WO2014091927A1 - Adhesive composition for optical films, adhesive optical film, and laminate - Google Patents
Adhesive composition for optical films, adhesive optical film, and laminate Download PDFInfo
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- WO2014091927A1 WO2014091927A1 PCT/JP2013/081882 JP2013081882W WO2014091927A1 WO 2014091927 A1 WO2014091927 A1 WO 2014091927A1 JP 2013081882 W JP2013081882 W JP 2013081882W WO 2014091927 A1 WO2014091927 A1 WO 2014091927A1
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- sensitive adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a pressure-sensitive adhesive composition for optical films, a pressure-sensitive adhesive optical film, and a laminate.
- image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. .
- high temperature or high temperature and humidity condition examples include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
- an optical film such as a polarizing film constituting the image display device is produced by adsorbing a dichroic dye to a polymer film such as polyvinyl alcohol, and stretching and orienting the film. For this reason, the optical film is easily shrunk under a high temperature or high humidity environment, and dimensional deformation is likely to occur. Moreover, once dimensional deformation occurs in the optical film, it is difficult to completely return to the original dimensions even if the temperature and humidity conditions are changed. As a result, the pressure-sensitive adhesive layer is cracked, peeled off or floated due to the influence of the stress caused by the dimensional change of the optical film, or light leakage due to the polarization axis distortion occurs in the image display device.
- the present invention exhibits excellent durability under high temperature and high humidity conditions, and can reduce light leakage when used for adhesion between an adherend such as a liquid crystal cell and an optical film such as a polarizing film. It is an object of the present invention to provide a pressure-sensitive adhesive composition for an optical film, and a pressure-sensitive adhesive optical film and a laminate using the same.
- the present inventors formed a pressure-sensitive adhesive layer using a pressure-sensitive adhesive composition having a predetermined viscoelastic property, and an adherend such as a liquid crystal cell and an optical film such as a polarizing film.
- the present inventors have found that light leakage can be reduced when used for adhesion to the substrate.
- the pressure-sensitive adhesive composition for an optical film includes an acrylic polymer (A) having a crosslinkable functional group and a crosslinker (B), and has a maximum deformation rate defined below of 10%.
- the strain recovery rate defined below is 50% or more.
- Measurement step 2 Increase the shear stress from 1000 Pa to 2000 Pa at a constant rate for 30 minutes while maintaining the temperature of the sample piece at 80 ° C. for 30 minutes.
- Measurement step 3 While decreasing the temperature of the sample piece from 80 ° C. to 23 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is reduced from 2000 Pa to 0 Pa at a constant rate for 15 minutes.
- the constituting alkyl chain (wherein the alkyl chain has 1 to 20 carbon atoms) can be a linear or branched alkyl chain.
- optical film pressure-sensitive adhesive composition according to any one of 1 to 4, wherein the acrylic polymer (A) having a crosslinkable functional group may have a weight average molecular weight of 500,000 to 2,000,000.
- the gel fraction may be 70% or more.
- the pressure-sensitive adhesive composition for an optical film includes an acrylic polymer (A) having a crosslinkable functional group, and a crosslinker (B).
- the acrylic polymer (A) having the crosslinkable functional group is 5 to 55% by mass of (meth) acrylic acid ester (a1) having no crosslinkable functional group and having a glass transition temperature (Tg) of 0 ° C. or higher; (Meth) acrylic acid ester (a2) having no crosslinkable functional group and having a glass transition temperature (Tg) of less than 0 ° C.
- a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition for optical films according to any one of 1 to 7 above is provided on one side or both sides of the optical film.
- the adhesive optical film described in 8 above can be an optical film selected from the group consisting of a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, and a light diffusion film.
- the laminated body which concerns on the other aspect of this invention is the adhesive for optical films in any one of said 1 thru
- the above-mentioned pressure-sensitive adhesive composition for optical films has moderate adhesive strength, exhibits excellent durability under high temperature conditions or high temperature and high humidity conditions, and adherends such as liquid crystal cells and optical films such as polarizing films. When used for adhesion to a film, light leakage can be reduced.
- the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive composition for an optical film is adhered to an adherend such as a liquid crystal cell with an appropriate adhesive force, and has excellent durability under high temperature conditions or high temperature and high humidity conditions. When it is used for adhesion to an adherend such as a liquid crystal cell, light leakage can be reduced.
- FIG. 1 is a graph schematically illustrating the change with time of the deformation rate of the optical film pressure-sensitive adhesive composition according to one embodiment of the present invention, measured using a rheometer.
- FIG. 2 is a diagram schematically illustrating a method of measuring the luminance of the image display device (liquid crystal display panel) in the embodiment of the present invention.
- FIG. 3 is a diagram illustrating a method for measuring the deformation rate of a test piece of the pressure-sensitive adhesive composition of the present invention using a rheometer.
- FIG. 4 is a cross-sectional view schematically showing an example of a laminate including a pressure-sensitive adhesive layer obtained using the pressure-sensitive adhesive composition for an optical film according to one embodiment of the present invention.
- parts means “parts by mass” and “%” means “mass%” unless otherwise specified.
- optical film pressure-sensitive adhesive composition is an acrylic resin having a crosslinkable functional group.
- Polymer (A) hereinafter sometimes simply referred to as “component (A)”
- crosslinking agent (B) hereinafter sometimes simply referred to as “component (B)”.
- the pressure-sensitive adhesive composition for an optical film according to this embodiment has a maximum deformation rate defined below of 10% or less and a strain recovery rate defined below of 50% or more.
- Maximum deformation rate For a test piece obtained by cutting a 1 mm thick adhesive sheet obtained by applying the optical film adhesive composition on a flat plate and drying it to ⁇ 8 mm, using a rheometer, the following measurement step Deformation rate (%) at the time when the deformation rate becomes maximum when performing 1 to 3 in order
- Final deformation ratio Deformation ratio (%) of the test piece after performing the following measurement steps 1 to 3 in order using a rheometer
- Measurement step 2 Increase the shear stress from 1000 Pa to 2000 Pa at a constant rate for 30 minutes while maintaining the temperature of the sample piece at 80 ° C. for 30 minutes.
- Measurement step 3 While decreasing the temperature of the sample piece from 80 ° C. to 23 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is reduced from 2000 Pa to 0 Pa at a constant rate for 15 minutes.
- the “maximum deformation rate” in the present invention is an index of the ease of deformation of the pressure-sensitive adhesive composition. It can be said that the larger the maximum deformation rate, the easier the pressure-sensitive adhesive composition is deformed.
- the maximum deformation rate exceeds 10%, the pressure-sensitive adhesive layer cannot follow the expansion or contraction of the pressure-sensitive adhesive adherend. May occur, preventing light leakage.
- the maximum strain rate is 10% or less in that birefringence generated in the pressure-sensitive adhesive can be more reliably prevented and light leakage can be further reduced. It is preferably 8% or less.
- the “strain recovery rate” in the present invention is an index of the ease of restoring a deformed pressure-sensitive adhesive composition, and it can be said that the greater the strain recovery rate, the easier the pressure-sensitive adhesive composition recovers from deformation.
- the strain recovery rate is less than 50%, the deformation of the pressure-sensitive adhesive layer is difficult to recover, so birefringence generated in the pressure-sensitive adhesive is not eliminated, and light It may not be possible to prevent leakage.
- the strain recovery rate is 50% or more in that birefringence generated in the pressure-sensitive adhesive can be quickly eliminated and light leakage can be further reduced. It is preferable that it is 70% or more.
- the “deformation rate (%)” at a certain point in time is ⁇ circumferential movement amount M ( ⁇ m) of ⁇ 8 mm jig installed in the rheometer ⁇ / ⁇ before performing the measurement steps 1 to 3 described above.
- the thickness of the sample piece T ( ⁇ m) ⁇ ⁇ 100 (%) is assumed (see FIG. 3).
- FIG. 1 is a graph for schematically explaining the change with time of the deformation rate of the optical film pressure-sensitive adhesive composition according to this embodiment, measured using a rheometer. That is, FIG. 1 shows the results of measuring the viscoelastic properties (rheological properties) of the optical film pressure-sensitive adhesive composition according to the present embodiment by sequentially performing the measurement steps 1 to 3 using a rheometer. . That is, the deformation rate of the optical film pressure-sensitive adhesive composition according to this embodiment is a value measured using a rheometer.
- Measurement steps 1 to 3 simulate deformation that occurs over a long period of time when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive composition for optical films according to this embodiment is formed on the surface of the adherend.
- the temperature and shear stress of the sample piece are increased at a constant rate for a predetermined time (15 minutes).
- the sample piece is held under a constant temperature (80 ° C.) and a constant shear stress (1000 Pa).
- the temperature and shear stress of the sample piece are decreased at a constant rate for a predetermined time (15 minutes).
- the deformation rate continues to increase during the measurement steps 1 and 2, and the deformation rate reaches the maximum (maximum deformation rate) at the end of the measurement step 2 (the deformation at the time when the deformation rate becomes the maximum).
- the rate is the maximum deformation rate.
- the deformation rate decreases with the temperature and shear stress of the sample piece, and at the end of the measurement step 3, the deformation rate in the measurement step 3 is minimized (final deformation rate).
- a strain recovery rate is calculated from the final deformation rate and the maximum deformation rate based on the equation (1).
- the “acrylic polymer” means at least one selected from acrylic acid, acrylate, acrylate, methacrylic acid, methacrylate, and methacrylic ester in the structural unit. A polymer containing 50% by mass or more.
- “(meth) acrylic acid” is a concept including acrylic acid and methacrylic acid.
- the “crosslinkable functional group” means a functional group capable of reacting with the crosslinking agent (B), and more specifically, a hydroxyl group, a carboxyl group, an amino group, an amide group, and an acid anhydride. It means at least one group selected from the group.
- the content of the component (A) in the pressure-sensitive adhesive composition according to this embodiment can be 90 to 99.99 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition according to this embodiment. It is preferably 8 parts by mass.
- the component (A) does not have a crosslinkable functional group and has a (meth) acrylic acid ester (a1) (hereinafter referred to as a glass transition temperature (Tg) of 0 ° C. or higher. (It may be simply referred to as “component (a1)”.) (Meth) acrylic acid having 5 to 55% by mass and having no crosslinkable functional group and having a glass transition temperature (Tg) of less than 0 ° C.
- Ester (a2) (hereinafter sometimes referred to simply as “component (a2)”) 44.5 to 94.5% by mass and monomer (a3) having a crosslinkable functional group (hereinafter simply referred to as “(a3) ) Component ”)) and a polymer of a monomer mixture containing 0.5 to 6% by mass.
- Component (a1) can be, for example, a (meth) acrylic acid ester represented by the following general formula (1) and having a Tg of 0 ° C. or higher.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched alkyl group, an alicyclic group, or an aromatic ring-containing group.
- Examples of the (a1) component (meth) acrylic acid ester having a Tg of 0 ° C. or higher include methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexadecyl acrylate, n -(Meth) acrylic acid alkyl ester having a linear alkyl group at the ester site such as hexadecyl methacrylate, stearyl acrylate, stearyl methacrylate; (meth) acrylic acid alkyl ester having a branched alkyl group at the ester site such as t-butyl acrylate, i-propyl methacrylate, i-butyl methacrylate, t-butyl methacrylate; (Meth) acrylic acid alkyl ester having an alicyclic group at an ester site such as cyclohexyl acryl
- the component (a1) is a (meth) acrylic acid alkyl ester in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to the present embodiment can further reduce light leakage of the image display device.
- the alkyl chain constituting the alkyl ester moiety of the (meth) acrylic acid alkyl ester is preferably a linear or branched alkyl chain, and more preferably has a branched alkyl chain.
- the number of carbon atoms of the alkyl chain is 1 to 20 (preferably 1) in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce light leakage of the image display device. More preferably, it is ⁇ 10).
- the content of the component (a1) in the monomer mixture for obtaining the polymer as the component (A) is less than 5% by mass, light leakage may not be sufficiently suppressed. When it exceeds%, the pressure-sensitive adhesive layer becomes too hard, and the workability of sticking may deteriorate or the durability may be adversely affected.
- the content of the component (a1) in the monomer mixture for obtaining the polymer as the component (A) is 5 It is preferably ⁇ 55 mass%, more preferably 10 to 40 mass%.
- Component (a2) can be, for example, a (meth) acrylic acid ester represented by the following general formula (2) and having a Tg of less than 0 ° C.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a linear or branched alkyl group, an alicyclic group, or an aromatic ring-containing group.
- Examples of the (a) component (meth) acrylic acid ester having a Tg of less than 0 ° C. include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, and n-hexyl.
- the component (a2) is a (meth) acrylic acid alkyl ester in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce light leakage
- the alkyl chain constituting the alkyl ester moiety of the acrylic acid alkyl ester is preferably a linear or branched alkyl chain, more preferably a linear alkyl chain.
- the number of carbon atoms of the alkyl chain is 1 to 20 (preferably 1) in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce light leakage of the image display device. More preferably, it is ⁇ 10).
- the content of the component (a2) in the monomer mixture for obtaining the polymer as the component (A) is less than 44.5% by mass, the balance of the adhesive properties is lost, and the adhesion to the adherend is reduced. On the other hand, if it exceeds 94.5% by mass, light leakage may not be sufficiently suppressed.
- the content of the component (a2) in the monomer mixture for obtaining the polymer as the component (A) is 44 It is preferably from 5 to 94.5% by mass, more preferably from 50 to 89.5% by mass, and even more preferably from 60 to 86% by mass.
- the (a3) component is a monomer other than the (a1) component and the (a2) component, and has a crosslinkable functional group.
- Examples of the component (a3) include carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, N, N-dimethylaminoethyl.
- the component (a3) is preferably an alkyl (meth) acrylate and an alkyl amide having a crosslinkable functional group, or one of them in terms of excellent crosslinking performance with the crosslinking agent as the component (B). More preferably, it is at least one selected from alkyl (meth) acrylate having a hydroxyl group, acrylic acid, and alkylamide.
- the pressure-sensitive adhesive composition according to this embodiment is a content of a monomer having an alkylene oxide group in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce light leakage. Is preferably 5% by mass or less, and more preferably not containing a monomer having an alkylene oxide group.
- the reactive emulsifier which has the (meth) acryl monomer which has an alkylene oxide group in a side chain, and an alkylene oxide group is mentioned, for example.
- the pressure-sensitive adhesive composition does not contain a monomer having an alkylene oxide group
- the content of the monomer having an alkylene oxide group in the pressure-sensitive adhesive composition is 2% by mass or less.
- the content of the monomer having an alkylene oxide group in the pressure-sensitive adhesive composition is preferably 0 to 2% by mass.
- Tg In the pressure-sensitive adhesive composition according to this embodiment, by achieving the predetermined maximum deformation rate and strain recovery rate, light leakage can be prevented and durability can be enhanced. It is preferably ⁇ 70 to 0 ° C., more preferably ⁇ 40 to ⁇ 10 ° C.
- the Tg of the component (A) is a value calculated by the following formula (2) (FOX formula).
- Tg A W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 (2)
- Tg A represents the glass transition temperature (K) of the component (A)
- Tg a1 , Tg a2 , and Tg a3 were prepared from the constituent monomers (a1), (a2), and (a3), respectively.
- the glass transition temperature (Tg (K)) of the homopolymer is shown, and W a1 , W a2 and W a3 are the weights of the constituent monomers (a1), (a2) and (a3) contained in the component (A), respectively. Indicates the fraction.
- Tg A is calculated as an absolute temperature (K) by the above formula (2), it is converted to a Celsius temperature (° C.) as necessary.
- the glass transition temperatures of homopolymers prepared from typical monomers are shown in Table 1 below. More specifically, for example, Polymer Handbook 4th Edition (Polymer Handbook Third Edition, Wiley-Interscience, 2003) It is described in.
- the component (A) is The weight average molecular weight (Mw) is preferably 500,000 to 2,000,000, more preferably 800,000 to 1,800,000.
- the weight average molecular weight of the component (A) is obtained by using GPC (gel permeation chromatography) and calculating the weight average molecular weight (Mw) in terms of standard polystyrene under the following conditions.
- ⁇ GPC measurement conditions Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation) GPC column configuration: The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm 3 Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C
- the component (A) according to this embodiment preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight) determined by GPC in the range of 4 to 7.
- the gel fraction of the adhesive composition which concerns on a form is 70% or more, and it is more preferable that it is 77% or more.
- the gel fraction is, for example, the type and amount of the component (a3) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, and the crosslinking that is the component (B). It can be adjusted according to the type and amount of the agent used.
- 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 3).
- Gel fraction (%) (dry weight (2) / dry weight (1)) ⁇ 100 (3)
- the crosslinking agent as the component (B) is not particularly limited as long as it is a crosslinking agent capable of crosslinking with the component (A) at room temperature or under heating.
- the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent. Among these, an isocyanate crosslinking agent is preferable.
- isocyanate-based crosslinking agent examples include xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like,
- isocyanate compounds and isocyanurates obtained by subjecting these to addition reaction with bivalent or higher alcohol compounds such as trimethylolpropane.
- urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
- an isocyanate type crosslinking agent and an epoxy crosslinking agent can also be used together.
- the content of the component (B) in the pressure-sensitive adhesive composition according to this embodiment is based on 100 parts by mass of the pressure-sensitive adhesive composition according to this embodiment from the viewpoint of achieving a predetermined gel fraction (for example, 70% or more). 0.01 to 3 parts by mass, preferably 0.1 to 1.5 parts by mass.
- the adhesive composition for optical films which concerns on this embodiment can further contain components other than (A) component and (B) component as needed.
- the pressure-sensitive adhesive composition according to the present embodiment includes (C) a silane coupling agent (hereinafter sometimes simply referred to as “component (C)”), as long as the effects of the present invention are not impaired.
- component (D) An ionic compound (hereinafter sometimes simply referred to as “component (D)”), an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
- Component (C) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, or methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. Meta) Acrylic Copo Silane coupling agents having a functional
- the content of the component (C) in the pressure-sensitive adhesive composition for optical films according to the present embodiment is from the viewpoint of maintaining good adhesion to the adherend, and the pressure-sensitive adhesive composition for optical films according to the present embodiment.
- the amount may be 0 to 0.5 parts by mass, and preferably 0.05 to 0.3 parts by mass with respect to 100 parts by mass.
- the adhesive composition which concerns on this embodiment may contain the ionic compound (D).
- the component (D) when the pressure-sensitive adhesive composition according to the present embodiment contains the component (D), when the pressure-sensitive adhesive layer is formed on the surface of the adherend using the pressure-sensitive adhesive composition according to the present embodiment, charging of the adherend is performed. Can be effectively prevented.
- the component (D) include an ionic compound that is composed of an anion and a cation and is liquid or solid at 25 ° C., specifically, an alkali metal salt, an ionic liquid (liquid at 25 ° C. Shape), surfactants and the like.
- alkali metal salt examples include compounds comprising an alkali metal cation such as lithium, sodium and potassium and an anion.
- cation constituting the ionic liquid piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyra Zolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like.
- anions constituting the ionic liquid include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4.
- ionic compound it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC.
- ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl.
- Carbazole tetrafluoroborate 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulf
- any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
- nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyls such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether.
- Sorbitan higher fatty acid esters such as ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as id, polyoxyethylene, polyoxypropylene, polyoxyalkylenes and their block copolymers such as polyoxyethylene butylene.
- cationic surfactant examples include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkyldimethylammonium ethosulphate and the like.
- anionic surfactant examples include sodium laurate, sodium oleate, N-acyl-N-methylglycine sodium salt, sodium carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium dodecylbenzenesulfonate, dialkylsulfosuccinate.
- amphoteric surfactant examples include carboxybetaine surfactants, aminocarboxylates, imidazolinium petines, lecithins, and alkylamine oxides.
- conductive polymers, conductive carbon, ammonium chloride, aluminum chloride, copper chloride, iron chloride, ammonium sulfate, and the like can be used.
- alkali metal salts are preferable, and lithium perchlorate is particularly preferably used.
- the content of the component (D) in the optical film pressure-sensitive adhesive composition according to this embodiment can be 0 to 3 parts by mass with respect to 100 parts by mass of the optical film pressure-sensitive adhesive composition according to this embodiment. 0.05 to 2.5 parts by mass is preferable.
- the polymerization method of component (A) is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of coalesces, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
- solution polymerization generally, a predetermined organic solvent, each monomer, a polymerization initiator, and a chain transfer agent used as necessary are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
- the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha;
- aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha
- aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil;
- Esters such as
- organic solvents for polymerization in the polymerization of the component (A), it is preferable to use an organic solvent that hardly causes chain transfer during the polymerization reaction, for example, esters and ketones.
- an organic solvent that hardly causes chain transfer during the polymerization reaction for example, esters and ketones.
- use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
- organic peroxides and azo compounds that can be used in ordinary solution polymerization.
- organic peroxides include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, and di-i-propyl peroxydicarbonate.
- azo compound examples include 2,2′-azobis-i-butyronitrile, 2,2 ′. -Azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
- a polymerization initiator that does not cause a graft reaction during the polymerization reaction of component (A) is preferable, and an azo type is particularly preferable.
- the amount used is usually from 0.01 to 2 parts by weight, preferably from 0.1 to 1.0 part by weight, based on 100 parts by weight of the total amount of monomers.
- the component (A) contained in the pressure-sensitive adhesive composition of the present invention it is normal not to use a chain transfer agent, but as long as it does not impair the object and effect of the present invention. It is possible to use.
- chain transfer agents examples include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, fluorene, 9
- Aromatic compounds such as phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; benzoquinone, 2, 3, 5, Benzoquinone derivatives such as 6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloro Methane, tribromomethane
- the polymerization temperature of the component (A) is generally about 30 to 180 ° C, preferably 40 to 150 ° C, more preferably 50 to 90 ° C.
- an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
- the adhesive composition which concerns on this embodiment is normally prepared by mixing the said (A) and (B) component and arbitrary components as needed simultaneously or in arbitrary orders. Moreover, when mixing (A) component and (B) component, when preparing (A) component by solution polymerization, (B) component is added to the solution containing (A) component after the completion of polymerization. In addition, when the component (A) is prepared by bulk polymerization, uniform mixing becomes difficult after the completion of the polymerization. Therefore, it is preferable to add and mix the component (B) during the polymerization.
- the pressure-sensitive adhesive composition according to this embodiment can be suitably used as an adhesive for optical films (described in detail later). According to the pressure-sensitive adhesive composition according to the present embodiment, it exhibited excellent durability under high temperature and high humidity conditions, and was used for adhesion between an adherend such as a liquid crystal cell and an optical film such as a polarizing film. In this case, light leakage can be reduced.
- the image display device includes a retardation film, since the retardation film is provided between the liquid crystal cell and the polarizing film, the pressure-sensitive adhesive composition according to this embodiment is provided between the retardation film and the polarizing film. An adhesive layer using can be provided.
- the pressure-sensitive adhesive composition according to this embodiment is used for bonding an adherend such as a liquid crystal cell and an optical film such as a polarizing film.
- an adherend such as a liquid crystal cell
- an optical film such as a polarizing film.
- the pressure-sensitive adhesive composition according to this embodiment can be used as an adhesive having the VA mode polarizing film or the IPS mode polarizing film as an adherend, but can achieve high image quality. In this respect, it can be suitably used as an adhesive having a VA mode polarizing film as an adherend.
- the pressure-sensitive adhesive composition according to this embodiment when used as an adhesive having a VA mode polarizing film as an adherend, a large-sized (for example, 10 inches or more, preferably 19 inches or more) image display.
- the large-sized image display device When the pressure-sensitive adhesive composition according to this embodiment is used to form the adhesive layer of the device, the large-sized image display device has a large shrinkage due to the stress caused by dimensional deformation, particularly because the polarizing film has a large shrinkage.
- the influence of peeling is large, and the influence of light leakage due to the distortion of the polarization axis is large.
- the adhesive layer is useful in that it can achieve high image quality by being excellent in durability and reducing light leakage.
- the light leakage prevention property that is one function and effect of the pressure-sensitive adhesive composition according to the present embodiment is due to the following two mechanisms of action. 1stly, when the stress resulting from shrinkage
- the strain recovery rate of the pressure-sensitive adhesive composition according to the present embodiment is 50% or more, so that the pressure-sensitive adhesive composition according to the present embodiment is deformed. Therefore, the distortion of the polarization axis due to the contraction of the polarizing film is quickly restored, and as a result, the light leakage of the image display device can be reduced.
- the deformation rate of the adhesive layer is small (the adhesive composition according to this embodiment).
- the above-mentioned maximum strain rate is 10% or less
- the first characteristic that moderately suppresses the shrinkage of the optical film and the second characteristic that quickly restores the deformation of the pressure-sensitive adhesive layer (this embodiment)
- the pressure-sensitive adhesive composition according to this embodiment has both the above-described strain recovery rate of 50% or more), and the adhesive composition according to this embodiment achieves high durability of the image display device, and The light leakage of the image display device can be reduced.
- An adhesive optical film according to another embodiment of the present invention is provided with an adhesive layer containing the optical film adhesive composition according to the above embodiment on one or both sides of the optical film.
- the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition on the optical film with a gravure coater, Mayer bar coater, air knife coater, roll coater, or the like. It may be formed by drying and crosslinking the pressure-sensitive adhesive composition applied thereon at room temperature or by heating, or by forming a pressure-sensitive adhesive layer on a release film and transferring it to the optical film. Good.
- the thickness of the pressure-sensitive adhesive layer is usually about 1 to 50 ⁇ m, preferably about 5 to 30 ⁇ m.
- Examples of the pressure-sensitive adhesive optical film according to the present embodiment include those used in image display devices such as FPD, such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, and the like. It can be an optical film selected from the group consisting of light diffusing films. The thickness of the optical film can be appropriately selected depending on the purpose of use, but is usually 10 to 500 ⁇ m, preferably about 15 to 300 ⁇ m.
- the laminated body which concerns on one Embodiment of this invention is the adhesive composition for optical films which concerns on the said embodiment provided between the glass substrate, the polarizing plate, and the said glass substrate and the said polarizing plate. And a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) obtained by molding into a film and heating.
- FIG. 4 is a cross-sectional view schematically showing an example (laminated body 200) of a laminated body according to an embodiment of the present invention.
- the laminate 200 includes a glass substrate 110, a polarizing film (polarizing plate) 130, and an adhesive layer 120 provided between the glass substrate 110 and the polarizing film 130.
- the laminate 200 includes a glass substrate 110, a pressure-sensitive adhesive layer 120 provided on the glass substrate 110, and a polarizing film 130 provided on the glass substrate 110 via the pressure-sensitive adhesive layer 120. Including. The glass substrate 110 and the polarizing film 130 are bonded via an adhesive layer 120.
- the adhesive layer 120 is formed on the surface of the adherend (glass substrate 110).
- the pressure-sensitive adhesive composition according to the present embodiment on the surface of the adherend, after applying the pressure-sensitive adhesive composition to the surface of a release film (separator) with good smoothness and drying the coating film, The transfer method which transfers the said coating film to the surface of a specific resin film can be mentioned.
- the laminate according to the present embodiment is included in, for example, an image display device (particularly a liquid crystal display device).
- the glass substrate included in the laminate according to the present embodiment is a glass substrate for a liquid crystal display device.
- the glass substrate which comprises the laminated body which concerns on this embodiment can be a glass substrate used for image display apparatuses.
- the image display device can be, for example, a TFT (thin film transistor) liquid crystal display device used for a liquid crystal television, a computer monitor, a mobile phone, a tablet, and the like.
- the laminate according to the present embodiment is a glass substrate, a polarizing film, and the optical film pressure-sensitive adhesive composition according to the embodiment, which is provided between the glass substrate and the polarizing film.
- the pressure-sensitive adhesive layer obtained by molding, heating and drying appropriately excellent durability can be exhibited under high temperature and high humidity conditions, and light leakage can be reduced.
- VA liquid crystal panel made by I / O Data Co., Ltd., removed from LCD-A191EW
- peeled polyester film peeled off adhesive film for evaluation
- the layers were bonded so that the layer was in contact with the liquid crystal panel and the evaluation pressure-sensitive adhesive-processed polarizing plate was crossed Nicol, and allowed to stand for 240 hours in an atmosphere at 80 ° C. And left for 2 hours. Thereafter, the VA liquid crystal panel on which the polarizing plate was bonded was connected to a personal computer in a dark room to display a full screen black.
- evaluation was performed using two types of light source (backlight), LED (LED method) and fluorescent lamp (non-LED method). As shown in FIG.
- R the range where light leakage occurred near the corner of the display monitor was visually measured.
- R is less than 20 mm, it can be used as a liquid crystal display panel.
- the adhesive processing polarizing plate for evaluation which peeled off the peeled polyester film was cut into a 15 inch size (233 mm ⁇ 309 mm), and an adhesive layer was formed on one surface of a non-alkali glass plate having a thickness of 0.5 mm. It stuck using the laminator roll so that the said glass plate might be touched. After pasting, a test plate was obtained by pressurizing in an autoclave (manufactured by Kurihara Seisakusho) under conditions of 0.5 MPa, 50 ° C., and 20 minutes. The test plate thus obtained was left under conditions of 60 ° C./90% RH for 500 hours.
- test plate After completion of the test, the test plate is taken out from the test environment and left to stand for 2 hours in a 23 ° C./50% RH atmosphere, and then visually observed for foaming (cohesion insufficient) and tearing (overcrosslinking) in the adhesive layer
- the wet heat durability was evaluated according to the following evaluation criteria.
- Foaming-Size No foaming is observed ⁇ : Foam diameter is 1 mm or less ⁇ : Foam diameter is greater than 1 mm
- Foaming-generation amount No foaming is observed ⁇ : The number of foams is 10 or less ⁇ : The number of foams is more than 10
- the compositions of Examples 1 to 15 were obtained using the compositions having a maximum deformation rate of 10% or less and a strain recovery rate of 50% or more.
- the pressure-sensitive adhesive composition according to the present embodiment has both the first characteristic in which the adhesive layer is appropriately suppressed from shrinkage of the optical film and the second characteristic in which deformation of the pressure-sensitive adhesive layer is quickly restored. By providing, high adhesive strength and excellent durability can be realized, and light leakage can be reduced.
- the compositions of Comparative Examples 1 to 6 do not satisfy both the maximum deformation rate of 10% or less and the strain recovery rate of 50% or more. It can be understood that the adhesive layer obtained by using the above does not achieve the first characteristic and the second characteristic at the same time, and therefore the light leakage cannot be sufficiently reduced.
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Abstract
Description
最大変形率:前記光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、レオメーターを用いて下記測定工程1ないし3を順に行った場合において、変形率が最大となる時点の変形率(%)
最終変形率:レオメーターを用いて下記測定工程1ないし3を順に行った後の該試験片の変形率(%)
歪み復元率:前記光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、下記式(1)に基づいて算出された値
歪み復元率(%)=(最大変形率-最終変形率)/最大変形率×100・・・(1)
測定工程1:前記試料片の温度を23℃から80℃まで15分間一定速度で増加させつつ、該試料片の剪断応力を0Paから1000Paまで15分間一定速度で増加させる
測定工程2:前記試料片の温度を80℃で30分間保持しつつ、剪断応力を1000Paから2000Paまで30分間一定速度で増加させる
測定工程3:前記試料片の温度を80℃から23℃まで15分間一定速度で減少させつつ、該試料片の剪断応力を2000Paから0Paまで15分間一定速度で減少させる 1. The pressure-sensitive adhesive composition for an optical film according to an aspect of the present invention includes an acrylic polymer (A) having a crosslinkable functional group and a crosslinker (B), and has a maximum deformation rate defined below of 10%. The strain recovery rate defined below is 50% or more.
Maximum deformation rate: For a test piece obtained by cutting a 1 mm thick adhesive sheet obtained by applying the optical film adhesive composition on a flat plate and drying it to Φ8 mm, using a rheometer, the following measurement step Deformation rate (%) at the time when the deformation rate becomes maximum when performing 1 to 3 in order
Final deformation ratio: Deformation ratio (%) of the test piece after performing the following
Strain recovery rate: About the test piece obtained by cutting the adhesive sheet of 1 mm thickness obtained by applying the adhesive composition for optical film on a flat plate and drying it to Φ8 mm, based on the following formula (1) Calculated value
Strain recovery rate (%) = (maximum deformation rate−final deformation rate) / maximum deformation rate × 100 (1)
Measurement step 1: While increasing the temperature of the sample piece from 23 ° C. to 80 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is increased from 0 Pa to 1000 Pa at a constant rate for 15 minutes.
Measurement step 2: Increase the shear stress from 1000 Pa to 2000 Pa at a constant rate for 30 minutes while maintaining the temperature of the sample piece at 80 ° C. for 30 minutes.
Measurement step 3: While decreasing the temperature of the sample piece from 80 ° C. to 23 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is reduced from 2000 Pa to 0 Pa at a constant rate for 15 minutes.
前記架橋性官能基を有するアクリル系ポリマー(A)が、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃以上の(メタ)アクリル酸エステル(a1)5~55質量%と、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃未満の(メタ)アクリル酸エステル(a2)44.5~94.5質量%と、
架橋性官能基を有するモノマー(a3)0.5~6質量%と、
を含むモノマー混合物の重合体であって(ここで、前記モノマー混合物中における前記(a1)、(a2)および(a3)の合計量は90~100質量%である。)、ゲル分率70%以上であることができる。 7). The pressure-sensitive adhesive composition for an optical film according to another aspect of the present invention includes an acrylic polymer (A) having a crosslinkable functional group, and a crosslinker (B).
The acrylic polymer (A) having the crosslinkable functional group is
5 to 55% by mass of (meth) acrylic acid ester (a1) having no crosslinkable functional group and having a glass transition temperature (Tg) of 0 ° C. or higher;
(Meth) acrylic acid ester (a2) having no crosslinkable functional group and having a glass transition temperature (Tg) of less than 0 ° C. (44.5 to 94.5% by mass);
0.5-6 mass% of monomer (a3) having a crosslinkable functional group;
(Wherein the total amount of the (a1), (a2) and (a3) in the monomer mixture is 90 to 100% by mass), and the gel fraction is 70%. That can be the end.
本発明の一実施形態に係る光学フィルム用粘着剤組成物(以下、単に「粘着剤組成物」と記載する場合もある。)は、架橋性官能基を有するアクリル系ポリマー(A)(以下、単に「(A)成分」と記載する場合もある。)と、架橋剤(B)(以下、単に「(B)成分」と記載する場合もある。)と、を含む。 1. Optical film pressure-sensitive adhesive composition An optical film pressure-sensitive adhesive composition according to an embodiment of the present invention (hereinafter, sometimes simply referred to as “pressure-sensitive adhesive composition”) is an acrylic resin having a crosslinkable functional group. Polymer (A) (hereinafter sometimes simply referred to as “component (A)”) and crosslinking agent (B) (hereinafter sometimes simply referred to as “component (B)”). Including.
最大変形率:前記光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、レオメーターを用いて下記測定工程1ないし3を順に行った場合において、変形率が最大となる時点の変形率(%)
最終変形率:レオメーターを用いて下記測定工程1ないし3を順に行った後の該試験片の変形率(%)
歪み復元率:本実施形態に係る光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、下記式(1)に基づいて算出された値
歪み復元率(%)=(最大変形率-最終変形率)/最大変形率×100・・・(1)
測定工程1:前記試料片の温度を23℃から80℃まで15分間一定速度で増加させつつ、該試料片の剪断応力を0Paから1000Paまで15分間一定速度で増加させる
測定工程2:前記試料片の温度を80℃で30分間保持しつつ、剪断応力を1000Paから2000Paまで30分間一定速度で増加させる
測定工程3:前記試料片の温度を80℃から23℃まで15分間一定速度で減少させつつ、該試料片の剪断応力を2000Paから0Paまで15分間一定速度で減少させる The pressure-sensitive adhesive composition for an optical film according to this embodiment has a maximum deformation rate defined below of 10% or less and a strain recovery rate defined below of 50% or more.
Maximum deformation rate: For a test piece obtained by cutting a 1 mm thick adhesive sheet obtained by applying the optical film adhesive composition on a flat plate and drying it to Φ8 mm, using a rheometer, the following measurement step Deformation rate (%) at the time when the deformation rate becomes maximum when performing 1 to 3 in order
Final deformation ratio: Deformation ratio (%) of the test piece after performing the following
Strain recovery rate: For a test piece obtained by cutting an adhesive sheet having a thickness of 1 mm obtained by applying and drying the adhesive composition for an optical film according to the present embodiment on a flat plate to Φ8 mm, the following formula (1 ) Calculated based on
Strain recovery rate (%) = (maximum deformation rate−final deformation rate) / maximum deformation rate × 100 (1)
Measurement step 1: While increasing the temperature of the sample piece from 23 ° C. to 80 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is increased from 0 Pa to 1000 Pa at a constant rate for 15 minutes.
Measurement step 2: Increase the shear stress from 1000 Pa to 2000 Pa at a constant rate for 30 minutes while maintaining the temperature of the sample piece at 80 ° C. for 30 minutes.
Measurement step 3: While decreasing the temperature of the sample piece from 80 ° C. to 23 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is reduced from 2000 Pa to 0 Pa at a constant rate for 15 minutes.
本発明における「最大変形率」は、粘着剤組成物の変形しやすさの指標であり、最大変形率が大きいほど、粘着剤組成物が変形しやすいといえる。本実施形態に係る光学フィルム用粘着剤組成物において、前記最大変形率が10%を超えると、粘着剤の被着体の膨張または収縮に粘着剤層が追従できない結果、粘着剤層に複屈折が生じ、光漏れを防止できない場合がある。本実施形態に係る光学フィルム用粘着剤組成物において、粘着剤に生じる複屈折をより確実に防止して、光漏れをより低減することができる点で、前記最大歪み率は10%以下であることが好ましく、8%以下であることがより好ましい。 1.1. Maximum Deformation Rate and Strain Restoration Rate The “maximum deformation rate” in the present invention is an index of the ease of deformation of the pressure-sensitive adhesive composition. It can be said that the larger the maximum deformation rate, the easier the pressure-sensitive adhesive composition is deformed. In the pressure-sensitive adhesive composition for an optical film according to this embodiment, if the maximum deformation rate exceeds 10%, the pressure-sensitive adhesive layer cannot follow the expansion or contraction of the pressure-sensitive adhesive adherend. May occur, preventing light leakage. In the pressure-sensitive adhesive composition for an optical film according to the present embodiment, the maximum strain rate is 10% or less in that birefringence generated in the pressure-sensitive adhesive can be more reliably prevented and light leakage can be further reduced. It is preferably 8% or less.
本発明において、「アクリル系ポリマー」とは、アクリル酸、アクリル酸塩、アクリル酸エステル、メタアクリル酸、メタクリル酸塩、およびメタクリル酸エステルから選ばれる少なくとも1種を構成単位中に50質量%以上含むポリマーをいう。また、本発明において、「(メタ)アクリル酸」とは、アクリル酸およびメタアクリル酸を含む概念である。また、本発明において、「架橋性官能基」とは、架橋剤(B)と反応し得る官能基をいい、より具体的には、水酸基、カルボキシル基、アミノ基、アミド基、および酸無水物基から選ばれる少なくとも1種の基をいう。 1.2. (A) Component In the present invention, the “acrylic polymer” means at least one selected from acrylic acid, acrylate, acrylate, methacrylic acid, methacrylate, and methacrylic ester in the structural unit. A polymer containing 50% by mass or more. In the present invention, “(meth) acrylic acid” is a concept including acrylic acid and methacrylic acid. In the present invention, the “crosslinkable functional group” means a functional group capable of reacting with the crosslinking agent (B), and more specifically, a hydroxyl group, a carboxyl group, an amino group, an amide group, and an acid anhydride. It means at least one group selected from the group.
(a1)成分は例えば、下記一般式(1)で表される、Tgが0℃以上の(メタ)アクリル酸エステルであることができる。 1.2.1. Component (a1) The component (a1) can be, for example, a (meth) acrylic acid ester represented by the following general formula (1) and having a Tg of 0 ° C. or higher.
t-ブチルアクリレート、i-プロピルメタクリレート、i-ブチルメタクリレート、t-ブチルメタクリレート等のエステル部位に分岐状アルキル基を有する(メタ)アクリル酸アルキルエステル;
シクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート等のエステル部位に脂環基を有する(メタ)アクリル酸アルキルエステル;
ベンジルメタクリレート、ベンジルアクリレート、2-ナフチルアクリレート等のエステル部位に芳香環基を有する(メタ)アクリル酸アルキルエステルが挙げられ、このうち1種を単独でまたは2種以上を組み合わせて使用することができる。このうち、本実施形態に係る粘着剤組成物を用いて形成された粘着剤層が画像表示装置の光漏れをより低減できる点で、(a1)成分は(メタ)アクリル酸アルキルエステルであって、該(メタ)アクリル酸アルキルエステルのアルキルエステル部位を構成するアルキル鎖が直鎖状または分岐状のアルキル鎖であることが好ましく、分岐状のアルキル鎖を有することがより好ましい。この場合、本実施形態に係る粘着剤組成物を用いて形成された粘着剤層が画像表示装置の光漏れをさらに低減できる点で、前記アルキル鎖の炭素原子数は1~20(好ましくは1~10)であることがさらに好ましい。 Examples of the (a1) component (meth) acrylic acid ester having a Tg of 0 ° C. or higher include methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexadecyl acrylate, n -(Meth) acrylic acid alkyl ester having a linear alkyl group at the ester site such as hexadecyl methacrylate, stearyl acrylate, stearyl methacrylate;
(meth) acrylic acid alkyl ester having a branched alkyl group at the ester site such as t-butyl acrylate, i-propyl methacrylate, i-butyl methacrylate, t-butyl methacrylate;
(Meth) acrylic acid alkyl ester having an alicyclic group at an ester site such as cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate;
(Meth) acrylic acid alkyl ester having an aromatic ring group at the ester site such as benzyl methacrylate, benzyl acrylate, 2-naphthyl acrylate, etc., among which one can be used alone or two or more can be used in combination. . Among these, the component (a1) is a (meth) acrylic acid alkyl ester in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to the present embodiment can further reduce light leakage of the image display device. The alkyl chain constituting the alkyl ester moiety of the (meth) acrylic acid alkyl ester is preferably a linear or branched alkyl chain, and more preferably has a branched alkyl chain. In this case, the number of carbon atoms of the alkyl chain is 1 to 20 (preferably 1) in that the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition according to this embodiment can further reduce light leakage of the image display device. More preferably, it is ~ 10).
(a2)成分は例えば、下記一般式(2)で表される、Tgが0℃未満の(メタ)アクリル酸エステルであることができる。 1.2.2. Component (a2) The component (a2) can be, for example, a (meth) acrylic acid ester represented by the following general formula (2) and having a Tg of less than 0 ° C.
(a3)成分は、(a1)成分および(a2)成分以外の単量体であって、架橋性官能基を有する。(a3)成分としては、例えば、カルボキシエチルアクリレート、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート
、2-ヒドロキシプロピルアクリレート、2-ヒドロキシプロピルメタクリレート、4-ヒドロキシブチルアクリレート、N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノエチルメタクリレート、N,N-ジエチルアミノエチルメタクリレート、アクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、アクリルアマイド、アクリロニトリルが挙げられ、このうち、架橋性官能基を有するモノマーを必須とする1種または2種以上を組み合わせて使用することができる。このうち、(a3)成分は、(B)成分である架橋剤との架橋性能に優れる点で、架橋性官能基を有するアルキル(メタ)アクリレートおよびアルキルアマイドあるいはいずれか一方であることが好ましく、水酸基を有するアルキル(メタ)アクリレート、アクリル酸、およびアルキルアマイドから選ばれる少なくとも1種であることがより好ましい。 1.2.3. (A3) Component The (a3) component is a monomer other than the (a1) component and the (a2) component, and has a crosslinkable functional group. Examples of the component (a3) include carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, N, N-dimethylaminoethyl. Acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, acrylamide, N, N-dimethylaminopropyl acrylamide, acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, acrylonitrile, Among these, it can be used combining 1 type (s) or 2 or more types which essentially require the monomer which has a crosslinkable functional group. Among these, the component (a3) is preferably an alkyl (meth) acrylate and an alkyl amide having a crosslinkable functional group, or one of them in terms of excellent crosslinking performance with the crosslinking agent as the component (B). More preferably, it is at least one selected from alkyl (meth) acrylate having a hydroxyl group, acrylic acid, and alkylamide.
本実施形態に係る粘着剤組成物では、所定の最大変形率および歪み復元率を達成できる観点から、(A)成分である重合体を得るための前記モノマー混合物中における前記(a1)成分、(a2)成分および(a3)成分の合計量が90~100質量%であることができ、95~100質量%であることが好ましい。 1.2.4. The total amount of the component (a1), the component (a2), and the component (a3) In the pressure-sensitive adhesive composition according to this embodiment, from the viewpoint of achieving a predetermined maximum deformation rate and strain recovery rate, The total amount of the component (a1), the component (a2) and the component (a3) in the monomer mixture for obtaining a coalescence can be 90 to 100% by mass, and preferably 95 to 100% by mass. .
本実施形態に係る粘着剤組成物では、所定の最大変形率および歪み復元率を達成することにより、光漏れを防止し、かつ耐久性を高めることができる観点から、(A)成分のTgは-70~0℃であることが好ましく、-40~-10℃であることがより好ましい。なお、本発明において、(A)成分のTgは、下記式(2)(FOXの式)により算出された値である。 1.2.5. Tg
In the pressure-sensitive adhesive composition according to this embodiment, by achieving the predetermined maximum deformation rate and strain recovery rate, light leakage can be prevented and durability can be enhanced. It is preferably −70 to 0 ° C., more preferably −40 to −10 ° C. In the present invention, the Tg of the component (A) is a value calculated by the following formula (2) (FOX formula).
(式中、TgAは、(A)成分のガラス転移温度(K)を示し、Tga1,Tga2,Tga3はそれぞれ、構成モノマー(a1),(a2),(a3)から調製されたホモポリマーのガラス転移温度(Tg(K))を示し、Wa1,Wa2,Wa3はそれぞれ、(A)成分中に含まれる、構成モノマー(a1),(a2),(a3)の重量分率を示す。)
なお、上記式(2)により、TgAは、絶対温度(K)として算出されるので、必要に応じて摂氏温度(℃)に換算される。 1 / Tg A = W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 (2)
(In the formula, Tg A represents the glass transition temperature (K) of the component (A), and Tg a1 , Tg a2 , and Tg a3 were prepared from the constituent monomers (a1), (a2), and (a3), respectively. The glass transition temperature (Tg (K)) of the homopolymer is shown, and W a1 , W a2 and W a3 are the weights of the constituent monomers (a1), (a2) and (a3) contained in the component (A), respectively. Indicates the fraction.)
In addition, since Tg A is calculated as an absolute temperature (K) by the above formula (2), it is converted to a Celsius temperature (° C.) as necessary.
また、本実施形態に係る粘着剤組成物において、所定の最大変形率および歪み復元率を達成することにより、光漏れを防止し、かつ耐久性を高めることができる観点から、(A)成分は、重量平均分子量(Mw)が50万~200万であることが好ましく、80万~180万であることがより好ましい。ここで、(A)成分の重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)を用い、下記の条件で標準ポリスチレン換算による重量平均分子量(Mw)を求めたものである。
<GPC測定条件>
測定装置:HLC-8120GPC(東ソー社製)
GPCカラム構成:以下の5連カラム(すべて東ソー社製)
(1)TSK-GEL HXL-H (ガードカラム)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
サンプル濃度:1.0mg/cm3 となるように、テトラヒドロフランで希釈
移動相溶媒:テトラヒドロフラン
流量:1.0cm3/min
カラム温度:40℃
また、本実施形態にかかる(A)成分は、上記GPCにより求められる分子量分布(重量平均分子量/数平均分子量)が4~7の範囲にあることが好ましい。 1.2.6. Weight average molecular weight (Mw)
In addition, in the pressure-sensitive adhesive composition according to this embodiment, from the viewpoint of preventing light leakage and increasing durability by achieving predetermined maximum deformation rate and strain recovery rate, the component (A) is The weight average molecular weight (Mw) is preferably 500,000 to 2,000,000, more preferably 800,000 to 1,800,000. Here, the weight average molecular weight of the component (A) is obtained by using GPC (gel permeation chromatography) and calculating the weight average molecular weight (Mw) in terms of standard polystyrene under the following conditions.
<GPC measurement conditions>
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC column configuration: The following five columns (all manufactured by Tosoh Corporation)
(1) TSK-GEL HXL-H (guard column)
(2) TSK-GEL G7000HXL
(3) TSK-GEL GMHXL
(4) TSK-GEL GMHXL
(5) TSK-GEL G2500HXL
Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm 3 Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 cm 3 / min
Column temperature: 40 ° C
The component (A) according to this embodiment preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight) determined by GPC in the range of 4 to 7.
さらに、本実施形態に係る粘着剤組成物において、所定の最大変形率および歪み復元率を達成することにより、光漏れを防止し、かつ耐久性を高めることができる観点から、本実施形態に係る粘着剤組成物のゲル分率が70%以上であることが好ましく、77%以上であることがより好ましい。 1.2.7. Gel fraction Further, in the pressure-sensitive adhesive composition according to the present embodiment, by achieving the predetermined maximum deformation rate and strain recovery rate, it is possible to prevent light leakage and enhance durability. It is preferable that the gel fraction of the adhesive composition which concerns on a form is 70% or more, and it is more preferable that it is 77% or more.
ゲル分率(%)=(乾燥重量(2)/乾燥重量(1))×100 ・・・(3) In the pressure-sensitive adhesive composition according to this embodiment, the gel fraction is, for example, the type and amount of the component (a3) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, and the crosslinking that is the component (B). It can be adjusted according to the type and amount of the agent used. As for the gel fraction, 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 3).
Gel fraction (%) = (dry weight (2) / dry weight (1)) × 100 (3)
本実施形態に係る粘着剤組成物において、(B)成分である架橋剤は、常温又は加熱下で(A)成分と架橋し得る架橋剤であれば特に限定されないが、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレ―ト架橋剤が挙げられ、このうち、イソシアネート系架橋剤が好ましい。 1.3. (B) Component In the pressure-sensitive adhesive composition according to the present embodiment, the crosslinking agent as the component (B) is not particularly limited as long as it is a crosslinking agent capable of crosslinking with the component (A) at room temperature or under heating. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, and a metal chelate crosslinking agent. Among these, an isocyanate crosslinking agent is preferable.
本実施形態に係る光学フィルム用粘着剤組成物は、必要に応じて、(A)成分および(B)成分以外の成分をさらに含むことができる。例えば、本実施形態に係る粘着剤組成物には、本発明の効果を損なわない範囲で、(C)シランカップリング剤(以下、単に「(C)成分」と記載することもある。)、(D)イオン性化合物(以下、単に「(D)成分」と記載する場合もある。)、酸化防止剤、紫外線吸収剤、粘着付与剤、可塑剤等が配合されていても良い。 1.4. Other components The adhesive composition for optical films which concerns on this embodiment can further contain components other than (A) component and (B) component as needed. For example, the pressure-sensitive adhesive composition according to the present embodiment includes (C) a silane coupling agent (hereinafter sometimes simply referred to as “component (C)”), as long as the effects of the present invention are not impaired. (D) An ionic compound (hereinafter sometimes simply referred to as “component (D)”), an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
本実施形態に係る光学フィルム用粘着剤組成物が(C)成分を含むことにより、本実施形態に係る光学フィルム用粘着剤組成物を用いて被着体の表面に粘着剤層を形成した場合、被着体との接着を良好に保つことができる。(C)成分は例えば、ビニルトリメトキシシラン,ビニルトリエトキシシラン及びメタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有ケイ素化合物;3-グリシドキシプロピルトリメトキシシラン,3-グリシドキシプロピルメチルジメトキシシラン及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ構造を有するケイ素化合物;3-アミノプロピルトリメトキシシラン,N-(2-アミノエチル)3-アミノプロピルトリメトキシシラン及びN-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン等のアミノ基含有ケイ素化合物;並びに3-クロロプロピルトリメトキシシラン;オリゴマー型シランカップリング剤等であってもよく、中でも、(メタ)アクリル系コポリマー(A)中に含まれる官能基と反応する官能基を有しているシランカップリング剤が湿熱環境下でハガレを生じさせにくいという点で好ましい。 1.4.1. (C) Silane coupling agent When the pressure-sensitive adhesive composition for an optical film according to this embodiment contains the component (C), the surface of the adherend is used with the pressure-sensitive adhesive composition for an optical film according to this embodiment. When the pressure-sensitive adhesive layer is formed, good adhesion with the adherend can be maintained. Component (C) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, or methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. Meta) Acrylic Copo Silane coupling agents having a functional group reactive with the functional group contained in the mer (A) is preferable because hardly cause peeling in wet heat environment.
また、本実施形態に係る粘着剤組成物は、イオン性化合物(D)を含んでいてもよい。本実施形態に係る粘着剤組成物が(D)成分を含むことにより、本実施形態に係る粘着剤組成物を用いて被着体の表面に粘着剤層を形成した場合、被着体の帯電を効果的に防止することができる。(D)成分としては、例えば、アニオンとカチオンとからなる、25℃で液体状、または固体状のイオン性化合物が挙げられ、具体的には、アルカリ金属塩、イオン性液体(25℃で液体状)、界面活性剤等が挙げられる。 1.4.2. (D) Ionic compound Moreover, the adhesive composition which concerns on this embodiment may contain the ionic compound (D). When the pressure-sensitive adhesive composition according to the present embodiment contains the component (D), when the pressure-sensitive adhesive layer is formed on the surface of the adherend using the pressure-sensitive adhesive composition according to the present embodiment, charging of the adherend is performed. Can be effectively prevented. Examples of the component (D) include an ionic compound that is composed of an anion and a cation and is liquid or solid at 25 ° C., specifically, an alkali metal salt, an ionic liquid (liquid at 25 ° C. Shape), surfactants and the like.
ダゾリウムブロミド、1-へキシル-3-メチルイミダゾリウムクロライド、1-へキシル-3-メチルイミダゾリウムテトラフルオロボレート、1-へキシル-3-メチルイミダゾリウムヘキサフルオロホスフェート、1-へキシル-3-メチルイミダゾリウムトリフルオロメタンスルホネート、1-オクチル-3-メチルイミダゾリウムテトラフルオロボレート、1-オクチル-3-メチルイミダゾリウムヘキサフルオロホスフェート、1-へキシル-2,3-ジメチルイミダゾリウムテトラフルオロボレート、1,2-ジメチル-3-プロピルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド、1-メチルピラゾリウムテトラフルオロボレート、3-メチルピラゾリウムテトラフルオロボレート、テトラヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、ジアリルジメチルアンモニウムテトラフルオロボレート、ジアリルジメチルアンモニウムトリフルオロメタンスルホネート、ジアリルジメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、ジアリルジメチルアンモニウムビス(ペンタフルオロエタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムテトラフルオロボレート、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムトリフルオロメタンスルホネート、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウムビス(ペンタフルオロエタンスルホニル)イミド、グリシジルトリメチルアンモニウムトリフルオロメタンスルホネート、グリシジルトリメチルアンモニウムビス(トリフルオロメタンスルホニル
)イミド、グリシジルトリメチルアンモニウムビス(ペンタフルオロエタンスルホニル)イミド、1-ブチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-ブチル-3-メチルピリジニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、1-エチル-3-メチルイミダゾリウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、ジアリルジメチルアンモニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、グリシジルトリメチルアンモニウム(トリフルオロメタンスルホニル)トリフルオロアセトアミド、N,N-ジメチル-N-エチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-エチル-N-ノニルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ブチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-プロピル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ブチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N-ペンチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジメチル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリメチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-プロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-メチル-N-ヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジエチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルプロピルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリエチルペンチルアンモニウムビス(トリフルオロメタンスルホ
ニル)イミド、トリエチルヘプチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-エチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N-ブチル-N-へキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジプロピル-N,N-ジヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N,N-ジブチル-N-メチル-N-ヘキシルアンモニウムビス(トリフルオロメタンスルホニル)イミド、トリオクチルメチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、N-メチル-N-エチル-N-プロピル-N-ペンチルアンモニウムビス(トリフルオロメタンスルホニル)イミド等が挙げられる。 And as said ionic compound, it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC. Specific examples of such ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl. Carbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluoro 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis ( Trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl- 3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1 -Hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3- Methyl pyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (penta Fluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethane Sulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethyl Ammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium ( Trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) an Ni (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-propylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-he Ptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- -Butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexyl Ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl- N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl -N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluorome Tansulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide and the like.
(A)成分の重合方法は、特に制限されるものではなく、溶液重合、乳化重合、懸濁重合などの公知の方法により重合できるが、重合により得られた共重合体の混合物を用いて、本発明の粘着剤組成物を製造するにあたり、処理工程が比較的簡単でかつ短時間で行える観点から、溶液重合により重合することが好ましい。 1.5. (A) Polymerization Method of Component (A) The polymerization method of component (A) is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of coalesces, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
本実施形態に係る粘着剤組成物は、通常、前記(A)および(B)成分および必要に応じて任意成分を、同時にあるいは任意の順番で混合して調製される。また、(A)成分と(B)成分とを混合するにあたり、(A)成分を溶液重合により調製した場合は、重合完了後の(A)成分を含む溶液に(B)成分を添加してもよく、(A)成分を塊状重合により調製する場合は、重合完了後では均一混合が困難になるため、この重合の途中で(B)成分を添加して混合することが好ましい。 1.6. Manufacture of an adhesive composition The adhesive composition which concerns on this embodiment is normally prepared by mixing the said (A) and (B) component and arbitrary components as needed simultaneously or in arbitrary orders. Moreover, when mixing (A) component and (B) component, when preparing (A) component by solution polymerization, (B) component is added to the solution containing (A) component after the completion of polymerization. In addition, when the component (A) is prepared by bulk polymerization, uniform mixing becomes difficult after the completion of the polymerization. Therefore, it is preferable to add and mix the component (B) during the polymerization.
本実施形態に係る粘着剤組成物は、光学フィルム(詳しくは後述する)の接着剤として好適に用いることができる。本実施形態に係る粘着剤組成物によれば、高温および多湿条件下で優れた耐久性を発揮し、かつ、液晶セル等の被着体と偏光フィルム等の光学フィルムとの接着に使用された場合、光漏れを低減することができる。なお、画像表示装置が位相差フィルムを含む場合、液晶セルと偏光フィルムとの間に位相差フィルムが設けられるため、位相差フィルムと偏光フィルムとの間に、本実施形態に係る粘着剤組成物を用いた接着剤層を設けることができる。 1.7. Applications and operational effects The pressure-sensitive adhesive composition according to this embodiment can be suitably used as an adhesive for optical films (described in detail later). According to the pressure-sensitive adhesive composition according to the present embodiment, it exhibited excellent durability under high temperature and high humidity conditions, and was used for adhesion between an adherend such as a liquid crystal cell and an optical film such as a polarizing film. In this case, light leakage can be reduced. When the image display device includes a retardation film, since the retardation film is provided between the liquid crystal cell and the polarizing film, the pressure-sensitive adhesive composition according to this embodiment is provided between the retardation film and the polarizing film. An adhesive layer using can be provided.
2.1.粘着型光学フィルム
本発明の別の一実施形態に係る粘着型光学フィルムは、上記実施形態に係る光学フィルム用粘着剤組成物を含む粘着剤層を、光学フィルムの片面または両面に設える。本実施形態に係る粘着型光学フィルムを作製するにあたり、上記粘着剤層は、光学フィルム上に、上記粘着剤組成物をグラビアコーター、メイヤーバーコーター、エアナイフコーター、ロールコーター等により塗布し、光学フィルム上に塗布された粘着剤組成物を常温または加熱により乾燥および架橋して形成されてもよく、または、粘着剤層を剥離フィルム上に設け、これを上記光学フィルムに転写して形成されてもよい。また、粘着剤層の厚みは、通常は1~50μm、好ましくは5~30μm程度である。なお、粘着型光学フィルムの使用前に、粘着剤層を保護するために、該粘着剤層の表面に剥離フィルムを積層させてもよい。 2. 2. Adhesive optical film and laminate 2.1. Adhesive Optical Film An adhesive optical film according to another embodiment of the present invention is provided with an adhesive layer containing the optical film adhesive composition according to the above embodiment on one or both sides of the optical film. In producing the pressure-sensitive adhesive optical film according to the present embodiment, the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition on the optical film with a gravure coater, Mayer bar coater, air knife coater, roll coater, or the like. It may be formed by drying and crosslinking the pressure-sensitive adhesive composition applied thereon at room temperature or by heating, or by forming a pressure-sensitive adhesive layer on a release film and transferring it to the optical film. Good. The thickness of the pressure-sensitive adhesive layer is usually about 1 to 50 μm, preferably about 5 to 30 μm. In addition, in order to protect an adhesive layer before using an adhesive optical film, you may laminate | stack a peeling film on the surface of this adhesive layer.
本発明の一実施形態に係る積層体は、ガラス基板と、偏光板と、前記ガラス基板と前記偏光板との間に設けられた、上記実施形態に係る光学フィルム用粘着剤組成物を膜状に成形し、加熱して得られる粘着剤層(粘着シート)と、を含む。 2.2. Laminated body The laminated body which concerns on one Embodiment of this invention is the adhesive composition for optical films which concerns on the said embodiment provided between the glass substrate, the polarizing plate, and the said glass substrate and the said polarizing plate. And a pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) obtained by molding into a film and heating.
図4は、本発明の一実施形態に係る積層体の一例(積層体200)を模式的に示す断面図である。積層体200は、図1に示されるように、ガラス基板110と、偏光フィルム(偏光板)130と、ガラス基板110と偏光フィルム130との間に設けられた粘着剤層120と、を含む。 2.2.1. Laminated Structure FIG. 4 is a cross-sectional view schematically showing an example (laminated body 200) of a laminated body according to an embodiment of the present invention. As shown in FIG. 1, the laminate 200 includes a
本実施形態に係る積層体を構成するガラス基板は、画像表示装置用に用いられるガラス基板であることができる。画像表示装置としては、例えば、液晶テレビ、コンピュータのモニタ、携帯電話、タブレットなどに用いられるTFT(薄膜トランジスタ)液晶表示装置であることができる。 2.2.2. Glass substrate The glass substrate which comprises the laminated body which concerns on this embodiment can be a glass substrate used for image display apparatuses. The image display device can be, for example, a TFT (thin film transistor) liquid crystal display device used for a liquid crystal television, a computer monitor, a mobile phone, a tablet, and the like.
本実施形態に係る積層体は、ガラス基板と、偏光フィルムと、前記ガラス基板と前記偏光フィルムとの間に設けられた、上記実施形態に係る光学フィルム用粘着剤組成物を膜状に成形し、適宜加熱、乾燥して得られる粘着剤層と、を含むことにより、高温多湿条件下で優れた耐久性を発揮し、かつ、光漏れを低減することができる。 2.2.3. Effect The laminate according to the present embodiment is a glass substrate, a polarizing film, and the optical film pressure-sensitive adhesive composition according to the embodiment, which is provided between the glass substrate and the polarizing film. By including the pressure-sensitive adhesive layer obtained by molding, heating and drying appropriately, excellent durability can be exhibited under high temperature and high humidity conditions, and light leakage can be reduced.
以下、本発明を下記実施例に基づいて説明するが、本発明は実施例に限定されない。 3. EXAMPLES Hereinafter, the present invention will be described based on the following examples, but the present invention is not limited to the examples.
攪拌機、還流冷却器、温度計および窒素導入管を備えた反応装置に、下記表2および表3に示す配合比率を有するモノマー混合物を仕込み、次に、酢酸エチルをモノマー濃度が50質量%になる配合量にて仕込んだ。次に、アゾビスイソブチロニトリル0.1質量部を加え、反応容器内の空気を窒素ガスで置換しながら撹拌を行い60℃に昇温した後、4時間反応させた。反応終了後、酢酸エチルで希釈して、(A)成分(アクリル系ポリマーA~L)を得た。 3.1. (A) Preparation of component A reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube was charged with a monomer mixture having the blending ratio shown in Tables 2 and 3 below, and then ethyl acetate was added to the monomer concentration. Was added in an amount of 50% by mass. Next, 0.1 part by mass of azobisisobutyronitrile was added, the mixture was stirred while the air in the reaction vessel was replaced with nitrogen gas, and the temperature was raised to 60 ° C., followed by reaction for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate to obtain component (A) (acrylic polymers A to L).
上記3.1.で得られた(A)成分を用いて、下記表3および表4の配合(固形分配合)にて各成分を添加して、実施例1~15および比較例1~5の粘着剤組成物の溶液を得た。この粘着剤組成物の溶液を剥離処理したポリエステルフィルムの表面に塗布して乾燥させることにより、厚さ20μmの粘着剤層を有する粘着シートを得た。この粘着シートをVAモード用偏光フィルムの片面に貼り付けた後、23℃/50%RHの条件で暗所にて7日間熟成させて、評価用粘着加工偏光板を得た。 3.2. Preparation of adhesive processing polarizing plate for evaluation Above 3.1. Using the component (A) obtained in the above, each component was added in the formulations shown in Tables 3 and 4 below (solid content formulation), and pressure-sensitive adhesive compositions of Examples 1 to 15 and Comparative Examples 1 to 5 Solution was obtained. The pressure-sensitive adhesive composition solution was applied to the surface of the peeled polyester film and dried to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a thickness of 20 μm. After sticking this pressure-sensitive adhesive sheet on one side of the polarizing film for VA mode, it was aged in a dark place at 23 ° C./50% RH for 7 days to obtain a pressure-sensitive adhesive processed polarizing plate for evaluation.
3.3.1.最大変形率および歪み復元率
表3および表4に示す実施例1~15および比較例1~5のアクリル系共重合体溶液を剥離処理したポリエステルフィルムの表面に塗布して乾燥させ、空気が入らないようにして厚さ1mmに成膜し、Φ8mmにカットして、試験片とした。この試験片についてレオメーター(型名:MCR300、日本シイベルヘグナー社製)を用いて上記測定工程1ないし3を順に行って上記最大変形率を測定し、かつ、上記(1)に基づいて歪み復元率を算出した。 3.3. Evaluation method 3.3.1. Maximum deformation rate and strain recovery rate The acrylic copolymer solutions of Examples 1 to 15 and Comparative Examples 1 to 5 shown in Tables 3 and 4 were applied to the surface of the release-treated polyester film and dried to allow air to enter. As a test piece, the film was formed to a thickness of 1 mm and cut to Φ8 mm. About this test piece, the said
19インチサイズのVA型液晶パネル(I・Oデータ社製、型式:LCD-A191EWから取り外したもの)に、剥離処理されたポリエステルフィルムをはがした評価用粘着加工偏光板を、粘着剤層が前記液晶パネルに接するように、かつ、前記評価用粘着加工偏光板がクロスニコルになるように貼り合わせて、80℃の雰囲気下で240時間放置した後、23℃/50%RH雰囲気下で2時間放置した。その後、前記偏光板を貼り合わせたVA型液晶パネルを暗室でパソコンに接続し全画面黒表示にした。本試験では、光源(バックライト)として、LED(LED方式)および蛍光灯(非LED方式)の2種を用いて評価を行った。この全画面黒表示のディスプレイモニターについて、図2に示されるように、各コーナー付近の直径1cmの領域における輝度(La,Lb,Lc,Ld)およびモニタ中央部分の直径1cmの領域における輝度(Lcenter)を輝度計(ハイランド社製、型名:RISA-COLOR/CD8)を用いて測定し、下記式(4)に基づいて光漏れ性(ΔL)を算出した。ΔLが小さいほど、(バックライトからの)光漏れが少ないことを意味し、通常、ΔLが2.0未満であれば液晶表示用パネルとしての使用が可能である。
ΔL=(La+Lb+Lc+Ld)/4-Lcenter ・・・(4) 3.3.2. Light leakage 19-inch size VA liquid crystal panel (made by I / O Data Co., Ltd., removed from LCD-A191EW) and peeled polyester film peeled off adhesive film for evaluation The layers were bonded so that the layer was in contact with the liquid crystal panel and the evaluation pressure-sensitive adhesive-processed polarizing plate was crossed Nicol, and allowed to stand for 240 hours in an atmosphere at 80 ° C. And left for 2 hours. Thereafter, the VA liquid crystal panel on which the polarizing plate was bonded was connected to a personal computer in a dark room to display a full screen black. In this test, evaluation was performed using two types of light source (backlight), LED (LED method) and fluorescent lamp (non-LED method). As shown in FIG. 2, the full screen black display monitor has luminance (La, Lb, Lc, Ld) in a 1 cm diameter area near each corner and luminance (Lcenter) in a 1 cm diameter area in the center of the monitor. ) Was measured using a luminance meter (manufactured by Highland, model name: RISA-COLOR / CD8), and light leakage (ΔL) was calculated based on the following formula (4). Smaller ΔL means less light leakage (from the backlight). Usually, if ΔL is less than 2.0, it can be used as a liquid crystal display panel.
ΔL = (La + Lb + Lc + Ld) / 4−Lcenter (4)
剥離処理されたポリエステルフィルムをはがした評価用粘着加工偏光板を15インチサイズ(233mm×309mm)に裁断し、厚さ0.5mmの無アルカリガラス板の片面に、粘着剤層が前記ガラス板に接するようにして、ラミネータロールを用いて貼り付けた。貼付後、オートクレーブ(栗原製作所製)にて0.5MPa、50℃、20分の条件で加圧処理して試験用プレートを得た。こうして得られた試験用プレートを60℃/90%RHの条件下に500時間放置した。試験終了後、試験用プレートを試験環境より取り出し、23℃/50%RH雰囲気下で2時間静置した後、粘着剤層における発泡(凝集力不足)、断裂(過架橋)を目視にて観察して、湿熱耐久性を下記評価基準にて評価した。 3.3.3. Wet heat durability The adhesive processing polarizing plate for evaluation which peeled off the peeled polyester film was cut into a 15 inch size (233 mm × 309 mm), and an adhesive layer was formed on one surface of a non-alkali glass plate having a thickness of 0.5 mm. It stuck using the laminator roll so that the said glass plate might be touched. After pasting, a test plate was obtained by pressurizing in an autoclave (manufactured by Kurihara Seisakusho) under conditions of 0.5 MPa, 50 ° C., and 20 minutes. The test plate thus obtained was left under conditions of 60 ° C./90% RH for 500 hours. After completion of the test, the test plate is taken out from the test environment and left to stand for 2 hours in a 23 ° C./50% RH atmosphere, and then visually observed for foaming (cohesion insufficient) and tearing (overcrosslinking) in the adhesive layer The wet heat durability was evaluated according to the following evaluation criteria.
○:発泡が全く見られない
△:発泡の直径が1mm以下
×:発泡の直径が1mmより大きい (Foaming-Size)
○: No foaming is observed Δ: Foam diameter is 1 mm or less ×: Foam diameter is greater than 1 mm
○:発泡が全く見られない
△:発泡の個数が10個以下
×:発泡の個数が10個より多い (Foaming-generation amount)
○: No foaming is observed Δ: The number of foams is 10 or less ×: The number of foams is more than 10
○:断裂が全く見られない
△:断裂が生じた面積が試験用プレートにおける貼り合わせ部分全体(100%)に対して5%未満
×:断裂が生じた面積が試験用プレートにおける貼り合わせ部分全体(100%)に対して5%以上 (Tear-size)
○: No tearing is observed Δ: The area where tearing occurs is less than 5% with respect to the entire bonding part (100%) in the test plate x: The area where tearing occurs is the entire bonding part in the test plate (100%) over 5%
○:断裂が全くない
△:試験用プレートの各端部付近の1cm幅領域のみに欠点がある
×:試験用プレートの各端部付近の1cm領域と領域外に欠点がある。 (Rear-position)
◯: No tearing Δ: Defects only in the 1 cm width region near each end of the test plate ×: Defects in the 1 cm region near each end of the test plate and outside the region
AA:アクリル酸
AM:アクリルアミド
BA:n-ブチルアクリレート
t-BA:ターシャリーブチルアクリレート
i-BMA:イソブチルメタクリレート
HEA:2-ヒドロキシエチルアクリレート
L-45:TDI系イソシアネート化合物(綜研化学社製 L-45)
MA:メチルアクリレート
MEA:メトキシエチルアクリレート
i-PMA:イソプロピルメタアクリレート
TD:XDI系イソシアネート化合物(三井武田薬品社製 TD-75)
KBM-403:3-グリシドキプロピルトリメトキシシラン(信越化学工業社製)
帯電防止剤((D)成分:イオン性化合物):1-オクチル-4-メチルピリジニウム・ビス(フルオロスルホニル)イミド Abbreviations in Table 2, Table 3, and Table 4 have the following meanings.
AA: Acrylic acid AM: Acrylamide BA: n-Butyl acrylate t-BA: Tertiary butyl acrylate i-BMA: Isobutyl methacrylate HEA: 2-hydroxyethyl acrylate L-45: TDI isocyanate compound (L-45 manufactured by Soken Chemical Co., Ltd.) )
MA: methyl acrylate MEA: methoxyethyl acrylate i-PMA: isopropyl methacrylate TD: XDI-based isocyanate compound (TD-75 manufactured by Mitsui Takeda)
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Antistatic agent (component (D): ionic compound): 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide
Claims (10)
- 架橋性官能基を有するアクリル系ポリマー(A)と、架橋剤(B)とを含み、
下記に定義される最大変形率が10%以下であり、かつ、下記に定義される歪み復元率が50%以上である、光学フィルム用粘着剤組成物。
最大変形率:前記光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、レオメーターを用いて下記測定工程1ないし3を順に行った場合において、変形率が最大となる時点の変形率(%)
最終変形率:レオメーターを用いて下記測定工程1ないし3を順に行った後の該試験片の変形率(%)
歪み復元率:前記光学フィルム用粘着剤組成物を平板上に塗布し乾燥して得られる厚さ1mmの粘着シートを、Φ8mmにカットして得られる試験片について、下記式(1)に基づいて算出された値
歪み復元率(%)=(最大変形率-最終変形率)/最大変形率×100・・・(1)
測定工程1:前記試料片の温度を23℃から80℃まで15分間一定速度で増加させつつ、該試料片の剪断応力を0Paから1000Paまで15分間一定速度で増加させる
測定工程2:前記試料片の温度を80℃で30分間保持しつつ、剪断応力を1000Paから2000Paまで30分間一定速度で増加させる
測定工程3:前記試料片の温度を80℃から23℃まで15分間一定速度で減少させつつ、該試料片の剪断応力を2000Paから0Paまで15分間一定速度で減少させる An acrylic polymer (A) having a crosslinkable functional group, and a crosslinking agent (B),
The pressure-sensitive adhesive composition for an optical film, wherein the maximum deformation rate defined below is 10% or less and the strain recovery rate defined below is 50% or more.
Maximum deformation rate: For a test piece obtained by cutting a 1 mm thick adhesive sheet obtained by applying the optical film adhesive composition on a flat plate and drying it to Φ8 mm, using a rheometer, the following measurement step Deformation rate (%) at the time when the deformation rate becomes maximum when performing 1 to 3 in order
Final deformation ratio: Deformation ratio (%) of the test piece after performing the following measurement steps 1 to 3 in order using a rheometer
Strain recovery rate: About the test piece obtained by cutting the adhesive sheet of 1 mm thickness obtained by applying the adhesive composition for optical film on a flat plate and drying it to Φ8 mm, based on the following formula (1) Calculated value
Strain recovery rate (%) = (maximum deformation rate−final deformation rate) / maximum deformation rate × 100 (1)
Measurement step 1: While increasing the temperature of the sample piece from 23 ° C. to 80 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is increased from 0 Pa to 1000 Pa at a constant rate for 15 minutes.
Measurement step 2: Increase the shear stress from 1000 Pa to 2000 Pa at a constant rate for 30 minutes while maintaining the temperature of the sample piece at 80 ° C. for 30 minutes.
Measurement step 3: While decreasing the temperature of the sample piece from 80 ° C. to 23 ° C. at a constant rate for 15 minutes, the shear stress of the sample piece is reduced from 2000 Pa to 0 Pa at a constant rate for 15 minutes. - 前記架橋性官能基を有するアクリル系ポリマー(A)が、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃以上の(メタ)アクリル酸エステル(a1)5~55質量%と、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃未満の(メタ)アクリル酸エステル(a2)44.5~94.5質量%と、
架橋性官能基を有するモノマー(a3)0.5~6質量%と、
を含むモノマー混合物の重合体である(ここで、前記モノマー混合物中における前記(a1)、(a2)および(a3)の合計量は90~100質量%である。)、請求項1に記載の光学フィルム用粘着剤組成物。 The acrylic polymer (A) having the crosslinkable functional group is
5 to 55% by mass of (meth) acrylic acid ester (a1) having no crosslinkable functional group and having a glass transition temperature (Tg) of 0 ° C. or higher;
(Meth) acrylic acid ester (a2) having no crosslinkable functional group and having a glass transition temperature (Tg) of less than 0 ° C. (44.5 to 94.5% by mass);
0.5-6 mass% of monomer (a3) having a crosslinkable functional group;
The polymer of a monomer mixture containing (wherein the total amount of (a1), (a2) and (a3) in the monomer mixture is 90 to 100% by mass). An adhesive composition for optical films. - 前記(メタ)アクリル酸エステル(a1)が(メタ)アクリル酸アルキルエステルであり、
前記(メタ)アクリル酸アルキルエステルのアルキルエステル部位を構成するアルキル鎖(ここで、前記アルキル鎖の炭素原子数は1~20である。)が直鎖状または分岐状のアルキル鎖である、請求項1または2に記載の光学フィルム用粘着剤組成物。 The (meth) acrylic acid ester (a1) is a (meth) acrylic acid alkyl ester,
The alkyl chain constituting the alkyl ester moiety of the (meth) acrylic acid alkyl ester (wherein the alkyl chain has 1 to 20 carbon atoms) is a linear or branched alkyl chain. Item 3. The pressure-sensitive adhesive composition for an optical film according to Item 1 or 2. - 前記架橋性官能基を有するアクリル系ポリマー(A)は、Tgが-70~0℃である、請求項1ないし3のいずれか1項に記載の光学フィルム用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 3, wherein the acrylic polymer (A) having a crosslinkable functional group has a Tg of -70 to 0 ° C.
- 前記架橋性官能基を有するアクリル系ポリマー(A)は、重量平均分子量が50万~200万である、請求項1ないし4のいずれか1項に記載の光学フィルム用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 4, wherein the acrylic polymer (A) having a crosslinkable functional group has a weight average molecular weight of 500,000 to 2,000,000.
- ゲル分率が70%以上である、請求項1ないし5のいずれか1項に記載の光学フィルム用粘着剤組成物。 The pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 5, wherein the gel fraction is 70% or more.
- 架橋性官能基を有するアクリル系ポリマー(A)と、架橋剤(B)とを含み、
前記架橋性官能基を有するアクリル系ポリマー(A)が、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃以上の(メタ)アクリル酸エステル(a1)5~55質量%と、
架橋性官能基を有さず、かつ、ガラス転移温度(Tg)が0℃未満の(メタ)アクリル酸エステル(a2)44.5~94.5質量%と、
架橋性官能基を有するモノマー(a3)0.5~6質量%と、
を含むモノマー混合物の重合体であって(ここで、前記モノマー混合物中における前記(a1)、(a2)および(a3)の合計量は90~100質量%である。)、かつ、ゲル分率70%以上である、光学フィルム用粘着剤組成物。 An acrylic polymer (A) having a crosslinkable functional group, and a crosslinking agent (B),
The acrylic polymer (A) having the crosslinkable functional group is
5 to 55% by mass of (meth) acrylic acid ester (a1) having no crosslinkable functional group and having a glass transition temperature (Tg) of 0 ° C. or higher;
(Meth) acrylic acid ester (a2) having no crosslinkable functional group and having a glass transition temperature (Tg) of less than 0 ° C. (44.5 to 94.5% by mass);
0.5-6 mass% of monomer (a3) having a crosslinkable functional group;
(Wherein the total amount of (a1), (a2) and (a3) in the monomer mixture is 90 to 100% by mass)) and a gel fraction The adhesive composition for optical films which is 70% or more. - 請求項1ないし7のいずれか1項に記載の光学フィルム用粘着剤組成物を含む粘着剤層を、光学フィルムの片面または両面に設える、粘着型光学フィルム。 A pressure-sensitive adhesive optical film in which a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 7 is provided on one side or both sides of the optical film.
- 偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、輝度向上フィルムおよび光拡散フィルムからなる群から選択される光学フィルムである、請求項8に記載の粘着型光学フィルム。 The pressure-sensitive adhesive optical film according to claim 8, which is an optical film selected from the group consisting of a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, and a light diffusion film.
- ガラス基板と、
偏光板と、
前記ガラス基板と前記偏光板との間に設けられた、請求項1ないし7のいずれか1項に記載の光学フィルム用粘着剤組成物を膜状に成形し、加熱して得られる粘着剤層と、
を含む、積層体。 A glass substrate;
A polarizing plate;
The adhesive layer obtained by shape | molding the adhesive composition for optical films of any one of Claim 1 thru | or 7 formed in the film form, and heating between the said glass substrate and the said polarizing plate. When,
A laminate comprising:
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Also Published As
Publication number | Publication date |
---|---|
KR20150087329A (en) | 2015-07-29 |
CN104837945B (en) | 2017-08-25 |
JP5887404B2 (en) | 2016-03-16 |
CN104837945A (en) | 2015-08-12 |
TW201428073A (en) | 2014-07-16 |
KR101757569B1 (en) | 2017-07-12 |
JPWO2014091927A1 (en) | 2017-01-05 |
TWI608064B (en) | 2017-12-11 |
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