能ラジカル重合性化合物はポリイソブチレンの架橋剤として機能するものである。 (3) Polyfunctional radically polymerizable compound The rubber-based pressure-sensitive adhesive composition of the present invention can further contain a polyfunctional radically polymerizable compound. In the present invention, the polyfunctional radically polymerizable compound functions as a crosslinking agent for polyisobutylene.
前記多官能ラジカル重合性化合物は、（メタ）アクリロイル基又はビニル基等の不飽和二重結合を有するラジカル重合性の官能基を少なくも２つ有する化合物である。多官能ラジカル重合性化合物の具体的としては、例えば、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－エチル－２－ブチルプロパンジオールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド付加物ジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルジ（メタ）アクリレート、ネオぺンチルグリコールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリート、ジオキサングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ＥＯ変性ジグリセリンテトラ（メタ）アクリレート等の（メタ）アクリル酸と多価アルコールとのエステル化物、９，９－ビス［４－（２－（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン等を挙げることができる。これらを１種単独で、又は２種以上の混合物として用いることができる。これらの中でも、ポリイソブチレンに対する相溶性の観点から、（メタ）アクリル酸と多価アルコールとのエステル化物が好ましく、（メタ）アクリロイル基を２つ有する２官能（メタ）アクリレート、（メタ）アクリロイル基を３つ以上有する３官能（メタ）アクリレートがより好ましく、トリシクロデカンジメタノールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレートが特に好ましい。
The polyfunctional radical polymerizable compound is a compound having at least two radical polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the polyfunctional radical polymerizable compound include, for example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) ) Acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) Cleats, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, EO-modified diglycerin tetra (meth) acrylate, etc., esterified products of (meth) acrylic acid and polyhydric alcohol, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, etc. Can be mentioned. These can be used singly or as a mixture of two or more. Among these, from the viewpoint of compatibility with polyisobutylene, an esterified product of (meth) acrylic acid and a polyhydric alcohol is preferable, and a bifunctional (meth) acrylate having two (meth) acryloyl groups, a (meth) acryloyl group. Are more preferable, and tricyclodecane dimethanol di (meth) acrylate and trimethylolpropane tri (meth) acrylate are particularly preferable.
前記多官能ラジカル重合性化合物の含有量は、前記ポリイソブチレン１００重量部に対して２０重量部以下であることが好ましく、１５重量以下であることがより好ましく、１０重量部以下であることがさらに好ましい。また、多官能ラジカル重合性化合物の含有量の下限値は特に限定されるものではないが、例えば、前記ポリイソブチレン１００重量部に対して０．１重量部以上であることが好ましく、０．５重量部以上であることがより好ましく、１重量部以上であることがさらに好ましい。多官能ラジカル重合性化合物の含有量が前記範囲にあることで、得られたゴム系粘着剤層の耐久性の観点から好ましい。
The content of the polyfunctional radically polymerizable compound is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less based on 100 parts by weight of the polyisobutylene. preferable. Further, the lower limit value of the content of the polyfunctional radical polymerizable compound is not particularly limited. For example, it is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polyisobutylene, More preferably, it is more than 1 part by weight, and still more preferably 1 part by weight. It is preferable from a viewpoint of durability of the obtained rubber-type adhesive layer that content of a polyfunctional radically polymerizable compound exists in the said range.
多官能ラジカル重合性化合物の分子量は、特に限定されないが、例えば、１０００以下程度であることが好ましく、５００以下程度であることがより好ましい。
The molecular weight of the polyfunctional radically polymerizable compound is not particularly limited, but is preferably about 1000 or less, and more preferably about 500 or less.
（４）粘着付与剤
本発明のゴム系粘着剤組成物は、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、及びこれらの水添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ができる。ゴム系粘着剤組成物に粘着付与剤を含むことで、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ゴム系粘着剤層を形成することができるため、好ましい。 (4) Tackifier The rubber-based pressure-sensitive adhesive composition of the present invention 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. A tackifier can be included. By including a tackifier in the rubber-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high temperature environment is formed. Is preferable.
本発明のゴム系粘着剤組成物は、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、及びこれらの水添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ができる。ゴム系粘着剤組成物に粘着付与剤を含むことで、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ゴム系粘着剤層を形成することができるため、好ましい。 (4) Tackifier The rubber-based pressure-sensitive adhesive composition of the present invention 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. A tackifier can be included. By including a tackifier in the rubber-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive layer having high adhesion to various adherends and having high durability even in a high temperature environment is formed. Is preferable.
前記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化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、ゴム系粘着剤組成物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 the tackifier containing the terpene skeleton include terpene polymers such as α-pinene polymer, β-pinene polymer and dipentene polymer, and modified terpene polymers (phenol-modified, styrene-modified, aromatic). Modified terpene resin and the like). 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 a hydride of a terpene polymer and other modified terpene resins and hydrogenated terpene phenol resins. Among these, a hydrogenated product of terpene phenol resin is preferable from the viewpoint of compatibility with the rubber-based pressure-sensitive adhesive composition and pressure-sensitive adhesive properties.
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.
前記粘着付与剤としては、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の市販品を使用することができる。
As the tackifier, for example, commercially available products such as the Clearon series, Polystar series, Superester series, Pencel series, Pine Crystal series, etc. manufactured by Yashara Chemical Co., Ltd. may be used. it can.
前記粘着付与剤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 is a hydrogenated product, the hydrogenation may be a partially hydrogenated product that has been partially hydrogenated, and all the double bonds in the compound are fully hydrogenated. It may be a hydrogenated product. In the present invention, a completely hydrogenated product is preferred from the viewpoints of adhesive properties, weather resistance and hue.
前記粘着付与剤が、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ポリイソブチレン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添物が好ましく、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。
The tackifier preferably contains a cyclohexanol skeleton from the viewpoint of adhesive properties. Although the detailed principle is unknown, it is thought that the cyclohexanol skeleton is more compatible with the base polymer polyisobutylene 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 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 tackifier has a softening point of 80 ° C. or higher because the tackifier can be kept soft without being softened even at high temperatures. The upper limit value of the softening point of the tackifier 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. The temperature is preferably about 200 ° C. or less, and preferably about 180 ° C. or less. 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.
前記粘着付与剤の重量平均分子量（Ｍｗ）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。前記粘着付与剤の重量平均分子量が前記範囲にあることで、ポリイソブチレンとの相溶性が良く、白化等の不具合を生じないため好ましい。
The weight average molecular weight (Mw) of the tackifier is not particularly limited, but is preferably 50,000 or less, preferably 30,000 or less, and more preferably 10,000 or less, It is more preferably 8000 or less, and particularly preferably 5000 or less. Moreover, the lower limit of the weight average molecular weight of the tackifier is not particularly limited, but is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more. It is preferable that the weight average molecular weight of the tackifier is in the above range because the compatibility with polyisobutylene is good and problems such as whitening do not occur.
前記粘着付与剤の添加量は、前記ポリイソブチレン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、粘着付与剤の添加量の下限値は特に限定されるものではないが、０．１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。粘着付与剤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、粘着付与剤の使用量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 addition amount of the tackifier is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and further preferably 20 parts by weight or less with respect to 100 parts by weight of the polyisobutylene. . Moreover, the lower limit of the addition amount of the tackifier is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and 5 parts by weight or more. More preferably. By making the usage-amount of a tackifier into the said range, since an adhesive characteristic can be improved, it is preferable. Moreover, when the usage-amount of a tackifier exceeds the said range and adds in large quantities, there exists a tendency for the cohesive force of an adhesive to fall, and it is unpreferable.
また、本発明のゴム系粘着剤組成物には、前記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以外の粘着付与剤を添加することもできる。当該粘着付与剤としては、石油樹脂系粘着付与剤を挙げることできる。前記石油系粘着付与剤としては、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。
Further, a tackifier other than the tackifier containing the terpene skeleton and the tackifier containing the rosin skeleton can be added to the rubber-based pressure-sensitive adhesive composition of the present invention. Examples of the tackifier include petroleum resin-based tackifiers. Examples of the petroleum-based tackifier include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic / aromatic petroleum resins, aliphatic / aliphatic resins. Examples thereof include cyclic petroleum resins, hydrogenated petroleum resins, coumarone resins, coumarone indene resins, and the like.
前記石油樹脂系粘着付与剤は、本発明の効果を損なわない範囲で用いることができるが、例えば、前記ポリイソブチレン１００重量部に対して、３０重量部以下程度で用いることができる。
The petroleum resin tackifier can be used within a range that does not impair the effects of the present invention. For example, it can be used in an amount of about 30 parts by weight or less with respect to 100 parts by weight of the polyisobutylene.
（５）その他の添加剤
前記ゴム系粘着剤組成物には、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、ｎ－ヘプタン、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。 (5) Other additives An organic solvent can be added as a diluent to the rubber-based pressure-sensitive adhesive composition. The diluent is not particularly limited, and examples thereof include toluene, xylene, n-heptane, dimethyl ether, and the like. These may be used alone or in combination of two or more. it can. Among these, toluene is preferable.
前記ゴム系粘着剤組成物には、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、ｎ－ヘプタン、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。 (5) Other additives An organic solvent can be added as a diluent to the rubber-based pressure-sensitive adhesive composition. The diluent is not particularly limited, and examples thereof include toluene, xylene, n-heptane, dimethyl ether, and the like. These may be used alone or in combination of two or more. it can. 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、ゴム系粘着剤組成物中に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 it is preferably added to the rubber-based pressure-sensitive adhesive composition at about 50 to 95% by weight, and 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.
本発明のゴム系粘着剤組成物には、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。添加剤の具体例としては、軟化剤、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。ゴム系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。ゴム系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。
Additives other than those described above can be added to the rubber-based pressure-sensitive adhesive composition of the present invention as long as the effects of the present invention are not impaired. Specific examples of the additive include a softening agent, 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 rubber-based pressure-sensitive adhesive composition can be appropriately set according to the purpose. The content (total amount) of the additive in the rubber-based 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．ゴム系粘着剤層
本発明のゴム系粘着剤層は、前記ゴム系粘着剤組成物から形成されたことを特徴とする。本発明のゴム系粘着剤層の製造方法は後述する。 2. Rubber-based pressure-sensitive adhesive layer The rubber-based pressure-sensitive adhesive layer of the present invention is formed from the rubber-based pressure-sensitive adhesive composition. The manufacturing method of the rubber-type adhesive layer of this invention is mentioned later.
本発明のゴム系粘着剤層は、前記ゴム系粘着剤組成物から形成されたことを特徴とする。本発明のゴム系粘着剤層の製造方法は後述する。 2. Rubber-based pressure-sensitive adhesive layer The rubber-based pressure-sensitive adhesive layer of the present invention is formed from the rubber-based pressure-sensitive adhesive composition. The manufacturing method of the rubber-type adhesive layer of this invention is mentioned later.
本発明のゴム系粘着剤層の厚みは、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、２５０μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、５０μｍ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 rubber-based pressure-sensitive adhesive layer of the present invention is not particularly limited and can be appropriately set according to the use, but is preferably 250 μm or less, more preferably 100 μm or less, More preferably, it is 50 μm or less. 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.
本発明のゴム系記粘着剤層の透湿度は、特に限定されるものではないが、５０ｇ／（ｍ２・ｄａｙ）以下であることが好ましく、３０ｇ／（ｍ２・ｄａｙ）以下がより好ましく、２０ｇ／（ｍ２・ｄａｙ）以下がさらに好ましく、１５ｇ／（ｍ２・ｄａｙ）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・ｄａｙ））が好ましい。ゴム系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、ゴム系粘着剤層の厚み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。
Moisture permeability of rubber SL adhesive layer of the present invention is not particularly limited, is preferably 50g / (m 2 · day) or less, 30g / (m 2 · day ) , more preferably less 20 g / (m 2 · day) or less is more preferable, and 15 g / (m 2 · day) or less is particularly preferable. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 · day)). When the moisture permeability of the rubber-based 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, It is preferable because deterioration due to the above can be suppressed. The moisture permeability is 40 ° C. and 92% R.D. when the rubber 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.
また、本発明の粘着剤層のゲル分率は、特に限定されないが、１０～９８％程度が好ましく、２５～９８％程度がより好ましく、４５～９０％程度であることがさらに好ましく、６０～８５％程度であることが特に好ましい。ゲル分率が前記範囲にあることで、耐久性と粘着力を両立できるため好ましい。なお、ゲル分率の測定方法は、実施例に記載の方法により測定することができる。
The gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably about 10 to 98%, more preferably about 25 to 98%, further preferably about 45 to 90%, and more preferably 60 to It is particularly preferably about 85%. It is preferable for the gel fraction to be in the above range since both durability and adhesive strength can be achieved. In addition, the measuring method of a gel fraction can be measured by the method as described in an Example.
３．ゴム系粘着剤層の製造方法
本発明のゴム系粘着剤層の製造方法は、前記ゴム系粘着剤組成物に、活性エネルギー線を照射して、前記ポリイソブチレンを架橋する工程を含むことを特徴とする。 3. Method for producing rubber-based pressure-sensitive adhesive layer The method for producing a rubber-based pressure-sensitive adhesive layer of the present invention includes a step of crosslinking the polyisobutylene by irradiating the rubber-based pressure-sensitive adhesive composition with active energy rays. And
本発明のゴム系粘着剤層の製造方法は、前記ゴム系粘着剤組成物に、活性エネルギー線を照射して、前記ポリイソブチレンを架橋する工程を含むことを特徴とする。 3. Method for producing rubber-based pressure-sensitive adhesive layer The method for producing a rubber-based pressure-sensitive adhesive layer of the present invention includes a step of crosslinking the polyisobutylene by irradiating the rubber-based pressure-sensitive adhesive composition with active energy rays. And
前記活性エネルギー線の照射は、通常、前記ゴム系粘着剤組成物を各種支持体等に塗布し、得られた塗布層に照射される。また、前記活性エネルギー線の照射は、塗布層に（他部材等を貼り合せることなく）直接照射してもよく、塗布層にセパレーター等の光学フィルムやガラス等の各種部材を貼り合せた後に照射してもよい。前記光学フィルムや各種部材に貼り合せた後に照射する場合は、当該光学フィルムや各種部材越しに活性エネルギー線を照射してもよく、当該光学フィルムや各種部材を剥離して、当該剥離した面から活性エネルギー線を照射してもよい。
The irradiation with the active energy ray is usually performed by applying the rubber-based pressure-sensitive adhesive composition to various supports and irradiating the obtained coating layer. In addition, the active energy ray may be irradiated directly on the coating layer (without bonding other members, etc.), or after bonding various members such as an optical film such as a separator or glass to the coating layer. May be. In the case of irradiation after bonding to the optical film or various members, active energy rays may be irradiated through the optical film or various members, and the optical film or various members are peeled off, and the peeled surface is used. You may irradiate an active energy ray.
前記ゴム系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 rubber-based 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.
本発明の製造方法においては、前記ゴム系粘着剤組成物の塗布層に活性エネルギー線を照射するものであるが、前記ゴム系粘着剤組成物が、希釈剤として有機溶媒を含有する場合は、塗布後、活性エネルギー線照射前に、加熱乾燥等により溶媒等を除去することが好ましい。
In the production method of the present invention, the coating layer of the rubber-based pressure-sensitive adhesive composition is irradiated with active energy rays, but when the rubber-based pressure-sensitive adhesive composition contains an organic solvent as a diluent, It is preferable to remove the solvent and the like by heat drying after application and before irradiation with active energy rays.
前記加熱乾燥温度は、特に限定されないが、残存溶媒を少なくする観点から、３０℃～９０℃程度が好ましく、６０℃～８０℃程度がより好ましい。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 not particularly limited, but is preferably about 30 ° C. to 90 ° C., more preferably about 60 ° C. to 80 ° C. from the viewpoint of reducing the residual solvent. 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.
前記活性エネルギー線としては、例えば、可視光線、紫外線、電子線等を挙げることができるが、これらの中でも、紫外線が好ましい。
Examples of the active energy rays include visible light, ultraviolet rays, and electron beams. Among these, ultraviolet rays are preferable.
紫外線の照射条件は、特に限定されるものではなく、架橋させるゴム系粘着剤組成の組成に応じて、任意の適切な条件に設定することができるが、例えば、照射積算光量が１００ｍＪ／ｃｍ２～２０００ｍＪ／ｃｍ２が好ましい。
The irradiation condition of ultraviolet rays is not particularly limited, and can be set to any appropriate condition depending on the composition of the rubber-based pressure-sensitive adhesive composition to be crosslinked. For example, the integrated irradiation light amount is 100 mJ / cm 2. ˜2000 mJ / cm 2 is preferred.
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ィルム、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.
本発明の製造方法により得られたゴム系粘着剤層の厚みや透湿度は、前述の通りである。
The thickness and moisture permeability of the rubber-based pressure-sensitive adhesive layer obtained by the production method of the present invention are as described above.
４．粘着剤層付光学フィルム
本発明のゴム系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ゴム系粘着剤層を有することを特徴とする。 4). Optical film with pressure-sensitive adhesive layer The optical film with a rubber-based pressure-sensitive adhesive layer of the present invention has an optical film and the rubber-based pressure-sensitive adhesive layer provided on the optical film.
本発明のゴム系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ゴム系粘着剤層を有することを特徴とする。 4). Optical film with pressure-sensitive adhesive layer The optical film with a rubber-based pressure-sensitive adhesive layer of the present invention has an optical film and the rubber-based pressure-sensitive adhesive layer provided on the optical film.
前記光学フィルム上にゴム系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ゴム系粘着剤組成物を塗布して、活性エネルギー線を照射することにより、ゴム系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、支持体等上にゴム系粘着剤層を形成し、当該ゴム系粘着剤層を光学フィルム上に転写して、ゴム系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、前記ゴム系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、そのままゴム系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 of forming a rubber-based pressure-sensitive adhesive layer on the optical film, the rubber-based pressure-sensitive adhesive layer is applied to the optical film by irradiating active energy rays. Can be formed on top. Further, as described above, an optical film with a rubber-based pressure-sensitive adhesive layer can be formed by forming a rubber-based pressure-sensitive adhesive layer on a support or the like and transferring the rubber-based pressure-sensitive adhesive layer onto the optical film. In this case, the release-treated sheet used in the production of the optical film with a rubber-based pressure-sensitive adhesive layer can be used as it is as a separator for the optical film with a rubber-based 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 protective film on one or both sides of the polarizer is generally used. In the present invention, a single-sided protective polarizing film is preferable from the viewpoint of reducing the thickness.
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り得ることができる。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 and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. 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。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。
The material for forming the protective film provided on one or both sides of the polarizer is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. 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 protective film include blends of the polymer. The protective film can also be formed as a cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone, or other thermosetting or ultraviolet curable resin. 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 protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesion to the various protective films. The adhesive used in the present invention can contain a metal compound filler.
前記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 protective film to which the polarizer is not adhered 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 protective film 5 only on one side of the polarizer 4, the pressure-sensitive adhesive layer 3 has the protective film 5 of the polarizer 4. It is preferable that it is formed on the non-side (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、光学フィルムや偏光子の表面に、アンカー層や透明樹脂層を形成したり、コロナ処理、プラズマ処理等の各種易接着処理を施した後に粘着剤層を形成することができる。また、粘着剤層の表面には易接着処理をおこなってもよい。
In addition, the pressure-sensitive adhesive layer can be formed after forming an anchor layer or a transparent resin layer on the surface of the optical film or polarizer, or after performing various easy adhesion treatments such as corona treatment and plasma treatment. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
５．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。 5). 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.
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。 5). 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.
６．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。 6). 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、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。 6). 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.
製造例１（偏光フィルム（１）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 (1))
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.
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 (1))
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、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（偏光フィルム（１））を作製した。
While applying a polyvinyl alcohol adhesive to the surface of the polarizing film (polarizer, thickness: 5 μm) of the optical film laminate according to the polarizer so that the thickness of the adhesive layer is 0.1 μm, protection is performed. After a film (a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 μm and subjected to corona treatment) was bonded, drying was performed at 50 ° C. for 5 minutes. Subsequently, the amorphous PET base material was peeled off to produce a piece protective polarizing film (polarizing film (1)) using a thin polarizer.
製造例２（偏光フィルム（２）の製造）
厚さ３０μｍのポリビニルアルコールフィルムを、速度比の異なるロール間において、３０℃、０．３％濃度のヨウ素溶液中で１分間染色しながら、３倍まで延伸した。その後、６０℃、４％濃度のホウ酸、１０％濃度のヨウ化カリウムを含む水溶液中に０．５分間浸漬しながら総合延伸倍率が６倍まで延伸した。次いで、３０℃、１．５％濃度のヨウ化カリウムを含む水溶液中に１０秒間浸漬することで洗浄した後、５０℃で４分間乾燥を行い、厚さ１２μｍの偏光子を得た。当該偏光子の片面に、片側にハードコード処理されている、ケン化処理した厚さ２５μｍのトリアセチルセルロースフィルムを、一方、前記偏光子の逆面に１３μｍのシクロオレフィン系樹脂フィルムを、それぞれ、ポリビニルアルコール系接着剤（接着剤層の厚さ：０．１μｍ）により貼り合せて、両保護偏光フィルム（偏光フィルム（２））を作製した。偏光フィルム（２）の構成は、ハードコート／トリアセチルセルロースフィルム／接着剤層／偏光子／接着剤層／シクロオレフィン系樹脂フィルムであった。 Production Example 2 (Production of Polarizing Film (2))
A 30 μm-thick polyvinyl alcohol film was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 12 μm. On one side of the polarizer, a saponified 25 μm-thick triacetyl cellulose film that is hard-coded on one side, and a 13 μm cycloolefin resin film on the opposite side of the polarizer, Both protective polarizing films (polarizing film (2)) were produced by bonding with a polyvinyl alcohol-based adhesive (adhesive layer thickness: 0.1 μm). The configuration of the polarizing film (2) was hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film.
厚さ３０μｍのポリビニルアルコールフィルムを、速度比の異なるロール間において、３０℃、０．３％濃度のヨウ素溶液中で１分間染色しながら、３倍まで延伸した。その後、６０℃、４％濃度のホウ酸、１０％濃度のヨウ化カリウムを含む水溶液中に０．５分間浸漬しながら総合延伸倍率が６倍まで延伸した。次いで、３０℃、１．５％濃度のヨウ化カリウムを含む水溶液中に１０秒間浸漬することで洗浄した後、５０℃で４分間乾燥を行い、厚さ１２μｍの偏光子を得た。当該偏光子の片面に、片側にハードコード処理されている、ケン化処理した厚さ２５μｍのトリアセチルセルロースフィルムを、一方、前記偏光子の逆面に１３μｍのシクロオレフィン系樹脂フィルムを、それぞれ、ポリビニルアルコール系接着剤（接着剤層の厚さ：０．１μｍ）により貼り合せて、両保護偏光フィルム（偏光フィルム（２））を作製した。偏光フィルム（２）の構成は、ハードコート／トリアセチルセルロースフィルム／接着剤層／偏光子／接着剤層／シクロオレフィン系樹脂フィルムであった。 Production Example 2 (Production of Polarizing Film (2))
A 30 μm-thick polyvinyl alcohol film was stretched up to 3 times while being dyed for 1 minute in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 12 μm. On one side of the polarizer, a saponified 25 μm-thick triacetyl cellulose film that is hard-coded on one side, and a 13 μm cycloolefin resin film on the opposite side of the polarizer, Both protective polarizing films (polarizing film (2)) were produced by bonding with a polyvinyl alcohol-based adhesive (adhesive layer thickness: 0.1 μm). The configuration of the polarizing film (2) was hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film.
製造例３（偏光フィルム（３）の製造）
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。前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（Ａ）を調製した。 Production Example 3 (Production of Polarizing Film (3))
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 Then, 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so that the solid content was 20%, and then 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 crosslinking agent, a silane coupling agent An acrylic pressure-sensitive adhesive composition (A) was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
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。前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（Ａ）を調製した。 Production Example 3 (Production of Polarizing Film (3))
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 Then, 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate as a polymerization solvent were added so that the solid content was 20%, and then 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 crosslinking agent, a silane coupling agent An acrylic pressure-sensitive adhesive composition (A) was prepared by adding 0.1 parts by weight (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).
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、１５５℃で３分乾燥させて、厚みが２０μｍのアクリル系粘着剤層（Ａ）を形成し、ポリエステルフィルム／アクリル系粘着剤層（Ａ）からなる粘着シートを作製した。
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. Next, the coating layer was dried at 155 ° C. for 3 minutes to form an acrylic pressure-sensitive adhesive layer (A) having a thickness of 20 μm, and a pressure-sensitive adhesive sheet composed of a polyester film / acrylic pressure-sensitive adhesive layer (A) was produced.
製造例１で得られた偏光フィルム（１）の保護フィルム（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）に、前記粘着シートの粘着剤層を貼り合せ、ポリエステルフィルム（セパレーター）／アクリル系粘着剤層（Ａ）／保護フィルム／接着剤層／偏光子の構成である偏光フィルム（３）を得た。
A pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is applied to the protective film of the polarizing film (1) obtained in Production Example 1 (a (meth) acrylic resin film having a lactone ring structure having a thickness of 20 μm subjected to corona treatment). In addition, a polarizing film (3) having a constitution of polyester film (separator) / acrylic pressure-sensitive adhesive layer (A) / protective film / adhesive layer / polarizer was obtained.
実施例１
（ゴム系組成物の調製）
ポリイソブチレン（商品名：ＯＰＰＡＮＯＬ Ｂ８０、Ｍｗ：約７５万、ＢＡＳＦ社製）１００重量部と、多官能ラジカル重合性化合物としてのトリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）５重量部、水素引抜型光重合開始剤であるベンゾフェノン（和光純薬工業（株）製）０．５部を配合したトルエン溶液（粘着剤溶液）を固形分が１５重量％になるように調整し、ゴム系粘着剤組成物（溶液）を調製した。 Example 1
(Preparation of rubber composition)
100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Toluene solution containing 5 parts by weight of functional acrylate, molecular weight: 304 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.5 part of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) as a hydrogen abstraction type photopolymerization initiator ( The pressure-sensitive adhesive solution was adjusted so that the solid content was 15% by weight to prepare a rubber-based pressure-sensitive adhesive composition (solution).
（ゴム系組成物の調製）
ポリイソブチレン（商品名：ＯＰＰＡＮＯＬ Ｂ８０、Ｍｗ：約７５万、ＢＡＳＦ社製）１００重量部と、多官能ラジカル重合性化合物としてのトリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）５重量部、水素引抜型光重合開始剤であるベンゾフェノン（和光純薬工業（株）製）０．５部を配合したトルエン溶液（粘着剤溶液）を固形分が１５重量％になるように調整し、ゴム系粘着剤組成物（溶液）を調製した。 Example 1
(Preparation of rubber composition)
100 parts by weight of polyisobutylene (trade name: OPPANOL B80, Mw: about 750,000, manufactured by BASF) and tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, 2) as a polyfunctional radical polymerizable compound Toluene solution containing 5 parts by weight of functional acrylate, molecular weight: 304 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.5 part of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) as a hydrogen abstraction type photopolymerization initiator ( The pressure-sensitive adhesive solution was adjusted so that the solid content was 15% by weight to prepare a rubber-based pressure-sensitive adhesive composition (solution).
（ゴム系粘着シートの形成）
得られたゴム系粘着剤組成物（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、８０℃で３分乾燥させて、ゴム系粘着剤層を形成し、ゴム系粘着剤層の厚みが５０μｍの粘着シートを作製した。また、前記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、剥離処理面と前記ゴム系粘着剤層が接するように貼り合せた。ゴム系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。 (Formation of rubber adhesive sheet)
The obtained rubber-based pressure-sensitive adhesive composition (solution) was applied to a release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) with one side being peel-treated with silicone. A layer was formed. Subsequently, the coating layer was dried at 80 ° C. for 3 minutes to form a rubber-based pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 μm was produced. Further, on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet, a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone is used. The layers were bonded so that the layers were in contact. The polyester film coated on both surfaces of the rubber pressure-sensitive adhesive layer functions as a release liner (separator).
得られたゴム系粘着剤組成物（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、８０℃で３分乾燥させて、ゴム系粘着剤層を形成し、ゴム系粘着剤層の厚みが５０μｍの粘着シートを作製した。また、前記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、剥離処理面と前記ゴム系粘着剤層が接するように貼り合せた。ゴム系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。 (Formation of rubber adhesive sheet)
The obtained rubber-based pressure-sensitive adhesive composition (solution) was applied to a release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) with one side being peel-treated with silicone. A layer was formed. Subsequently, the coating layer was dried at 80 ° C. for 3 minutes to form a rubber-based pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a thickness of 50 μm was produced. Further, on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet, a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone is used. The layers were bonded so that the layers were in contact. The polyester film coated on both surfaces of the rubber pressure-sensitive adhesive layer functions as a release liner (separator).
一方のセパレーターを剥離し、セパレーターを剥離した側から、室温で紫外線を照射し、ゴム系粘着剤層／セパレーターからなるゴム系粘着シートを得た。前記紫外線照射は、ＵＶＡ領域にて、光量１０００ｍＪ／ｃｍ２であった。
One separator was peeled off, and ultraviolet rays were irradiated at room temperature from the side where the separator was peeled off to obtain a rubber-based pressure-sensitive adhesive sheet comprising a rubber-based pressure-sensitive adhesive layer / separator. In the UVA region, the UV irradiation was a light amount of 1000 mJ / cm 2 .
実施例２～２２、比較例１～３、５
表１に記載の組成及び膜厚にした以外は実施例１と同様にして、ゴム系粘着シートを作製した。 Examples 2 to 22, Comparative Examples 1 to 3, 5
A rubber-based pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the composition and film thickness described in Table 1 were used.
表１に記載の組成及び膜厚にした以外は実施例１と同様にして、ゴム系粘着シートを作製した。 Examples 2 to 22, Comparative Examples 1 to 3, 5
A rubber-based pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the composition and film thickness described in Table 1 were used.
比較例４
（アクリル系粘着シートの作製）
製造例３で作製したアクリル系粘着剤組成物（Ａ）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５０μｍ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て、アクリル系粘着シートを得た。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。 Comparative Example 4
(Production of acrylic adhesive sheet)
The acrylic pressure-sensitive adhesive composition (A) produced in Production Example 3 was applied to a release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone. Thus, a coating layer was formed. Next, 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 50 μm was prepared. 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 and the pressure-sensitive adhesive layer are in contact with each other. Thus, an acrylic pressure-sensitive adhesive sheet was obtained. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
（アクリル系粘着シートの作製）
製造例３で作製したアクリル系粘着剤組成物（Ａ）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５０μｍ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て、アクリル系粘着シートを得た。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。 Comparative Example 4
(Production of acrylic adhesive sheet)
The acrylic pressure-sensitive adhesive composition (A) produced in Production Example 3 was applied to a release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone. Thus, a coating layer was formed. Next, 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 50 μm was prepared. 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 and the pressure-sensitive adhesive layer are in contact with each other. Thus, an acrylic pressure-sensitive adhesive sheet was obtained. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).
実施例、比較例で得られた粘着剤組成物、粘着シートについて、以下の評価を行った。評価結果を表１に示す。
The following evaluation was performed on the pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples. The evaluation results are shown in Table 1.
＜耐久性１（偏光フィルム（１））＞
製造例１で得られた偏光フィルム（１）と実施例及び比較例で得られた粘着シートを、それぞれ、偏光フィルム（１）の偏光子と前記粘着シートの粘着剤層と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、保護フィルム／接着剤層／偏光子／粘着剤層／セパレーターであった。 <Durability 1 (polarizing film (1))>
The polarizing film (1) obtained in Production Example 1 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were laminated such that the polarizer of the polarizing film (1) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet were in contact with each other. Thus, a polarizing film with an adhesive layer was obtained. 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 protective film / adhesive layer / polarizer / adhesive layer / separator.
製造例１で得られた偏光フィルム（１）と実施例及び比較例で得られた粘着シートを、それぞれ、偏光フィルム（１）の偏光子と前記粘着シートの粘着剤層と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、保護フィルム／接着剤層／偏光子／粘着剤層／セパレーターであった。 <Durability 1 (polarizing film (1))>
The polarizing film (1) obtained in Production Example 1 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were laminated such that the polarizer of the polarizing film (1) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet were in contact with each other. Thus, a polarizing film with an adhesive layer was obtained. 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 protective film / adhesive layer / polarizer / adhesive layer / separator.
前記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９５℃の環境下に５００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。 The separator of the obtained polarizing film with an adhesive layer is peeled off, the test piece is bonded to a glass plate, and the state after being put in an environment of 95 ° C. for 500 hours is observed visually or using a magnifying glass (20 times). did. 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.
◎：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。 The separator of the obtained polarizing film with an adhesive layer is peeled off, the test piece is bonded to a glass plate, and the state after being put in an environment of 95 ° C. for 500 hours is observed visually or using a magnifying glass (20 times). did. 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.
＜耐久性２（偏光フィルム（２））＞
製造例２で得られた偏光フィルム（２）と実施例及び比較例で得られた粘着シートを、それぞれ、偏光フィルム（２）のシクロオレフィン系樹脂フィルムと前記粘着シートの粘着剤層と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、ハードコート／トリアセチルセルロースフィルム／接着剤層／偏光子／接着剤層／シクロオレフィン系樹脂フィルム／粘着剤層／セパレーターであった。 <Durability 2 (polarizing film (2))>
The polarizing film (2) obtained in Production Example 2 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples are respectively in contact with the cycloolefin resin film of the polarizing film (2) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. Thus, a polarizing film with a pressure-sensitive adhesive layer was obtained. 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 hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film / adhesive layer / separator.
製造例２で得られた偏光フィルム（２）と実施例及び比較例で得られた粘着シートを、それぞれ、偏光フィルム（２）のシクロオレフィン系樹脂フィルムと前記粘着シートの粘着剤層と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、ハードコート／トリアセチルセルロースフィルム／接着剤層／偏光子／接着剤層／シクロオレフィン系樹脂フィルム／粘着剤層／セパレーターであった。 <Durability 2 (polarizing film (2))>
The polarizing film (2) obtained in Production Example 2 and the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples are respectively in contact with the cycloolefin resin film of the polarizing film (2) and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. Thus, a polarizing film with a pressure-sensitive adhesive layer was obtained. 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 hard coat / triacetyl cellulose film / adhesive layer / polarizer / adhesive layer / cycloolefin resin film / adhesive layer / separator.
前記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９５℃の環境下に５００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。＜耐久性１＞試験と同様の評価基準により評価した。
The separator of the obtained polarizing film with an adhesive layer is peeled off, the test piece is bonded to a glass plate, and the state after being put in an environment of 95 ° C. for 500 hours is observed visually or using a magnifying glass (20 times). did. <Durability 1> Evaluation was performed according to the same evaluation criteria as in the test.
＜耐久性３（偏光フィルム（３））＞
実施例及び比較例で得られた粘着シートの粘着剤層と２０μｍの直線偏光分離フィルム（商品名：Ｄ－ＢＥＦ、３Ｍ社製）を貼り合せて粘着剤層付輝度向上フィルムを作製した。 <Durability 3 (Polarizing film (3))>
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples and a 20 μm linearly polarized light separating film (trade name: D-BEF, manufactured by 3M Company) were bonded to produce a brightness enhancement film with a pressure-sensitive adhesive layer.
実施例及び比較例で得られた粘着シートの粘着剤層と２０μｍの直線偏光分離フィルム（商品名：Ｄ－ＢＥＦ、３Ｍ社製）を貼り合せて粘着剤層付輝度向上フィルムを作製した。 <Durability 3 (Polarizing film (3))>
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples and a 20 μm linearly polarized light separating film (trade name: D-BEF, manufactured by 3M Company) were bonded to produce a brightness enhancement film with a pressure-sensitive adhesive layer.
前記粘着剤層付輝度向上フィルムと製造例３で得られた偏光フィルム（３）を、前記粘着剤層付輝度向上フィルムの粘着剤層と、製造例３で得られた偏光フィルム（３）の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、ポリエステルフィルム（セパレーター）／アクリル系粘着剤層（Ａ）／保護フィルム／接着剤層／偏光子／実施例、比較例で得られた粘着剤層／輝度向上フィルムであった。
The brightness-enhancing film with the pressure-sensitive adhesive layer and the polarizing film (3) obtained in Production Example 3 are the same as the pressure-sensitive adhesive layer of the brightness-enhancing film with the pressure-sensitive adhesive layer and the polarizing film (3) obtained in Production Example 3. It laminated | stacked so that a polarizer might contact | connect and obtained the polarizing film with an adhesive layer. The release liner of the pressure-sensitive adhesive layer was left as a separator. The composition of the obtained polarizing film with a pressure-sensitive adhesive layer was as follows: polyester film (separator) / acrylic pressure-sensitive adhesive layer (A) / protective film / adhesive layer / polarizer / Example, pressure-sensitive adhesive layer obtained in Comparative Example / It was a brightness enhancement film.
前記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９５℃の環境下に５００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。＜耐久性１＞試験と同様の評価基準により評価した。
The separator of the obtained polarizing film with an adhesive layer is peeled off, the test piece is bonded to a glass plate, and the state after being put in an environment of 95 ° C. for 500 hours is observed visually or using a magnifying glass (20 times). did. <Durability 1> Evaluation was performed according to the same evaluation criteria as in the test.
前記＜耐久性１＞及び＜耐久性２＞試験では、それぞれ、耐久性試験の被着体（ガラス板）への偏光フィルムの積層は、実施例及び比較例で得られた粘着剤層を介してなされたが、前記＜耐久性３＞試験では、製造例３で得られたアクリル系粘着剤層（Ａ）を介して耐久性試験の被着体（ガラス板）と偏光フィルムが積層された。
In the <Durability 1> and <Durability 2> tests, the polarizing film was laminated on the adherend (glass plate) in the durability test via the pressure-sensitive adhesive layers obtained in Examples and Comparative Examples, respectively. However, in the <Durability 3> test, the adherend (glass plate) and the polarizing film of the durability test were laminated through the acrylic pressure-sensitive adhesive layer (A) obtained in Production Example 3. .
＜ゲル分率＞
凧糸と、孔径０．２μｍのテトラフルオロエチレン樹脂製多孔質膜（商品名：ニトフロンＮＴＦ１１２２、日東電工（株）製）との合計重量を予め測定した（Ｗａ（ｍｇ））。得られた粘着シートから、粘着剤層を約１ｇ採取し、前記多孔質膜に巾着状に包み、口を凧糸で縛った後、包みの重量を測定した（Ｗｂ（ｍｇ））。この包みを容量５０ｍＬのスクリュー瓶に入れ、該スクリュー瓶にトルエンを満たした。これを室温で７日間放置した後、前記包みを取り出して１３０℃で２時間乾燥させ、該包みの重量を測定し（Ｗｃ（ｍｇ））、次式によりゲル分率を求めた。
ゲル分率（％）＝（Ｗｃ－Ｗａ）／（Ｗｂ－Ｗａ）×１００ <Gel fraction>
The total weight of the kite string and a porous membrane made of tetrafluoroethylene resin having a pore diameter of 0.2 μm (trade name: NITOFLON NTF1122, manufactured by Nitto Denko Corporation) was measured in advance (W a (mg)). About 1 g of the pressure-sensitive adhesive layer was collected from the obtained pressure-sensitive adhesive sheet, wrapped in a purse-like shape in the porous membrane, and the mouth was tied with a string, and the weight of the wrap was measured (W b (mg)). This packet was placed in a 50-mL screw bottle, and the screw bottle was filled with toluene. After leaving this at room temperature for 7 days, the packet was taken out and dried at 130 ° C. for 2 hours, the weight of the packet was measured (W c (mg)), and the gel fraction was determined by the following formula.
Gel fraction (%) = (W c −W a ) / (W b −W a ) × 100
凧糸と、孔径０．２μｍのテトラフルオロエチレン樹脂製多孔質膜（商品名：ニトフロンＮＴＦ１１２２、日東電工（株）製）との合計重量を予め測定した（Ｗａ（ｍｇ））。得られた粘着シートから、粘着剤層を約１ｇ採取し、前記多孔質膜に巾着状に包み、口を凧糸で縛った後、包みの重量を測定した（Ｗｂ（ｍｇ））。この包みを容量５０ｍＬのスクリュー瓶に入れ、該スクリュー瓶にトルエンを満たした。これを室温で７日間放置した後、前記包みを取り出して１３０℃で２時間乾燥させ、該包みの重量を測定し（Ｗｃ（ｍｇ））、次式によりゲル分率を求めた。
ゲル分率（％）＝（Ｗｃ－Ｗａ）／（Ｗｂ－Ｗａ）×１００ <Gel fraction>
The total weight of the kite string and a porous membrane made of tetrafluoroethylene resin having a pore diameter of 0.2 μm (trade name: NITOFLON NTF1122, manufactured by Nitto Denko Corporation) was measured in advance (W a (mg)). About 1 g of the pressure-sensitive adhesive layer was collected from the obtained pressure-sensitive adhesive sheet, wrapped in a purse-like shape in the porous membrane, and the mouth was tied with a string, and the weight of the wrap was measured (W b (mg)). This packet was placed in a 50-mL screw bottle, and the screw bottle was filled with toluene. After leaving this at room temperature for 7 days, the packet was taken out and dried at 130 ° C. for 2 hours, the weight of the packet was measured (W c (mg)), and the gel fraction was determined by the following formula.
Gel fraction (%) = (W c −W a ) / (W b −W a ) × 100
＜透湿度＞
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。 <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 sheet was bonded to a triacetyl cellulose 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, the moisture permeability test method (cup method, JIS
According to Z 0208), the water vapor transmission rate (water vapor transmission rate) was measured.
Measurement temperature: 40 ° C
Relative humidity: 92%
Measurement time: 24 hours A constant temperature and humidity chamber was used for the measurement.
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。 <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 sheet was bonded to a triacetyl cellulose 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, the moisture permeability test method (cup method, JIS
According to Z 0208), the water vapor transmission rate (water vapor transmission rate) was measured.
Measurement temperature: 40 ° C
Relative humidity: 92%
Measurement time: 24 hours A constant temperature and humidity chamber was used for the measurement.
表１中の表記は以下の通りである。
＜ポリイソブチレン＞
ＯＰＰＡＮＯＬ Ｂ８０：ポリイソブチレン（Ｍｗ：約７５万、ＢＡＳＦ社製）
ＯＰＰＡＮＯＬ Ｂ１００：ポリイソブチレン（Ｍｗ：約１６８万、ＢＡＳＦ社製）
＜それ以外のポリマー＞
アクリル系樹脂：比較例４で得られたアクリル系粘着剤組成物
＜粘着付与剤＞
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１６０℃、水酸基価が６０である完全水添テルペンフェノール
＜多官能ラジカル重合性化合物＞
Ａ－ＤＣＰ：トリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）
ＤＣＰ：トリシクロデカンジメタノールジメタクリレート（商品名：ＮＫエステルＤＣＰ、２官能メタクリレート、分子量：３３２、新中村化学工業（株）製）
Ａ－ＴＭＰＴＡ：トリメチロールプロパントリアクリレート（商品名：ＮＫエステルＡ－ＴＭＰＴ、３官能アクリレート、分子量：２９６、新中村化学工業（株）製）
＜光重合開始剤＞
ベンゾフェノン：水素引抜型光重合開始剤
イルガキュア１８４：開裂型光開始剤、１－ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製） The notations in Table 1 are as follows.
<Polyisobutylene>
OPPANOL B80: Polyisobutylene (Mw: approx. 750,000, manufactured by BASF)
OPPANOL B100: Polyisobutylene (Mw: about 1680,000, manufactured by BASF)
<Other polymers>
Acrylic resin: acrylic pressure-sensitive adhesive composition obtained in Comparative Example 4 <Tackifier>
Completely hydrogenated terpenephenol (A): Completely hydrogenated terpenephenol with a softening point of 135 ° C. and a hydroxyl value of 160 Completely hydrogenated terpenephenol (B): Completely hydrogenated with a softening point of 160 ° C. and a hydroxyl value of 60 Terpene phenol <Polyfunctional radical polymerizable compound>
A-DCP: Tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (trade name: NK ester DCP, bifunctional methacrylate, molecular weight: 332, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-TMPTA: trimethylolpropane triacrylate (trade name: NK ester A-TMPT, trifunctional acrylate, molecular weight: 296, manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator>
Benzophenone: Hydrogen abstraction type photopolymerization initiator Irgacure 184: Cleavage type photoinitiator, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF)
＜ポリイソブチレン＞
ＯＰＰＡＮＯＬ Ｂ８０：ポリイソブチレン（Ｍｗ：約７５万、ＢＡＳＦ社製）
ＯＰＰＡＮＯＬ Ｂ１００：ポリイソブチレン（Ｍｗ：約１６８万、ＢＡＳＦ社製）
＜それ以外のポリマー＞
アクリル系樹脂：比較例４で得られたアクリル系粘着剤組成物
＜粘着付与剤＞
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１６０℃、水酸基価が６０である完全水添テルペンフェノール
＜多官能ラジカル重合性化合物＞
Ａ－ＤＣＰ：トリシクロデカンジメタノールジアクリレート（商品名：ＮＫエステルＡ－ＤＣＰ、２官能アクリレート、分子量：３０４、新中村化学工業（株）製）
ＤＣＰ：トリシクロデカンジメタノールジメタクリレート（商品名：ＮＫエステルＤＣＰ、２官能メタクリレート、分子量：３３２、新中村化学工業（株）製）
Ａ－ＴＭＰＴＡ：トリメチロールプロパントリアクリレート（商品名：ＮＫエステルＡ－ＴＭＰＴ、３官能アクリレート、分子量：２９６、新中村化学工業（株）製）
＜光重合開始剤＞
ベンゾフェノン：水素引抜型光重合開始剤
イルガキュア１８４：開裂型光開始剤、１－ヒドロキシシクロヘキシルフェニルケトン（ＢＡＳＦ社製） The notations in Table 1 are as follows.
<Polyisobutylene>
OPPANOL B80: Polyisobutylene (Mw: approx. 750,000, manufactured by BASF)
OPPANOL B100: Polyisobutylene (Mw: about 1680,000, manufactured by BASF)
<Other polymers>
Acrylic resin: acrylic pressure-sensitive adhesive composition obtained in Comparative Example 4 <Tackifier>
Completely hydrogenated terpenephenol (A): Completely hydrogenated terpenephenol with a softening point of 135 ° C. and a hydroxyl value of 160 Completely hydrogenated terpenephenol (B): Completely hydrogenated with a softening point of 160 ° C. and a hydroxyl value of 60 Terpene phenol <Polyfunctional radical polymerizable compound>
A-DCP: Tricyclodecane dimethanol diacrylate (trade name: NK ester A-DCP, bifunctional acrylate, molecular weight: 304, manufactured by Shin-Nakamura Chemical Co., Ltd.)
DCP: Tricyclodecane dimethanol dimethacrylate (trade name: NK ester DCP, bifunctional methacrylate, molecular weight: 332, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-TMPTA: trimethylolpropane triacrylate (trade name: NK ester A-TMPT, trifunctional acrylate, molecular weight: 296, manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator>
Benzophenone: Hydrogen abstraction type photopolymerization initiator Irgacure 184: Cleavage type photoinitiator, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF)
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 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 OFSYMBOLS 1 Polarizing film with an adhesive layer 2 Polarizing film 3 Adhesive layer 4 Polarizer 5 Protective film 6 Brightness improvement film 7 Prism sheet 10 Optical member
２ 偏光フィルム
３ 粘着剤層
４ 偏光子
５ 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
Claims (18)
- ポリイソブチレン、及び水素引抜型光重合開始剤を含むことを特徴とするゴム系粘着剤組成物。 A rubber-based pressure-sensitive adhesive composition comprising polyisobutylene and a hydrogen abstraction type photopolymerization initiator.
- 多官能ラジカル重合性化合物を、前記ポリイソブチレン１００重量部に対して２０重量部以下含むことを特徴とする請求項１に記載のゴム系粘着剤組成物。 The rubber-based pressure-sensitive adhesive composition according to claim 1, comprising a polyfunctional radical polymerizable compound in an amount of 20 parts by weight or less based on 100 parts by weight of the polyisobutylene.
- 前記多官能ラジカル重合性化合物が、（メタ）アクリロイル基を少なくとも２つ有する化合物であることを特徴とする請求項２に記載のゴム系粘着剤組成物。 The rubber-based pressure-sensitive adhesive composition according to claim 2, wherein the polyfunctional radical polymerizable compound is a compound having at least two (meth) acryloyl groups.
- 前記（メタ）アクリロイル基を少なくとも２つ有する化合物が、（メタ）アクリロイル基を２つ有する２官能（メタ）アクリレート及び／又は（メタ）アクリロイル基を３つ有する３官能（メタ）アクリレートであることを特徴とする請求項３に記載のゴム系粘着剤組成物。 The compound having at least two (meth) acryloyl groups is a bifunctional (meth) acrylate having two (meth) acryloyl groups and / or a trifunctional (meth) acrylate having three (meth) acryloyl groups. The rubber-based pressure-sensitive adhesive composition according to claim 3.
- 前記水素引抜型光重合開始剤が、ベンゾフェノン系化合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ゴム系粘着剤組成物。 5. The rubber-based pressure-sensitive adhesive composition according to claim 1, wherein the hydrogen abstraction type photopolymerization initiator is a benzophenone-based compound.
- 前記水素引抜型光重合開始剤の含有量が、前記ポリイソブチレン１００重量部に対して、０．００１～１０重量部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ゴム系粘着剤組成物。 6. The rubber system according to claim 1, wherein the content of the hydrogen abstraction type photopolymerization initiator is 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyisobutylene. Adhesive composition.
- 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、及びこれらの水添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請求項１～６のいずれかに記載のゴム系粘着剤組成物。 7. A tackifier containing a terpene skeleton, a tackifier containing a rosin skeleton, and at least one tackifier selected from the group consisting of hydrogenated products thereof. A rubber-based pressure-sensitive adhesive composition according to claim 1.
- 活性エネルギー線の照射により架橋されることを特徴とする請求項１～７のいずれかに記載のゴム系粘着剤組成物。 The rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is crosslinked by irradiation with active energy rays.
- 前記活性エネルギー線が、紫外線であることを特徴とする請求項８に記載のゴム系粘着剤組成物。 The rubber-based pressure-sensitive adhesive composition according to claim 8, wherein the active energy rays are ultraviolet rays.
- 前記ゴム系粘着剤組成物から形成した厚み５０μｍのゴム系粘着剤層の、４０℃、９２％Ｒ．Ｈ．における透湿度が、５０ｇ／（ｍ２・ｄａｙ）以下であることを特徴とする請求項１～９のいずれかに記載のゴム系粘着剤組成物。 The rubber-based pressure-sensitive adhesive layer having a thickness of 50 μm formed from the rubber-based pressure-sensitive adhesive composition was subjected to 40 ° C. and 92% R.D. H. The rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 9, wherein the moisture permeability is 50 g / (m 2 · day) or less.
- 請求項１～１０のいずれかに記載のゴム系粘着剤組成物から形成されたことを特徴とするゴム系粘着剤層。 A rubber-based pressure-sensitive adhesive layer formed from the rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 10.
- 光学フィルム、及び当該光学フィルム上に設けられた請求項１１に記載のゴム系粘着剤層を有することを特徴とするゴム系粘着剤層付光学フィルム。 An optical film with a rubber-based pressure-sensitive adhesive layer, comprising: an optical film; and the rubber-based pressure-sensitive adhesive layer according to claim 11 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 protective film on at least one surface of a polarizer.
- 前記偏光フィルムが、偏光子の片面のみに保護フィルムを有する片面保護偏光フィルムであって、前記ゴム系粘着剤層が、偏光子の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に記載のゴム系粘着剤層付光学フィルム。 The polarizing film is a single-sided protective polarizing film having a protective film only on one side of the polarizer, and the rubber-based pressure-sensitive adhesive layer is laminated on the side not having the protective film of the polarizer, The optical film with a rubber-based pressure-sensitive adhesive layer according to claim 13.
- 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に記載のゴム系粘着剤層付光学フィルム。 The optical film with a rubber-based pressure-sensitive adhesive layer according to claim 12, wherein the optical film is a brightness enhancement film.
- 請求項１１に記載のゴム系粘着剤層と、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。 A rubber-based 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.
- 請求項１２～１５のいずれかに記載のゴム系粘着剤層付光学フィルム、及び請求項１６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 a rubber-based pressure-sensitive adhesive layer according to any one of claims 12 to 15 and an optical member according to claim 16.
- 請求項１～１０のいずれかに記載のゴム系粘着剤組成物に、活性エネルギー線を照射して、前記ポリイソブチレンを架橋する工程を含むことを特徴とするゴム系粘着剤層の製造方法。
A method for producing a rubber-based pressure-sensitive adhesive layer, comprising a step of irradiating an active energy ray to the rubber-based pressure-sensitive adhesive composition according to any one of claims 1 to 10 to crosslink the polyisobutylene.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201680072809.2A CN108368401B (en) | 2015-12-25 | 2016-12-21 | Rubber-based pressure-sensitive adhesive composition, rubber-based pressure-sensitive adhesive layer, optical film with rubber-based pressure-sensitive adhesive layer, optical member, image display device, and method for producing rubber-based pressure-sensitive adhesive layer |
| KR1020187015789A KR102580624B1 (en) | 2015-12-25 | 2016-12-21 | Rubber-based adhesive composition, rubber-based adhesive layer, optical film having a rubber-based adhesive layer, optical member, image display device, and method for producing the rubber-based adhesive layer |
| SG11201805047QA SG11201805047QA (en) | 2015-12-25 | 2016-12-21 | Rubber-based pressure-sensitive-adhesive composition, rubber-based pressure-sensitive-adhesive layer, rubber-based pressure-sensitive-adhesive layer attached optical film, optical member, image display device, and method for producing rubber-based pressure-sensitive-adhesive layer |
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| JP2015254395 | 2015-12-25 | ||
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| JP2016243991A JP6873682B2 (en) | 2015-12-25 | 2016-12-16 | A method for manufacturing a rubber-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive layer, an optical film with a rubber-based pressure-sensitive adhesive layer, an optical member, an image display device, and a rubber-based pressure-sensitive adhesive layer. |
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| PCT/JP2016/088191 WO2017110913A1 (en) | 2015-12-25 | 2016-12-21 | Rubber-based adhesive composition, rubber-based adhesive layer, optical film with rubber-based adhesive layer, optical member, image display device, and method for producing rubber-based adhesive layer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200098976A (en) * | 2019-02-13 | 2020-08-21 | 서울대학교산학협력단 | Semi-interpenetrating polymer network structure type adhesive film improved heat resistance and manufacturing method of the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006011365A (en) * | 2004-05-26 | 2006-01-12 | Nitto Denko Corp | Adhesive optical member |
| JP2010009027A (en) * | 2008-05-27 | 2010-01-14 | Nitto Denko Corp | Adhesive polarization plate, image display, and method for manufacturing them |
| JP2010260933A (en) * | 2009-04-30 | 2010-11-18 | Bridgestone Corp | Rubber composition for seismic isolation structure |
| JP2013022920A (en) * | 2011-07-25 | 2013-02-04 | Lintec Corp | Gas barrier film laminate and electronic component |
| WO2015129625A1 (en) * | 2014-02-25 | 2015-09-03 | リンテック株式会社 | Adhesive composition, adhesive sheet, and electronic device |
-
2016
- 2016-12-21 WO PCT/JP2016/088191 patent/WO2017110913A1/en active Application Filing
- 2016-12-22 TW TW111148941A patent/TW202313904A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006011365A (en) * | 2004-05-26 | 2006-01-12 | Nitto Denko Corp | Adhesive optical member |
| JP2010009027A (en) * | 2008-05-27 | 2010-01-14 | Nitto Denko Corp | Adhesive polarization plate, image display, and method for manufacturing them |
| JP2010260933A (en) * | 2009-04-30 | 2010-11-18 | Bridgestone Corp | Rubber composition for seismic isolation structure |
| JP2013022920A (en) * | 2011-07-25 | 2013-02-04 | Lintec Corp | Gas barrier film laminate and electronic component |
| WO2015129625A1 (en) * | 2014-02-25 | 2015-09-03 | リンテック株式会社 | Adhesive composition, adhesive sheet, and electronic device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200098976A (en) * | 2019-02-13 | 2020-08-21 | 서울대학교산학협력단 | Semi-interpenetrating polymer network structure type adhesive film improved heat resistance and manufacturing method of the same |
| KR102208996B1 (en) | 2019-02-13 | 2021-01-28 | 서울대학교산학협력단 | Semi-interpenetrating polymer network structure type adhesive film improved heat resistance and manufacturing method of the same |
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