WO2018056367A1 - 粘着剤組成物 - Google Patents
粘着剤組成物 Download PDFInfo
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- WO2018056367A1 WO2018056367A1 PCT/JP2017/034139 JP2017034139W WO2018056367A1 WO 2018056367 A1 WO2018056367 A1 WO 2018056367A1 JP 2017034139 W JP2017034139 W JP 2017034139W WO 2018056367 A1 WO2018056367 A1 WO 2018056367A1
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- meth
- pressure
- sensitive adhesive
- acrylate
- adhesive layer
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Definitions
- the present invention relates to a pressure-sensitive adhesive composition useful as an optical member used in a liquid crystal display device, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, an optical film with a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive layer, and an optical laminate, Moreover, it is related with the (meth) acrylic-type resin for adhesive compositions.
- An optical film typified by a polarizing plate formed by laminating and laminating a transparent resin film on one or both sides of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device or an organic EL display device. Yes.
- An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). For this reason, the optical film with an adhesive layer by which the adhesive layer was previously provided in the one surface as an optical film is known.
- image display devices such as liquid crystal display devices and organic EL display devices have been developed for mobile device applications such as smartphones and tablet terminals and in-vehicle device applications such as car navigation systems.
- mobile device applications such as smartphones and tablet terminals
- in-vehicle device applications such as car navigation systems.
- image display devices such as liquid crystal display devices and organic EL display devices
- mobile device applications such as smartphones and tablet terminals
- in-vehicle device applications such as car navigation systems.
- Durability is similarly required for an optical film with an adhesive layer that constitutes an image display device or the like. That is, the pressure-sensitive adhesive layer incorporated in an image display device or the like may be placed in a high temperature or high temperature and high humidity environment, or may be placed in an environment where high and low temperatures are repeated.
- the optical film is required to be able to suppress problems such as floating and peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which the optical film is bonded, foaming of the pressure-sensitive adhesive layer, and the like even under these circumstances. It is also required that the optical characteristics do not deteriorate.
- the pressure-sensitive adhesive layer is required to have a higher durability performance than a general optical film due to a strong shrinkage stress in a high temperature environment. Due to the increasing demand for improving the durability of the image display device described above, recently, the durability required for the pressure-sensitive adhesive layer has become very severe.
- an object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting excellent durability even under such severe durability conditions, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive It is providing the optical film with an adhesive layer and optical laminated body containing a layer.
- Another object of the present invention is to provide a (meth) acrylic resin for pressure-sensitive adhesive compositions capable of forming a pressure-sensitive adhesive layer exhibiting excellent durability even under the severe durability conditions described above.
- the (meth) acrylic resin (A) comprises a structural unit derived from an alkyl acrylate (a3) having a glass transition temperature of the homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more
- the crosslinking agent (B) is an isocyanate compound.
- the ratio of the crosslinking agent (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A), according to any one of [1] to [7] Adhesive composition.
- the silane compound (C) is represented by the following formula (c1) (In the formula, B represents an alkanediyl group having 3 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group.
- —CH 2 — may be substituted with —O— or —CO—
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
- the pressure-sensitive adhesive composition according to any one of [1] to [8], which is a silane compound represented by: [10]
- the ratio of the silane compound (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A), according to any one of [1] to [9] Adhesive composition.
- the anion constituting the ionic compound (D) is at least one selected from the group consisting of a bis (trifluoromethanesulfonyl) imide anion, a bis (fluorosulfonyl) imide anion, and a tetra (pentafluorophenyl) borate anion.
- a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [14].
- the pressure-sensitive adhesive layer according to [15] wherein the pressure-sensitive adhesive layer has a gel fraction of 70 to 90%.
- An optical film with an adhesive layer comprising an optical film and an adhesive layer laminated on at least one surface of the optical film, wherein the adhesive layer is described in [15] or [16].
- An optical film with an adhesive layer which is an adhesive layer.
- An optical laminate comprising the optical film with the pressure-sensitive adhesive layer according to [17] and a base material laminated on the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer.
- a structural unit derived from an acetoacetyl group-containing (meth) acrylate (a1) and a structural unit derived from a hydroxy group-containing (meth) acrylate (a2), and the mass ratio of the structural units (a2) / (a1) Is a (meth) acrylic resin (A) for pressure-sensitive adhesive compositions having a weight average molecular weight of at least 1 million in terms of polystyrene.
- the (meth) acrylic resin (A) comprises a structural unit derived from an alkyl acrylate (a3) having a homopolymer glass transition temperature of less than 0 ° C., and an alkyl acrylate having a homopolymer glass transition temperature of 0 ° C.
- Mass ratio of structural unit derived from alkyl acrylate (a3) whose homopolymer glass transition temperature is less than 0 ° C. and structural unit derived from alkyl acrylate (a4) whose homopolymer glass transition temperature is 0 ° C. or higher (The (meth) acrylic resin (A) for pressure-sensitive adhesive compositions according to [19] or [20], wherein a3) / (a4) is 0.1 to 4.
- the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth) acrylic resin (A) is 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A).
- the (meth) acrylic resin (A) further comprises a structural unit derived from a (meth) acrylamide monomer, for the pressure-sensitive adhesive composition according to any one of [19] to [22] ) Acrylic resin (A).
- a pressure-sensitive adhesive layer having excellent durability even under severe durability conditions, the optical film with the pressure-sensitive adhesive layer, and an optical laminate can be formed.
- a pressure-sensitive adhesive layer having excellent durability can be formed even under severe durability conditions.
- FIG. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer according to the present invention.
- FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the polarizing plate.
- FIG. 3 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate.
- FIG. 4 is a schematic cross-sectional view showing an example of an optical laminate according to the present invention.
- FIG. 5 is a schematic cross-sectional view showing another example of the optical layered body according to the present invention.
- FIG. 6 is a schematic cross-sectional view showing still another example of the optical laminate according to the present invention.
- FIG. 7 is a schematic cross-sectional view showing another example of the optical laminate according to the present invention.
- FIG. 8 is a schematic cross-sectional view showing still another example of the optical laminate according to the present invention.
- the pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic resin (A), a crosslinking agent (B), and a silane compound (C).
- the (meth) acrylic resin (A) is preferably a structural unit derived from a (meth) acrylic monomer, preferably 50% with respect to 100% by mass of all the structural units constituting the (meth) acrylic resin (A).
- (meth) acryl means acryl or methacryl
- “(meth) acrylate”, “(meth) acryloyl”, and the like are acrylate or methacrylate, acryloyl or methacryloyl, respectively.
- durability refers to, for example, at the interface between the pressure-sensitive adhesive layer and the optical member adjacent thereto in a high temperature environment, a high temperature and high humidity environment, or an environment where high and low temperatures are repeated. It refers to a characteristic that can prevent floating and peeling (sometimes referred to as peeling resistance) and a characteristic that can suppress problems such as foaming of the pressure-sensitive adhesive layer (sometimes referred to as foaming resistance).
- the cohesive failure resistance refers to a property capable of suppressing cohesive failure (or tearing) of the pressure-sensitive adhesive layer.
- the acetoacetyl group-containing (meth) acrylate (a1) may contain a substituent other than the acetoacetyl group, and examples of the substituent include a cyano group.
- Specific examples of the acetoacetyl group-containing (meth) acrylate (a1) include, for example, acetoacetoxyalkyl (meth) acrylate such as acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate Acetoacetoxy C 2-10 alkyl (meth) acrylate such as; acetoacetyl group-containing (meth) acrylate having a substituent, for example, cyanoacetoacetoxy C 2-10 alkyl (meth) acrylate such as 2-cyanoacetoacetoxyethyl (meth) acrylate ) Acrylate and the like.
- acetoacetoxyethyl (meth) acrylate acetoacetoxypropyl (meth) acrylate, and acetoacetoxybutyl (meth) acrylate are preferable from the viewpoint of durability and availability of the pressure-sensitive adhesive layer.
- -Acetoacetoxyethyl (meth) acrylate is preferred.
- These acetoacetyl group-containing (meth) acrylates (a1) can be used alone or in combination of two or more.
- hydroxy group-containing (meth) acrylate (a2) include, for example, 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, (meth) acrylic acid 1-hydroxy pentyl, (meth) (meth) 1-hydroxy-C 1-8 alkyl acrylate such as acrylic acid 1-hydroxy-heptyl; 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl (Meth) acrylic acid 2-hydroxy C 2-9 alkyl such as propyl, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate; 3-hydroxypropyl acrylate, 3-hydroxybutyrate (meth) acrylate , (Meth) acrylic acid 3-hydroxy pentyl, (meth) acrylate, 3-hydroxyhexyl, (meth) (meth) acrylic acid
- (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl and the like (Meth) acrylic acid 3-hydroxy C 2-7 alkyl; (meth) acrylic acid 3 such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, etc.
- the proportion of the structural unit derived from the acetoacetyl group-containing (meth) acrylate (a1) is preferably 0.01 to 10 parts by weight, more preferably 100 parts by weight of all the structural units constituting the (meth) acrylic resin. Is 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass.
- the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate (a2) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin.
- the amount is preferably 1 to 10 parts by mass, more preferably 1.5 to 5 parts by mass.
- the mass ratio (a2) / (a1) of the structural unit derived from the acetoacetyl group-containing (meth) acrylate (a1) and the structural unit derived from the hydroxy group-containing (meth) acrylate (a2) is 0.5 to 5, preferably Is 0.7 to 4.5, more preferably 1 to 4, still more preferably 1.2 to 3.7, and particularly preferably 1.5 to 3.5.
- these mass ratios are within the above range, the durability of the pressure-sensitive adhesive layer can be further improved.
- the (meth) acrylic resin (A) is derived from a structural unit derived from an alkyl acrylate (a3) having a glass transition temperature of the homopolymer of less than 0 ° C. and from an alkyl acrylate (a4) having a glass transition temperature of the homopolymer of 0 ° C. or higher. These structural units may be further included.
- alkyl acrylate (a3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C. examples include, for example, ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- And alkyl such as i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate and n-dodecyl acrylate Examples thereof include linear or branched alkyl acrylates having a group having about 2 to 12 carbon atoms.
- the alkyl acrylate (a3) may be an alkyl acrylate having a cycloaliphatic structure (cycloalkyl acrylate).
- the alkyl acrylate has 2 to 10 carbon atoms.
- n-butyl acrylate is used, the followability can be enhanced, and for example, it is advantageous in peeling resistance.
- These alkyl acrylates (a3) can be used alone or in combination of two or more.
- alkyl acrylate (a4) having a homopolymer Tg of 0 ° C. or higher examples include methyl acrylate, cycloalkyl acrylate (eg, cyclohexyl acrylate, isobornyl acrylate, etc.), stearyl acrylate, t-butyl acrylate, and the like. Acrylate is preferred. When methyl acrylate is used, the strength of the pressure-sensitive adhesive layer during high-temperature durability can be increased, and for example, the cohesive fracture resistance can be improved. These alkyl acrylates (a4) can be used alone or in combination of two or more. For the Tg of the alkyl acrylate homopolymer, reference values such as POLYMER HANDBOOK (Wiley-Interscience) can be referred to.
- the total proportion of the structural units (a3) and (a4) derived from the alkyl acrylate is the durability and reworkability of the pressure-sensitive adhesive layer with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). From a viewpoint, it may be 40 mass parts or more, for example.
- the lower limit of the total ratio of the structural units (a3) and (a4) is preferably 50 parts by mass, more preferably 60 parts by mass, still more preferably 70 parts by mass, and particularly preferably 75 parts by mass.
- the upper limit of the total ratio of the structural units (a3) and (a4) is preferably 98 parts by mass, more preferably 95 parts by mass, and still more preferably 90 parts by mass.
- the total proportion of the structural units (a3) and (a4) may be any combination of the lower limit value and the upper limit value, for example, 50 to 98 parts by mass, preferably 70 to 95 parts by mass, more preferably 75 to 95 parts by mass. Part.
- alkyl acrylate (a3) with homopolymer Tg of less than 0 ° C and alkyl acrylate (a4) with homopolymer Tg of 0 ° C or higher achieves both cohesive fracture resistance and follow-up properties (peeling resistance) It is possible to improve durability against dimensional changes of the optical film (for example, polarizing plate).
- the followability improves, and the proportion of the structural unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C. or higher increases. As the result, the cohesive fracture resistance is improved. Further, when the alkyl acrylate (a4) having a glass transition temperature of the homopolymer of 0 ° C. or higher is contained in a higher proportion than the alkyl acrylate (a3) having a glass transition temperature of the homopolymer of less than 0 ° C., the durability is further improved. It shows excellent durability even under harsh endurance conditions.
- the (meth) acrylic resin (A) may further contain a structural unit derived from a substituent-containing alkyl acrylate.
- substituent-containing alkyl acrylate for example, an alkyl acrylate in which a substituent is introduced into the alkyl group in the alkyl acrylates (a3) and (a4) (in other words, a hydrogen atom of the alkyl group is substituted with a substituent) Is mentioned.
- the substituent may be, for example, an aryl group (for example, phenyl group), an aryloxy group (for example, phenoxy group), an alkoxy group (for example, methoxy group, ethoxy group, etc.), and the like.
- substituent-containing alkyl acrylate examples include arylalkyl acrylate (eg, benzyl acrylate, phenethyl acrylate, etc.), alkoxyalkyl acrylate (eg, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), aryloxyalkyl acrylate (eg, phenoxyethyl acrylate, etc.) ), Aryloxy polyalkylene glycol monoacrylate, polyalkylene glycol monoacrylate and the like.
- arylalkyl acrylate eg, benzyl acrylate, phenethyl acrylate, etc.
- alkoxyalkyl acrylate eg, 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.
- aryloxyalkyl acrylate eg, phenoxyethyl acrylate, etc.
- the alkylene group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C 1-6 alkylene group such as a methylene group, an ethylene group or a propylene group, preferably an ethylene group. These repeating units can be appropriately selected.
- the repeating unit of the alkylene group may be, for example, 1-7, preferably 1-5, especially 1 or 2.
- These alkyl acrylates can be used alone or in combination of two or more. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, white spots of the polarizing plate during the durability test can be improved.
- antistatic performance can be improved by including the alkyl acrylate containing ether structures, such as an alkoxy group and a polyalkylene glycol structure.
- alkyl acrylate containing ether structures such as an alkoxy group and a polyalkylene glycol structure.
- aryloxyalkyl acrylate and aryloxypolyalkylene glycol acrylate are desirable to include.
- Specific examples include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytriethylene glycol acrylate, and phenoxytetraethylene glycol acrylate.
- the proportion of the structural unit derived from the substituent-containing alkyl acrylate is, for example, 0 to 40 parts by weight, preferably 3 to 30 parts by weight with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). More preferably, it may be 5 to 25 parts by mass, particularly 7 to 21 parts by mass. When the ratio is in the above range, the above-described characteristics such as white spots, antistatic properties and durability can be further improved.
- (Meth) acrylic resin (A) can contain structural units derived from other monomers than the above structural units.
- Other monomers can be used alone or in combination of two or more.
- Other monomers include monomers having polar functional groups other than hydroxy groups, (meth) acrylamide monomers, styrene monomers, vinyl monomers, and a plurality of (meth) monomers in the molecule. And monomers having an acryloyl group.
- Examples of the monomer having a polar functional group other than a hydroxy group include (meth) acrylates having a substituent such as a heterocyclic group such as an epoxy group, a substituted or unsubstituted amino group, and a carboxyl group.
- acryloylmorpholine vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl Monomers having a heterocyclic group such as (meth) acrylate and 2,5-dihydrofuran; aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.
- Monomers having a substituted or unsubstituted amino group (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (for example, carboxyethyl (meth) acrylate Monomers are exemplified with a carboxyl group such as carboxymethyl pentyl (meth) acrylate). These monomers can be used alone or in combination of two or more.
- the structural unit derived from the monomer which has an amino group is not included substantially from a viewpoint of preventing the fall of the peelability of the separate film which can be laminated
- that it does not contain substantially means that it is less than 1.0 mass part with respect to 100 mass parts of all the structural units which comprise (meth) acrylic-type resin (A).
- the durability can be effectively improved even if the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is small, by containing a small amount of the structural unit derived from the carboxyl group-containing (meth) acrylate. Further, it is possible to further improve the durability while suppressing the corrosion of ITO.
- the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is 1.0 part by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin.
- the upper limit of the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is preferably 0.8 parts by mass, more preferably 0.5 parts by mass, still more preferably 0.3 parts by mass, particularly preferably 0.2. Part by mass, particularly preferably 0.15 part by mass.
- the lower limit of the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.005 parts by mass, particularly preferably 0.01 parts by mass. Especially 0.05 parts by mass.
- the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate may be any combination of these upper limit value and lower limit value, for example, 0 to 1 part by mass, preferably 0 to 0.8 part by mass, more preferably Is 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.3 parts by mass, particularly preferably 0.01 to 0.2 parts by mass, especially 0.05 to 0.15 parts by mass. Good.
- the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is at most the upper limit value, the ITO corrosivity can be suppressed, and when it is at least the lower limit value, the durability can be improved.
- Examples of (meth) acrylamide monomers include N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxy Methyl) acryl Amides, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methyleth
- the durability of the pressure-sensitive adhesive layer can be further improved.
- N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide, etc. preferable.
- the proportion of the structural unit derived from the (meth) acrylamide monomer is 5 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin.
- the upper limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 3 parts by mass, more preferably 2 parts by mass, and even more preferably 1 part by mass.
- the lower limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.01 parts by mass, particularly preferably 0.1 parts by mass. Part.
- the proportion of the structural unit derived from the (meth) acrylamide monomer may be any combination of these upper limit value and lower limit value, for example, 0 to 5 parts by mass, preferably 0.001 to 3 parts by mass.
- the amount may be preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass.
- styrenic monomer examples include styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluoro Halogenated styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene, and the like.
- alkyl styrene such as methyl sty
- vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, and the like; conjugated diene monomers such as butadiene, isoprene, and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
- fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate
- vinyl halides such as vinyl chloride and vinyl bromide
- vinylidene chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, and the like
- conjugated diene monomers such
- Examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol.
- (meth) acryloyl in the molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate
- a monomer having a group a monomer having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate;
- the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography GPC is preferably 1 million or more in order to further improve the durability of the pressure-sensitive adhesive layer.
- the lower limit value of Mw is more preferably 1.1 million, still more preferably 1.2 million, and particularly 1.3 million.
- the upper limit value of Mw is not particularly limited, but is preferably 2.5 million, more preferably 2.2 million, from the viewpoint of coating properties when the pressure-sensitive adhesive composition is processed into a sheet (for example, coated on a substrate). More preferably, it is 2 million.
- Mw may be an arbitrary combination of these upper limit value and lower limit value, and may be, for example, 1 to 2.5 million, more preferably 1.1 million to 2.2 million, and still more preferably 1.2 to 2 million.
- the molecular weight distribution represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is usually 1 to 10, preferably 2 to 8, and more preferably 3 to 6.
- the (meth) acrylic resin (A) preferably has a single peak when the Mw on the GPC emission curve is in the range of 1,000 to 2.5 million.
- the (meth) acrylic resin (A) having a peak number of 1 it is advantageous for improving the durability of the pressure-sensitive adhesive layer, the optical film with the pressure-sensitive adhesive layer, and the optical laminate including the same.
- “Having a single peak” in the above range of the obtained emission curve means having only one maximum value in the range of Mw 1,000 to 2.5 million.
- a peak having an S / N ratio of 30 or more in the GPC emission curve is defined.
- the number of peaks in the GPC discharge curve and the Mw and Mn of the (meth) acrylic resin (A) can be determined according to the GPC measurement conditions described in the Examples section.
- the viscosity at 25 ° C. is preferably 30,000 mPa ⁇ s or less, and is preferably from 100 to 20,000 mPa -It is more preferable that it is s.
- the viscosity is in the above range, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate.
- the viscosity can be measured with a Brookfield viscometer.
- the glass transition temperature (Tg) of the (meth) acrylic resin (A) may be, for example, ⁇ 60 to 20 ° C., preferably ⁇ 50 to 10 ° C., and more preferably ⁇ 40 to 0 ° C. When the glass transition temperature is in the above range, it is advantageous for improving the durability of the pressure-sensitive adhesive layer.
- the glass transition temperature can be measured with a differential scanning calorimeter (DSC).
- the (meth) acrylic resin (A) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and the solution polymerization method is particularly preferable.
- a solution polymerization method for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added in a nitrogen atmosphere, and the temperature is about 40 to 90 ° C., preferably about 50 to 80 ° C. A method of stirring for about an hour can be mentioned.
- a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization.
- the monomer or thermal initiator may be added to an organic solvent.
- the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator, or the like is used.
- the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone.
- thermal polymerization initiators examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) Azo) compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide , Diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxy Organic peroxides such as decanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) per
- the ratio of the polymerization initiator is about 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the (meth) acrylic resin (A).
- a polymerization method using active energy rays such as ultraviolet rays may be used.
- organic solvent examples include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the like.
- the pressure-sensitive adhesive composition of the present invention contains a crosslinking agent (B).
- the crosslinking agent (B) may be any one that can react with a polar functional group containing a hydroxy group or an acetoacetyl group in the (meth) acrylic resin (A).
- the hydroxyl group or acetoacetyl group introduced into the side chain of the (meth) acrylic resin (A) reacts with the crosslinking agent (B), and durability (for example, the foaming resistance, A crosslinked structure advantageous in terms of peelability and cohesive failure resistance is formed.
- crosslinking agent (B) examples include conventional crosslinking agents such as isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, and the like, particularly in terms of pot life and crosslinking speed of the pressure-sensitive adhesive composition. From the viewpoints of the durability of the optical film with an adhesive layer and the optical laminate, and the like, an isocyanate compound is preferable.
- the isocyanate compound a compound having at least two isocyanato groups (—NCO) in the molecule is preferable.
- an aliphatic isocyanate compound eg, hexamethylene diisocyanate
- an alicyclic isocyanate compound eg, isophorone diisocyanate
- aromatic isocyanate compounds for example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.).
- the crosslinking agent (B) is an adduct (adduct) of the isocyanate compound with a polyhydric alcohol compound [for example, an adduct with glycerol, trimethylolpropane, etc.], an isocyanurate, a burette compound, a polyether polyol, It may be a derivative such as a urethane prepolymer type isocyanate compound obtained by addition reaction with polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol or the like.
- a crosslinking agent (B) can be used individually or in combination of 2 or more types.
- aromatic isocyanate compounds such as tolylene diisocyanate and xylylene diisocyanate
- aliphatic isocyanate compounds such as hexamethylene diisocyanate
- polyhydric alcohol compounds thereof such as glycerol and trimethylol
- Adducts such as propane).
- the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof, the durability of the optical film with an adhesive layer can be improved. In particular, durability can be further improved when the adduct is a tolylene diisocyanate compound and / or a polyhydric alcohol compound thereof.
- the ratio of the crosslinking agent (B) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the (meth) acrylic resin (A). 15 to 1 part by mass, especially 0.2 to 0.5 part by mass.
- the ratio of the crosslinking agent (B) is not more than the above upper limit value, it is advantageous for improvement of peeling resistance, and when it is not less than the above lower limit value, it is advantageous for improvement of foam resistance and reworkability.
- the pressure-sensitive adhesive composition contains a silane compound (C).
- a silane compound (C) By including the silane compound (C), adhesion (or adhesiveness) between the pressure-sensitive adhesive layer and a base material (for example, a metal layer, a transparent electrode, a glass substrate, etc.) can be improved.
- the silane compound (C) may be any silane compound that can be bonded to the reactive group (for example, hydroxyl group or acetoacetyl group) of the (meth) acrylic resin (A), and examples thereof include vinyltrimethoxysilane, vinyltrimethoxysilane, and vinyltrimethoxysilane.
- the silane compound (C) may be a silicone oligomer type compound.
- the silicone oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldi or trimethoxysilane-tetramethoxysilane oligomer, 3 -Mercaptoalkyl group-containing oligomers such as mercaptomethyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer
- the mercaptoalkyl group of the mercaptoalkyl group-containing oligomer is substituted with other substituents [for example, 3-glycidoxypropyl group, (meth) acryloyloxypropyl group, vinyl group, amino group, And the like
- the silane compound (C) may preferably be a silane compound represented by the following formula (c1).
- the pressure-sensitive adhesive composition contains a silane compound represented by the following formula (c1), the adhesiveness (or adhesiveness) can be further improved, so that a pressure-sensitive adhesive layer having excellent peeling resistance can be formed. Furthermore, the pressure-sensitive adhesive layer is excellent in reworkability. In particular, even when the pressure-sensitive adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate) in a high-temperature environment, adhesion (or adhesiveness) can be maintained and high durability can be exhibited.
- a transparent electrode for example, an ITO substrate
- B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group.
- —CH 2 — may be substituted with —O— or —CO—
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- R 2 , R 3 , R 4 , R 5 and R 6 are each Independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
- B represents, for example, an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group ( For example, 1,2-cyclobutylene group), cyclopentylene group (for example, 1,2-cyclopentylene group), cyclohexylene group (for example, 1,2-cyclohexylene group), cyclooctylene group (for example, 1,2 A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as —cyclooctylene group; or —CH 2 — constituting the alkanediyl group and the alicyclic hydrocarbon group is —O— Or represents a group substituted by -CO-.
- an alkanediyl group having 1 to 20 carbon atoms
- Preferred B is an alkanediyl group having 1 to 10 carbon atoms.
- R 1 represents, for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, or a pentyl group
- R 2 , R 3 , R 4 , R 5 and R 6 are each independently, for example, an alkyl group having 1 to 5 carbon atoms exemplified for the above R 1 ; or, for example, a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group , S-butoxy group, t-butoxy group and the like, and an alkoxy group having 1 to 5 carbon atoms.
- Preferred R 2 , R 3 , R 4 , R 5 and R 6 are
- silane compound (c1) examples include (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3-bis ( Trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,4-bis (triethoxysilyl) butane, 1,5-bis (trimethoxy) Silyl) pentane, 1,5-bis (triethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,6-bis (tripropoxysilyl) Hexane, 1,8-bis (trimethoxysilyl) octane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (
- 1,2-bis (trimethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane can be effectively improved in peeling resistance.
- Bis (triC 1-3 alkoxysilyl) C 1 such as 1,5-bis (trimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane
- a -10 alkane is preferable, and 1,6-bis (trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are particularly preferable.
- These silane compounds (c1) can be used alone or in combination of two or more.
- the proportion of the silane compound (C) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the (meth) acrylic resin (A). 0.1 to 1 part by mass, particularly preferably 0.2 to 0.5 part by mass.
- the ratio of the silane compound (C) is not more than the above upper limit value, it is advantageous for suppressing bleeding out of the silane compound (C) from the adhesive layer, and when it is not less than the above lower limit value, Adhesiveness (or adhesiveness) with a material (for example, a metal layer or a glass substrate) can be easily improved, which is advantageous in improving peeling resistance.
- the pressure-sensitive adhesive composition of the present invention may further contain an antistatic agent.
- an antistatic agent By containing the antistatic agent, the antistatic property of the pressure-sensitive adhesive layer can be improved, and for example, problems due to static electricity generated when a release film, a protective film or the like is peeled can be suppressed.
- the antistatic agent include conventional ones, and an ionic antistatic agent (ionic compound (D)) is preferable.
- the cation constituting the ionic antistatic agent (ionic compound (D)) include organic cations and inorganic cations.
- Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.
- Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation.
- the anion constituting the ionic antistatic agent (ionic compound (D)) may be either an inorganic anion or an organic anion, but an anion containing a fluorine atom is preferred from the viewpoint of excellent antistatic performance.
- anion containing a fluorine atom examples include hexafluorophosphate anion (PF 6 ⁇ ), bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N ⁇ ], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B ⁇ ] and the like.
- PF 6 ⁇ hexafluorophosphate anion
- bis (trifluoromethanesulfonyl) imide anion bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ]
- bis (fluorosulfonyl) imide anion (FSO 2 ) 2 N ⁇ ]
- tetra (pentafluorophenyl) borate anion (C 6
- bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ]
- tetra (pentafluorophenyl) borate anion ( It is preferably at least one selected from the group consisting of C 6 F5) 4 B ⁇ ].
- An ionic antistatic agent (ionic compound (D)) that is solid at room temperature is preferred in that the antistatic performance of the pressure-sensitive adhesive composition is excellent over time.
- the ionic compound (D) is preferably an ionic compound composed of an anion containing a fluorine atom and an organic cation.
- the proportion of the ionic antistatic agent (ionic compound (D)) is, for example, from 0.01 to 10 parts by mass, preferably from 0.1 to 5 parts per 100 parts by mass of the (meth) acrylic resin (A).
- the amount may be 1 part by mass, more preferably 1 to 3 parts by mass.
- the pressure-sensitive adhesive composition of the present invention comprises a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and light scattering fine particles.
- a solvent e.g., a solvent for polyurethane, polystyrene, polystyrene, polystymer, polystackifier, poly(ethylene glycol)-propymer, poly(ethylene glycol)-propylene glycol dimethacrylate, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, poly(ethylene glycol) terpolymer, polyst copolymer for polyst copolymer for polyst copolymer, polyst copolymer, polyst copolymer, polyst copo
- crosslinking catalyst examples include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.
- the pressure-sensitive adhesive composition of the present invention can contain a rust preventive agent from the viewpoint of enhancing the metal corrosion resistance of the pressure-sensitive adhesive layer, the optical film with the pressure-sensitive adhesive layer, and the optical laminate including these.
- the rust inhibitor include triazole compounds such as benzotriazole compounds; thiazole compounds such as benzothiazole compounds; imidazole compounds such as benzylimidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; Examples include pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoates; benzyl mercapto compounds; di-sec-butyl sulfide; and diphenyl sulfoxide.
- the pressure-sensitive adhesive composition of the present invention does not substantially contain a photopolymerization initiator and a decomposition product thereof. This is because the photopolymerization initiator and its decomposition product in the pressure-sensitive adhesive composition may inhibit formation of a pressure-sensitive adhesive layer having excellent durability.
- substantially not containing means that it is 1.0 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition. Most preferably, it is at most 0.001 part by mass, more preferably at most 0 part by mass.
- the pressure-sensitive adhesive composition of the present invention contains the specific (meth) acrylic resin (A), the crosslinking agent (B) and the silane compound (C) as described above, the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition.
- the durability of the layer can be improved, and peeling (or floating) and foaming of the interface can be effectively suppressed even in a high temperature environment.
- the pressure-sensitive adhesive layer can effectively relieve the stress, so that white spots due to the shrinkage of the optical film (for example, the deflection plate) can be prevented.
- the (meth) acrylic resin (A) contained in the pressure-sensitive adhesive composition of the present invention has two functional groups having different reactivity, that is, a hydroxy group and an acetoacetyl group in the side chain.
- the pressure-sensitive adhesive composition can form a pressure-sensitive adhesive layer having a cross-linking structure and a cross-linking density that are optimal for the development of excellent durability because it contains structural units having respective functional groups at a specific mass ratio. It is estimated to be.
- Pressure-sensitive adhesive layer optical film with pressure-sensitive adhesive layer, and production method thereof
- the present invention includes a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer is obtained by, for example, dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of an optical film or a release film. Can be formed.
- the present invention also includes an optical film with an adhesive layer comprising an optical film and the adhesive layer laminated on at least one surface of the optical film.
- the pressure-sensitive adhesive layer and the optical film with the pressure-sensitive adhesive layer of the present invention are formed from the pressure-sensitive adhesive composition, they have excellent durability even under severe durability conditions (for example, durability conditions of 100 ° C. or higher).
- FIG. 1 is a schematic sectional view showing an example of an optical film with an adhesive layer of the present invention.
- the optical film 1 with an adhesive layer shown in FIG. 1 is an optical film in which an optical film 10 and an adhesive layer 20 are laminated on one side of the optical film.
- the pressure-sensitive adhesive layer 20 is usually laminated directly on the surface of the optical film 10.
- the pressure-sensitive adhesive layer 20 may be laminated on both surfaces of the optical film 10.
- a primer layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the pressure-sensitive adhesive layer 20, or the surface activation treatment (for example, plasma treatment, corona treatment and the like are preferably performed, and corona treatment is particularly preferable.
- the pressure-sensitive adhesive layer 20 is usually laminated on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. (Preferably directly laminated).
- the pressure-sensitive adhesive layer 20 may be laminated on the outer surface of either the first or second resin film 3 or 4, and both outer surfaces May be laminated.
- a separate antistatic layer may be provided between the optical film 10 and the pressure-sensitive adhesive layer 20.
- silicon materials such as polysiloxane, inorganic metal materials such as tin-doped indium oxide and tin-doped antimony oxide, and organic polymer materials such as polythiophene, polystyrene sulfonic acid, and polyaniline can be used.
- the optical film 1 with an adhesive layer may include a separate film (release film) laminated on the outer surface of the adhesive layer 20.
- This separate film is usually peeled and removed when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on a transparent conductive electrode or a glass substrate).
- the separate film is obtained by, for example, performing a release treatment such as a silicone treatment on the surface on which the adhesive layer 20 of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarate is formed. Good.
- the optical film 1 with the pressure-sensitive adhesive layer is obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of the optical film 10. And can be obtained by forming the pressure-sensitive adhesive layer 20. Moreover, the optical film 1 with an adhesive layer forms the adhesive layer 20 on the mold release process surface of a separate film similarly to the above, and laminates
- the thickness of the pressure-sensitive adhesive layer is usually 2 to 40 ⁇ m, and preferably 5 to 30 ⁇ m, more preferably 10 from the viewpoints of durability of the optical film with the pressure-sensitive adhesive layer and reworkability of the optical film with the pressure-sensitive adhesive layer. ⁇ 25 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is not more than the upper limit value, the reworkability is good, and when it is more than the lower limit value, the followability (or followability) of the pressure-sensitive adhesive layer with respect to the dimensional change of the optical film is good.
- the adhesive layer preferably exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C. Thereby, durability of the optical film with an adhesive layer can be improved more effectively.
- “Shows a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C.” means that the storage elastic modulus is a value within the above range at any temperature within this range. Since the storage elastic modulus usually decreases gradually as the temperature rises, if both the storage elastic modulus at 23 ° C. and 80 ° C. are within the above range, the storage elastic modulus within the above range is exhibited at the temperature in this range. Can be assumed.
- the storage elastic modulus of the pressure-sensitive adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device “DYNAMIC ANALYZER RDA II” manufactured by REOMETRIC.
- Gel fraction can be used as an index of crosslinking density. Since the pressure-sensitive adhesive layer of the present invention has a predetermined crosslinking density, it exhibits a predetermined gel fraction. That is, the gel fraction of the pressure-sensitive adhesive layer of the present invention may be, for example, 70 to 90% by mass, preferably 75 to 90% by mass, and more preferably 75 to 85% by mass. When the gel fraction is at least the lower limit value, it is advantageous for foaming resistance and reworkability of the pressure-sensitive adhesive layer, and when the gel fraction is at most the upper limit value, it is advantageous for peeling resistance. The gel fraction can be measured by the method described in the Examples section.
- the pressure-sensitive adhesive layer of the present invention has a predetermined adhesive strength. That is, the pressure-sensitive adhesive layer is bonded to a glass substrate, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer after 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% is preferably 0. It is 5 to 25N, more preferably 0.5 to 20N, still more preferably 0.5 to 15N, particularly preferably 1 to 10N, especially 1.5 to 10N. When the adhesive strength is not less than the lower limit, it is advantageous for reworkability. The adhesive strength can be measured by the method described in the Examples section.
- the optical film 10 constituting the optical film 1 with a pressure-sensitive adhesive layer may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device.
- the optical film 10 may have a single layer structure (for example, an optical functional film such as a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light collecting film, etc.)
- a multilayer structure for example, a polarizing plate, a phase difference plate, etc. may be used.
- the optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and particularly preferably a polarizing plate or a polarizer.
- the optical film means a film that functions for image display (display screen or the like) (for example, a film that functions for improving the visibility of an image).
- the polarizing plate means that a resin film or a resin layer is laminated on at least one surface of a polarizer
- the retardation plate means a resin film on at least one surface of the retardation film. Or the thing on which the resin layer was laminated
- FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate.
- the polarizing plate 10a shown in FIG. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated (or laminated) on one surface of the polarizer 2, and the polarizing plate 10b shown in FIG. This is a double-sided protective polarizing plate in which the second resin film 4 is further laminated (or laminated) on the other surface of the polarizer 2.
- the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown).
- the polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.
- the polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis).
- a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used.
- the dichroic dye include iodine and dichroic organic dyes.
- the polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin.
- the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, ammonium group). (Meth) acrylamide etc.) and vinyl acetate.
- the saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more.
- the polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes.
- the average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000.
- the average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.
- a film made of a polyvinyl alcohol resin is used as the original film of the polarizer 2.
- a polyvinyl alcohol-type resin can be formed into a film by a well-known method.
- the thickness of the raw film is usually 1 to 150 ⁇ m, and is preferably 10 ⁇ m or more in consideration of easiness of stretching.
- the polarizer 2 is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried.
- the thickness of the polarizer 2 is usually 1 to 30 ⁇ m, and preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly 10 ⁇ m or less from the viewpoint of thinning the optical film 1 with an adhesive layer.
- a polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film uses a single film of a polyvinyl alcohol-based resin film as a raw film, and the uniaxial stretching treatment and dichroic dye of this film are used.
- a substrate having a polyvinyl alcohol resin layer by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to a substrate film, followed by drying, in addition to a method for performing a dyeing process (method (1)).
- the base film As the base film, a film made of a thermoplastic resin similar to the thermoplastic resin that can constitute the first and second resin films 3 and 4 described later can be used, and preferably a polyester-based resin such as polyethylene terephthalate. , Polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resins, polystyrene resins, and the like.
- the thin film polarizer 2 can be easily manufactured, and for example, the polarizer 2 having a thickness of 7 ⁇ m or less can be easily manufactured.
- the first and second resin films 3 and 4 are each independently a light-transmitting, preferably optically transparent thermoplastic resin such as a chain polyolefin resin (for example, a polyethylene resin, a polypropylene resin, etc.). ), Polyolefin resins such as cyclic polyolefin resins (such as norbornene resins); cellulose resins (such as cellulose ester resins); polyester resins (such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate); polycarbonate Resin (for example, polycarbonate derived from bisphenol such as 2,2-bis (4-hydroxyphenyl) propane); (meth) acrylic resin; polystyrene resin; polyetheretherketone resin; polysulfone resin Fat, or mixtures thereof, may be a film made of copolymer.
- a chain polyolefin resin for example, a polyethylene resin, a polypropylene resin, etc.
- Polyolefin resins
- the first and second resin films 3 and 4 are films composed of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, a (meth) acrylic resin, and the like, respectively.
- a film composed of a cellulose resin and a cyclic polyolefin resin is preferable.
- chain polyolefin resin examples include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.
- the cyclic polyolefin-based resin is a general term for resins containing, as polymerization units, cyclic olefins whose representative examples are norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or their derivatives.
- Cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins and hydrogenated products thereof, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, and aromatic compounds having a vinyl group And a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof.
- norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferred.
- the cellulose resin is preferably a cellulose ester resin, that is, a cellulose partial or completely esterified product, and examples thereof include cellulose acetate ester, propionate ester, butyrate ester, and mixed ester thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
- the polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol.
- the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.
- Polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol.
- an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferable.
- the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) isobutane, polycarbonates derived from bisphenols such as 1,1-bis (4-hydroxyphenyl) ethane and the like.
- the (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a structural unit derived from a methacrylic ester (for example, containing 50% by mass or more).
- the copolymer is preferably a copolymer in which another copolymer component is copolymerized.
- the (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of methacrylic acid esters include C 1 -C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like.
- Examples of the copolymer component that can be copolymerized with the methacrylic acid ester include acrylic acid esters.
- the acrylic ester is preferably a C 1 -C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like.
- Specific examples of other copolymerization components include unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, ⁇ -methylstyrene, and vinyl toluene; vinylcyan such as (meth) acrylonitrile.
- (Meth) acrylic resin may have a ring structure in the polymer main chain in that the durability of the film can be improved.
- the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure, or a lactone ring structure.
- Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure
- specific examples of the cyclic imide structure include a glutarimide structure and a succinimide structure. Examples include butyrolactone ring structure and valerolactone ring structure.
- the (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film-formability on the film and impact resistance of the film.
- Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester as an essential component.
- the acrylic rubber particles have a single-layer structure consisting essentially of this elastic polymer, or an elastic polymer in one layer. And a multilayer structure having Examples of the elastic polymer include a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith.
- the number of carbon atoms of the alkyl group is preferably 4 or more.
- Examples of other vinyl monomers that can be copolymerized with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate. And aromatic vinyl compounds such as styrene, vinylcyan compounds such as (meth) acrylonitrile, and the like.
- crosslinkable monomer examples include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di ( Examples include (meth) acrylates of polyhydric alcohols such as (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.
- the content of the acrylic rubber particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic resin.
- the content of the acrylic rubber particles is usually 80 parts by mass or less, preferably 60 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin.
- the first and second resin films 3 and 4 can contain usual additives in the technical field of the present invention.
- the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, and a heat stabilizer.
- the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano (meth) acrylate compounds, nickel complex salts, and the like.
- Each of the first and second resin films 3 and 4 may be an unstretched film or a uniaxially or biaxially stretched film.
- the first resin film 3 and / or the second resin film 4 may be a protective film that plays a role of protecting the polarizer 2, or may be a protective film having an optical function such as a retardation film described later. Good.
- the first resin film 3 and the second resin film 4 may be the same or different films.
- the first resin film 3 and / or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). Further, a surface treatment layer (coating layer) such as an antifouling layer or a conductive layer may be provided.
- the thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 ⁇ m, preferably 5 to 100 ⁇ m, more preferably 5 to 60 ⁇ m, still more preferably 50 ⁇ m or less (eg 1 to 40 ⁇ m), particularly 30 ⁇ m or less (for example, 5 to 25 ⁇ m).
- a polarizing plate for small and medium-sized devices such as smartphones and tablet terminals is often used as a thin film having a thickness of 30 ⁇ m or less as the first resin film 3 and / or the second resin film 4 because of the demand for thinning.
- Such a polarizing plate has a weak force to suppress the contraction force of the polarizer 2 and tends to have insufficient durability.
- the optical film 1 with the pressure-sensitive adhesive layer of the present invention has good durability.
- the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer.
- an adhesive forming the adhesive layer a water-based adhesive or an active energy ray-curable adhesive can be used.
- a conventional water-based adhesive for example, an adhesive comprising a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, And crosslinking agents such as amine compounds and polyvalent metal salts.
- a water-based adhesive made of a polyvinyl alcohol-based resin aqueous solution can be suitably used.
- a curing step for curing at a temperature of about 20 to 45 ° C. may be provided.
- the active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams.
- a curable composition containing a polymerizable compound and a photopolymerization initiator light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and preferably an ultraviolet curable adhesive.
- an active energy ray-curable adhesive When an active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying process is performed as necessary, and then an active energy ray is irradiated. A curing step of curing the active energy ray-curable adhesive is performed.
- the light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
- the adhesive for bonding these resin films may be the same type of adhesive or a different type of adhesive.
- the polarizing plates 10a and 10b can further include other films or layers. Specific examples thereof include a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like.
- the protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from scratches and dirt. After the optical film 1 with an adhesive layer is bonded onto, for example, a metal layer or a substrate, it is peeled off. It is customary to be removed.
- the base film is composed of a thermoplastic resin, for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like. be able to.
- a thermoplastic resin for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like.
- phase difference plate The phase difference film contained in the phase difference plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and second resin films 3 and 4.
- thermoplastic resins for example, polyvinyl alcohol resins, polyarylate resins, polyimide resins, polyether sulfone resins, polyvinylidene fluoride / polymethyl methacrylate resins, liquid crystal polyester resins, It can be a stretched film obtained by stretching a resin film made of an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin or the like to about 1.01 to 6 times.
- a polycarbonate film, a cyclic olefin resin film, a (meth) acrylic resin film or a cellulose resin film is preferably a uniaxially stretched or biaxially stretched film.
- a zero retardation film is also included in the retardation film.
- a zero retardation film can also be used as a protective film.
- a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like is also applicable as the retardation film.
- the zero retardation film refers to a film having both an in-plane retardation value Re and a thickness direction retardation value Rth of ⁇ 15 to 15 nm.
- This retardation film is suitably used for an IPS mode liquid crystal display device.
- the in-plane retardation value R e and the thickness direction retardation value R th are both preferably ⁇ 10 to 10 nm, and more preferably both ⁇ 5 to 5 nm.
- the in-plane retardation value R e and the thickness direction retardation value R th here are values at a wavelength of 590 nm.
- n x is a refractive index in a slow axis direction (x-axis direction) in the film plane
- n y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane)
- nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface)
- d is the thickness of the film.
- a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin
- a cellulose resin, a polyolefin resin, or a (meth) acrylic resin is preferably used because the retardation value is easily controlled and easily available.
- a film that exhibits optical anisotropy by applying and orienting a liquid crystalline compound and a film that exhibits optical anisotropy by applying an inorganic layered compound can be used as the retardation film.
- a so-called temperature compensation type retardation film, and a rod-like liquid crystal sold under the trade name “NH film” from JX Nippon Mining & Energy Co., Ltd. are tilted.
- orientation type film examples include a biaxial orientation type film sold by Sumitomo Chemical Co., Ltd. under the trade name “new VAC film”.
- stacked on the at least one surface of retardation film may be the above-mentioned protective film, for example.
- the present invention includes an optical laminate including the optical film with the pressure-sensitive adhesive layer and a substrate laminated on the pressure-sensitive adhesive layer side of the optical film with the pressure-sensitive adhesive layer. Since the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, the optical layered body of the present invention has excellent durability even under severe durability conditions (for example, durability conditions of 100 ° C. or higher).
- the substrate examples include conventional substrates such as glass substrates, ITO (tin-doped indium oxide) substrates, plastic films, organic conductive films, metal layers, overcoat resin layers, and the like.
- substrates such as glass substrates, ITO (tin-doped indium oxide) substrates, plastic films, organic conductive films, metal layers, overcoat resin layers, and the like.
- 4 to 8 are schematic cross-sectional views showing examples of the optical layered body according to the present invention.
- the optical layered body 5 shown in FIG. 4 has a metal layer 30 (or a metal wiring layer 30) laminated on a substrate 40 and an adhesive film 1a (or a polarizing plate 1a with an adhesive layer). It is the optical laminated body laminated
- the optical film 1a with an adhesive layer is obtained by laminating an adhesive layer 20 on the surface of the polarizing plate 10a on the polarizer 2 side.
- the optical laminate 6 shown in FIG. 5 is obtained by laminating the metal layer 30 laminated on the substrate 40 on the surface on the pressure-sensitive adhesive layer side of the optical film 1b with pressure-sensitive adhesive layer (or the polarizing plate 1b with pressure-sensitive adhesive layer). It is an optical laminate.
- the optical film 1b with an adhesive layer is an optical film in which an adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.
- the optical laminates 5 and 6 can be obtained by laminating the optical film with adhesive layer (1a, 1b) via the adhesive layer 20 to the metal layer 30 laminated on the substrate 40.
- the substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate.
- a glass substrate As the material of the glass substrate, soda lime glass, low alkali glass, non-alkali glass, or the like can be used.
- the metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof.
- the metal layer 30 includes, for example, at least one metal element selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals. It may be a layer containing. Among these, from the viewpoint of conductivity, it may be a layer containing at least one metal element selected from aluminum, copper, silver and gold, more preferably from the viewpoint of conductivity and cost. It may be a layer containing an element, and more preferably a layer containing an aluminum element as a main component (50 mass% or more of all metal components constituting the metal layer 30).
- the metal layer 30 may be a transparent electrode layer such as ITO, for example, and may have a transparent electrode layer made of a metal oxide such as ITO together with the metal layer 30.
- ITO transparent electrode layer
- the method for preparing the metal layer 30 is not particularly limited, and may be a metal foil, which may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an ink jet printing method, or a gravure printing method.
- the metal layer is preferably formed by a sputtering method, an ink jet printing method, or a gravure printing method, and more preferably a metal layer formed by sputtering.
- the thickness of the metal layer 30 is not particularly limited, but is usually 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and usually 0.01 ⁇ m or more.
- the line width of the metal wiring is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and usually 0.5 ⁇ m or more. It is.
- the optical laminate 7 shown in FIG. 6 is an optical laminate in which the adhesive layer 20 of the optical film 1 with an adhesive layer is laminated on a substrate 40.
- the optical laminated body 8 shown in FIG. 7 has a resin layer 50 further laminated on the surface of the metal layer 30 laminated on the substrate 40 (on the surface opposite to the substrate 40). It is an optical laminate laminated on the surface of the optical film 1 on the pressure-sensitive adhesive layer 20 side.
- resin which forms the resin layer 50 resin etc. which comprise the 1st or 2nd resin film of the said illustration are mentioned, for example.
- a plurality of metal layers 30 are laminated on a substrate 40 at predetermined intervals in the vertical and horizontal directions, and between the metal layers 30 (or gaps) and between the metal layers 30. It is the same as the optical laminate 7 except that the resin layer 50 is formed (or laminated) on the surface (on the surface opposite to the substrate 40).
- the metal layer 30 is, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in the touch input type liquid crystal display device ).
- the plurality of metal layers 30 may or may not be in contact with the pressure-sensitive adhesive layer 20 in whole or in part. Further, the metal layer 30 may be a continuous film containing the above metal or alloy. The resin layer 50 may be omitted.
- optical film (1, 1a, 1b) and the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) were bonded to produce an optical laminate, some trouble occurred.
- a so-called rework operation is required in which the optical film with the pressure-sensitive adhesive layer is peeled off from the substrate 40 or the metal layer 30 and another optical film 1 with the pressure-sensitive adhesive layer is reattached to the substrate 40 or the metal layer 30. May be.
- the optical film 1 with a pressure-sensitive adhesive layer according to the present invention is less likely to cause fogging or adhesive residue on the surface of the glass substrate or transparent electrode after being peeled off, and is excellent in reworkability.
- the pressure-sensitive adhesive layer, the optical film with the pressure-sensitive adhesive layer and the optical laminate of the present invention can be used for image display devices such as liquid crystal display devices and organic EL display devices, and the image display device is excellent. Have high durability.
- the liquid crystal display device may be a touch input type liquid crystal display device having a touch panel function.
- the touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight.
- the configuration of the touch panel may be a known method (for example, an out-cell type, an on-cell type, an in-cell type, etc.), and the operation method of the touch panel may be a known method, for example, a resistive film type, a capacitance type (surface type static type). (Capacitance method, projection type capacitance method) or the like.
- the optical film with an adhesive layer according to the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both.
- the driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method.
- the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the liquid crystal cell.
- an organic EL display device includes, for example, a structure in which a lower electrode, an organic EL layer of a portion that is operated by a substance having an optical effect, and an upper electrode are stacked in each pixel formed on the substrate from the substrate side.
- light from the organic EL that emits light when an electric current is passed through the organic EL layer is recognized through at least one of the electrodes (translucent conductive film).
- the present invention includes a (meth) acrylic resin (A) for a pressure-sensitive adhesive composition.
- the (meth) acrylic resin (A) for the pressure-sensitive adhesive composition is the same as the above-mentioned (meth) acrylic resin (A), and preferred structural units constituting the (meth) acrylic resin (A) and The preferred ratio of the structural unit is the same.
- the (meth) acrylic resin (A) for the pressure-sensitive adhesive composition is preferably a (meth) acrylic resin for the pressure-sensitive adhesive composition used for the optical film with the pressure-sensitive adhesive layer.
- the (meth) acrylic resin (A) for the pressure-sensitive adhesive composition is derived from a structural unit derived from an acetoacetyl group-containing (meth) acrylate (a1) and a hydroxy group-containing (meth) acrylate (a2).
- the mass ratio (a2) / (a1) of the structural units is 0.5 to 5, and the weight average molecular weight (Mw) is 1 million or more in terms of polystyrene.
- Such a (meth) acrylic resin (A) for a pressure-sensitive adhesive composition has a pressure-sensitive adhesive layer having excellent durability and good reworkability even in a high-temperature environment (for example, a high-temperature environment of 100 ° C. or higher). Can be formed.
- the obtained (meth) acrylic resin (A-1) had a weight average molecular weight Mw of 1.39 million and a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn of 3.9.
- the weight average molecular weight Mw and the number average molecular weight Mn were measured by high performance liquid chromatography (manufactured by Japan Waters, “Waters 2695 (main body)” and “Waters 2414 (detector)”), column: Shodex GPC.
- KF-806L (exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m) were connected in series, and tetrahydrofuran was used as an eluent, and measurement was performed in terms of standard polystyrene under conditions of a sample concentration of 1 mg / mL, a sample introduction amount of 100 ⁇ L, a temperature of 35 ° C., and a flow rate of 1 mL / min. The conditions for obtaining the GPC discharge curve were also the same.
- the glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere, a measurement temperature range of ⁇ 80 to 50 ° C., and a temperature increase rate of 10 ° C./min. It measured on condition of this.
- DSC differential scanning calorimeter
- Table 1 shows the composition of the monomer in each production example (the numerical values in Table 1 are parts by mass) and the weight average molecular weight and molecular weight distribution (Mw / Mn) of the obtained (meth) acrylic resin.
- BA normal butyl acrylate (glass transition temperature of homopolymer: ⁇ 54 ° C.)
- MA methyl acrylate (glass transition temperature of homopolymer: 10 ° C.)
- AAEM Acetoacetoxyethyl methacrylate (a1) HEA: 2-hydroxyethyl acrylate (a2)
- PEA Phenoxyethyl acrylate
- PEA2 Phenoxydiethylene glycol acrylate
- BMAA Butoxymethylacrylamide AA: Acrylic acid
- (Crosslinking agent) B-1 Trimethylolpropane adduct of tolylene diisocyanate in ethyl acetate solution (solid content concentration 75%), trade name “Coronate L” obtained from Tosoh Corporation.
- Silane compound C-1 1,6-bis (trimethoxysilyl) hexane.
- a transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 ⁇ m-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted.
- a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 ⁇ m is formed on the surface opposite to the triacetyl cellulose film in the polarizer.
- a bonded polarizing plate was produced through an adhesive made of an aqueous resin solution.
- the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) is 300 mm ⁇ 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut
- the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. A non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate. About the obtained optical laminated body, the heat test which hold
- the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm ⁇ 150 mm.
- the separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate.
- the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere having a temperature of 23 ° C.
- the optical film was peeled from the test piece together with the pressure-sensitive adhesive layer in the direction of 180 ° at a speed of 300 mm / min.
- Table 3 shows the average peeling force at the time of peeling as the adhesive strength. When the adhesive strength is 15 N or less, the rework property is excellent, and when it is 0.5 N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.
- the gel fraction evaluation method of the adhesive sheet of this invention is shown.
- the gel fraction is a value measured according to the following (a) to (d).
- a pressure-sensitive adhesive sheet having an area of about 8 cm ⁇ about 8 cm and a metal mesh made of SUS304 (about 10 cm ⁇ about 10 cm) (the mass is Wm) are bonded.
- C The mesh stapled in (2) above is placed in a glass container, and 60 mL of ethyl acetate is added and immersed, and then the glass container is stored at room temperature for 3 days.
- the mass ratio (a2) / (a1) of AAEM (a1) to HEA (a2) is in the range of 0.5 to 5.
- the optical laminates of Examples 1 to 9 exhibit superior durability as compared with the optical laminates of Comparative Examples 1 to 7 whose mass ratio is outside the range of 0.5 to 5.
- the optical laminated body of Example 4 containing 0.1 part by mass of AA and Example 5 containing 0.5 part by mass of BMAA exhibits further excellent durability. .
- Example 10-12> Preparation of pressure-sensitive adhesive composition
- the solid content of the solution was 100 parts.
- the crosslinking agent (B) and the silane compound (C) in the amount (parts by mass) shown in 5 were mixed, and ethyl acetate was added so that the solid content concentration was 14% to obtain a pressure-sensitive adhesive composition.
- the compounding quantity of each compounding component shown in Table 5 is the number of parts by mass as an active ingredient contained therein when the used product contains a solvent or the like.
- the optical film with pressure-sensitive adhesive layer (P-2) produced in (8) above is 300 mm ⁇ 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut
- the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized.
- a non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate.
- maintains for 500 hours on dry conditions with a temperature of 105 degreeC was implemented.
- the optical layered body after each test was visually observed, and the presence or absence of appearance changes such as lifting, peeling and foaming of the pressure-sensitive adhesive layer was visually observed, and durability was evaluated according to evaluation criteria. The results are shown in Table 6.
- the mass ratio (a2) / (a1) of AAEM (a1) to HEA (a2) is in the range of 0.5 to 5.
- the examples show superior durability compared to the post-production laminate of the comparative example in which the mass ratio is outside the range of 0.5-5.
- the alkyl acrylate (a4) having a Tg of the homopolymer of 0 ° C. or higher is contained in a larger proportion than the alkyl acrylate (a3) having a glass transition temperature of the homopolymer of less than 0 ° C. Even if it is a more severe durability test, it shows good durability.
- a transparent protective film (trade name [25KCHCN-TC] manufactured by Toppan Printing Co., Ltd.) obtained by applying a 7 ⁇ m hard coat layer to a 25 ⁇ m thick triacetyl cellulose film on one side of the obtained polarizing film A ) was bonded via an adhesive made of an aqueous solution of a polyvinyl alcohol resin.
- a cycloolefin resin film (trade name [ZF14-023] manufactured by Nippon Zeon Co., Ltd.) having a thickness of 23 ⁇ m is placed on the surface of the polarizing film A opposite to the surface on which the transparent protective film is bonded.
- a polarizing plate A was obtained by bonding through an adhesive composed of an aqueous solution of an alcohol resin.
- the surface of the cycloolefin-based resin film opposite to the surface in contact with the polarizer is subjected to corona discharge treatment for improving adhesion, and then the pressure-sensitive adhesive layer produced in (12) above is a separate film.
- the opposite surface adheresive layer surface
- Adhesive strength evaluation of optical film with pressure-sensitive adhesive layer “(5) Pressure-sensitive adhesive” except that the optical film with pressure-sensitive adhesive layer was replaced with the optical film with pressure-sensitive adhesive layer (P-3) prepared in (13) above.
- the adhesive strength of the optical film with adhesive layer (P-3) was evaluated in the same manner as in “Evaluation of adhesive strength of optical film with adhesive layer”. The results are shown in Table 8.
- the surface resistance value of the adhesive was measured using a surface resistivity measuring device [“HIESTA-up MCP manufactured by Mitsubishi Chemical Corporation”. -HT450 "(trade name)]. The measurement was performed under the measurement conditions of an applied voltage of 250 V and an applied time of 10 seconds. If the surface resistance value is 1.0 ⁇ 10 12 ⁇ / ⁇ or less, good antistatic properties can be obtained.
- SYMBOLS 1,1a, 1b Optical film with an adhesive layer, 2 ... Polarizer, 3 ... 1st resin film, 4 ... 2nd resin film, 5, 6, 7, 8, 9 ... Optical laminated body, 10 ... Optical film DESCRIPTION OF SYMBOLS 10a, 10b ... Polarizing plate, 20 ... Adhesive layer, 30 ... Metal layer, 40 ... Substrate, 50 ... Resin layer.
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Abstract
Description
本発明は、液晶表示装置等に利用される光学部材として有用な粘着剤組成物、該粘着剤組成物からなる粘着剤層、該粘着剤層を含む粘着剤層付光学フィルム及び光学積層体、並びに粘着剤組成物用(メタ)アクリル系樹脂に関する。
本発明の他の目的は、上記苛酷な耐久条件においても、優れた耐久性を示す粘着剤層を形成可能な粘着剤組成物用(メタ)アクリル系樹脂を提供することにある。
すなわち、本発明には、以下のものが含まれる。
[1](メタ)アクリル系樹脂(A)、架橋剤(B)及びシラン化合物(C)を含む粘着剤組成物であって、前記(メタ)アクリル系樹脂(A)は、アセトアセチル基含有(メタ)アクリレート(a1)由来の構成単位とヒドロキシ基含有(メタ)アクリレート(a2)由来の構成単位とを含み、前記構成単位の質量比(a2)/(a1)は0.5~5である、粘着剤組成物。
[2](メタ)アクリル系樹脂(A)の重量平均分子量は、ポリスチレン換算で、100万以上である、[1]に記載の粘着剤組成物。
[3](メタ)アクリル系樹脂(A)は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位とをさらに含む、[1]又は[2]に記載の粘着剤組成物。
[4]ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位との質量比(a3)/(a4)は0.1~4である、[1]~[3]のいずれかに記載の粘着剤組成物。
[5](メタ)アクリル系樹脂(A)に含まれるカルボキシル基含有(メタ)アクリレート由来の構成単位の割合は、(メタ)アクリル系樹脂(A)を構成する全構成単位100質量部に対して1.0質量部以下である、[1]~[4]のいずれかに記載の粘着剤組成物。
[6](メタ)アクリル系樹脂(A)は、(メタ)アクリルアミド系単量体由来の構成単位をさらに含む、[1]~[5]のいずれかに記載の粘着剤組成物。
[7]架橋剤(B)は、イソシアネート系化合物である、[1]~[6]のいずれかに記載の粘着剤組成物。
[8]架橋剤(B)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して、0.01~10質量部である、[1]~[7]のいずれかに記載の粘着剤組成物。
[9]シラン化合物(C)は、下記式(c1)
で表されるシラン化合物である、[1]~[8]のいずれかに記載の粘着剤組成物。
[10]シラン化合物(C)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して、0.01~10質量部である、[1]~[9]のいずれかに記載の粘着剤組成物。
[11]光重合開始剤及びその分解物を実質的に含有しない、[1]~[10]のいずれかに記載の粘着剤組成物。
[12]さらに、イオン性化合物(D)を含む、[1]~[11]のいずれかに記載の粘着剤組成物。
[13]イオン性化合物(D)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して0.01~10質量部である、[12]に記載の粘着剤組成物。
[14]イオン性化合物(D)を構成するアニオンは、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、及びテトラ(ペンタフルオロフェニル)ボレートアニオンからなる群から選択される少なくとも1種である、[12]又は[13]に記載の粘着剤組成物。
[15][1]~[14]のいずれかに記載の粘着剤組成物からなる粘着剤層。
[16]前記粘着剤層のゲル分率が70~90%である、[15]に記載の粘着剤層。
[17]光学フィルムと、該光学フィルムの少なくとも一方の面に積層された粘着剤層とを含む粘着剤層付光学フィルムであって、該粘着剤層は、[15]又は[16]に記載の粘着剤層である、粘着剤層付光学フィルム。
[18][17]に記載の粘着剤層付光学フィルムと、該粘着剤層付光学フィルムの粘着剤層側に積層された基材とを含む、光学積層体。
[19]アセトアセチル基含有(メタ)アクリレート(a1)由来の構成単位とヒドロキシ基含有(メタ)アクリレート(a2)由来の構成単位とを含み、前記構成単位の質量比(a2)/(a1)は0.5~5であり、かつ重量平均分子量は、ポリスチレン換算で、100万以上である、粘着剤組成物用(メタ)アクリル系樹脂(A)。
[20](メタ)アクリル系樹脂(A)は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位とをさらに含む、[19]に記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
[21]ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位との質量比(a3)/(a4)は0.1~4である、[19]又は[20]に記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
[22](メタ)アクリル系樹脂(A)に含まれるカルボキシル基含有(メタ)アクリレート由来の構成単位の割合は、(メタ)アクリル系樹脂(A)を構成する全構成単位100質量部に対して1.0質量部以下である、[19]~[21]のいずれかに記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
[23](メタ)アクリル系樹脂(A)は、(メタ)アクリルアミド系単量体由来の構成単位をさらに含む、[19]~[22]のいずれかに記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
本発明の粘着剤組成物は、(メタ)アクリル系樹脂(A)、架橋剤(B)及びシラン化合物(C)を含む。
(メタ)アクリル系樹脂(A)は、(メタ)アクリル系樹脂(A)を構成する全構成単位100質量%に対して、(メタ)アクリル系単量体由来の構成単位を、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上含む重合体又は共重合体であって、アセトアセチル基含有(メタ)アクリレート(a1)由来の構成単位及びヒドロキシ基含有(メタ)アクリレート(a2)由来の構成単位を含み、前記構成単位の質量比(a2)/(a1)が0.5~5である。本発明の粘着剤組成物は、(メタ)アクリル系樹脂(A)が、特定の質量比の構成単位(a1)及び(a2)を含むため、高温環境下であっても、優れた耐久性を有する粘着剤層を形成できる。
なお、アルキルアクリレートのホモポリマーのTgは、例えばPOLYMER HANDBOOK(Wiley-Interscience)などの文献値を参照できる。
一方、カルボキシル基を有する単量体由来の構成単位[カルボキシル基含有(メタ)アクリレート由来の構成単位]を含有すると耐久性をさらに向上できる。本発明では、カルボキシル基含有(メタ)アクリレート由来の構成単位の割合が少なくても有効に耐久性を向上することができるため、カルボキシル基含有(メタ)アクリレート由来の構成単位を少量含有させることにより、ITOの腐食を抑制しつつ、耐久性をさらに向上させることが可能である。
(メタ)アクリルアミド系単量体由来の構造単位を含むことで粘着剤層の耐久性をさらに向上させることができる。特に、これらのうち、N-(メトキシメチル)アクリルアミド、N-(エトキシメチル)アクリルアミド、N-(プロポキシメチル)アクリルアミド、N-(ブトキシメチル)アクリルアミド、N-(2-メチルプロポキシメチル)アクリルアミドなどが好ましい。
本発明の粘着剤組成物は、架橋剤(B)を含む。該架橋剤(B)は、(メタ)アクリル系樹脂(A)中のヒドロキシ基又はアセトアセチル基を含む極性官能基と反応可能なものであればよい。本発明では、(メタ)アクリル系樹脂(A)の側鎖に導入されたヒドロキシル基又はアセトアセチル基と架橋剤(B)とが反応し、耐久性(例えば粘着剤層の耐発泡性、耐剥がれ性及び耐凝集破壊性等)に有利な架橋構造を形成する。
粘着剤組成物は、シラン化合物(C)を含む。該シラン化合物(C)を含むことにより、粘着剤層と、基材(例えば金属層、透明電極、ガラス基板等)などとの密着性(又は接着性)を向上できる。シラン化合物(C)としては、(メタ)アクリル系樹脂(A)の反応性基(例えばヒドロキシル基、アセトアセチル基)と結合可能なシラン化合物であればよく、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、ビニルトリス(2-メトキシエトキシ)シラン、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トリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルエトキシジメチルシラン、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、3-クロロプロピルメチルジメトキシシラン、3-クロロプロピルトリメトキシシラン、3-メタクリロイルオキシプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、1,3-ビス(3’-トリメトキシプロピル)ウレアなどが挙げられる。
さらに該粘着剤層はリワーク性にも優れる。特に、高温環境下で、粘着剤層を透明電極(例えばITO基板等)に適用(又は積層)した場合においても、密着性(又は接着性)を維持でき、高い耐久性を示すことができる。
本発明の粘着剤組成物は、帯電防止剤をさらに含んでよい。帯電防止剤を含むことで、粘着剤層の帯電防止性を向上でき、例えば、離形フィルム、保護フィルムなどを剥離した際に生じる静電気による不具合などを抑制することができる。帯電防止剤としては、慣用のものが挙げられ、イオン性帯電防止剤(イオン性化合物(D))が好適である。イオン性帯電防止剤(イオン性化合物(D))を構成するカチオンとしては、有機カチオン、無機カチオンなどが挙げられる。有機カチオンとしては、例えば、ピリジニウムカチオン、イミダゾリウムカチオン、アンモニウムカチオン、スルホニウムカチオン、ホスホニウムカチオンなどが挙げられる。無機カチオンとしては、例えば、リチウムカチオン、カリウムカチオン、ナトリウムカチオン、セシウムカチオンなどのアルカリ金属カチオン、マグネシウムカチオン、カルシウムカチオンなどのアルカリ土類金属カチオンなどが挙げられる。イオン性帯電防止剤(イオン性化合物(D))を構成するアニオンとしては、無機アニオン及び有機アニオンのいずれでもよいが、帯電防止性能に優れるという点で、フッ素原子を含むアニオンが好ましい。フッ素原子を含むアニオンとしては、例えばヘキサフルオロホスフェートアニオン(PF6 -)、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CF3SO2)2N-]、ビス(フルオロスルホニル)イミドアニオン[(FSO2)2N-]、テトラ(ペンタフルオロフェニル)ボレートアニオン[(C6F5)4B-]などが挙げられる。これらの帯電防止剤は単独又は二種以上組み合わせて使用できる。特に、ビス(トリフルオロメタンスルホニル)イミドアニオン[(CF3SO2)2N-]、ビス(フルオロスルホニル)イミドアニオン[(FSO2)2N-]、及びテトラ(ペンタフルオロフェニル)ボレートアニオン[(C6F5)4B-]からなる群から選択される少なくとも1種であることが好ましい。粘着剤組成物の帯電防止性能の経時安定性に優れるという点で、室温で固体であるイオン性帯電防止剤(イオン性化合物(D))が好ましい。また、イオン性化合物(D)は、フッ素原子を含むアニオンと有機カチオンとからなるイオン性化合物であることが好ましい。
本発明の粘着剤組成物は、溶剤、架橋触媒、紫外線吸収剤、耐候安定剤、タッキファイヤー、可塑剤、軟化剤、染料、顔料、無機フィラー、光散乱性微粒子等の添加剤を単独又は二種以上含むことができる。また、粘着剤組成物に紫外線硬化性化合物を配合し、粘着剤層を形成した後に紫外線を照射して硬化させ、より硬い粘着剤層とすることもできる。
架橋触媒としては、例えばヘキサメチレンジアミン、エチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、トリメチレンジアミン、ポリアミノ樹脂及びメラミン樹脂等のアミン系化合物などが挙げられる。
本発明は、前記粘着剤組成物からなる粘着剤層を包含する。該粘着剤層は、例えば、前記粘着剤組成物を、溶剤に溶解又は分散して溶剤含有の粘着剤組成物とし、次いで、これを光学フィルム又は離形フィルムの表面に塗布・乾燥することにより形成できる。
粘着剤層付光学フィルム1を構成する光学フィルム10は、液晶表示装置等の画像表示装置に組み込まれ得る各種の光学フィルム(光学特性を有するフィルム)であってよい。
該光学フィルム10は、単層構造(例えば偏光子、位相差フィルム、輝度向上フィルム、防眩フィルム、反射防止フィルム、拡散フィルム、集光フィルム等の光学機能性フィルムなど)であってもよく、多層構造(例えば偏光板、位相差板など)であってもよい。光学フィルム10は、偏光板、偏光子、位相差板又は位相差フィルムが好ましく、特に偏光板又は偏光子が好ましい。なお、本明細書において、光学フィルムとは、画像表示(表示画面等)のために機能するフィルム(例えば、画像の見やすさの向上のために機能するフィルム)を意味する。また、本明細書において偏光板とは、偏光子の少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味し、位相差板とは、位相差フィルムの少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味する。
図2及び図3は、偏光板の層構成の例を示す概略断面図である。図2に示される偏光板10aは、偏光子2の一方の面に第1樹脂フィルム3が積層(又は積層貼合)された片面保護偏光板であり、図3に示される偏光板10bは、偏光子2の他方の面にさらに第2樹脂フィルム4が積層(又は積層貼合)された両面保護偏光板である。第1,第2樹脂フィルム3,4は、図示しない接着剤層や粘着剤層を介して偏光子2に貼合することができる。なお、偏光板10a,10bは、第1,第2樹脂フィルム3,4以外の他のフィルムや層を含んでいてよい。
(メタ)アクリル系樹脂は、メタクリル酸エステル由来の構成単位を二種以上含んでいてもよい。メタクリル酸エステルとしては、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のメタクリル酸のC1~C4アルキルエステルが挙げられる。
位相差板に含まれる位相差フィルムは、上述のとおり、光学異方性を示す光学フィルムであり、第1,第2樹脂フィルム3,4に用いることができるものとして上で例示した熱可塑性樹脂のほか、例えば、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリイミド系樹脂、ポリエーテルサルホン系樹脂、ポリビニリデンフルオライド/ポリメチルメタクリレート系樹脂、液晶ポリエステル系樹脂、エチレン-酢酸ビニル共重合体ケン化物、ポリ塩化ビニル系樹脂等からなる樹脂フィルムを1.01~6倍程度に延伸することにより得られる延伸フィルムであることができる。これらのうち、ポリカーボネート系樹脂フィルムや環状オレフィン系樹脂フィルム、(メタ)アクリル系樹脂フィルム又はセルロース系樹脂フィルムを一軸延伸又は二軸延伸した延伸フィルムが好ましい。また本明細書においては、ゼロレタデーションフィルムも位相差フィルムに含まれる。但し、ゼロレタデーションフィルムを保護フィルムとして用いることもできる。そのほか、一軸性位相差フィルム、広視野角位相差フィルム、低光弾性率位相差フィルム等と称されるフィルムも位相差フィルムとして適用可能である。
Re=(nx-ny)×d
Rth=〔(nx+ny)/2-nz〕×d
で定義される。式中、nxはフィルム面内の遅相軸方向(x軸方向)の屈折率であり、nyはフィルム面内の進相軸方向(面内でx軸に直交するy軸方向)の屈折率であり、nzはフィルム厚み方向(フィルム面に垂直なz軸方向)の屈折率であり、dはフィルムの厚みである。
本発明は、前記粘着剤層付光学フィルムと、該粘着剤層付光学フィルムの粘着剤層側に積層された基材とを含む光学積層体を包含する。本発明の光学積層体は、粘着剤層が前記粘着剤組成物から形成されるため、苛酷な耐久条件(例えば、100℃以上の耐久条件)においても優れた耐久性を有する。
本発明の粘着剤層、粘着剤層付光学フィルム及び光学積層体は、液晶表示装置や有機EL表示装置等の画像表示装置に用いることができ、該画像表示装置は優れた耐久性を有する。
有機EL表示装置は、例えば、基板上に形成された各画素内に、基板側から下部電極、光学効果を有する物質により作動する部位の有機EL層、及び上部電極が積層された構成を備えるものであることができ、有機EL層に電流を流すことによって発光する有機ELからの光を、少なくとも電極のうち一方の電極(透光性の導電膜)を通して認識するようになっている。
本発明は、粘着剤組成物用(メタ)アクリル系樹脂(A)を包含する。該粘着剤組成物用(メタ)アクリル系樹脂(A)は、上述の(メタ)アクリル系樹脂(A)と同じものであり、(メタ)アクリル系樹脂(A)を構成する好ましい構成単位及び該構成単位の好ましい割合等も同じである。また、該粘着剤組成物用(メタ)アクリル系樹脂(A)は、好ましくは粘着剤層付光学フィルムに用いられる粘着剤組成物用(メタ)アクリル系樹脂である。また、粘着剤組成物用(メタ)アクリル系樹脂(A)を適用する粘着剤組成物としては、特に限定されないが、好ましくは上記[1]に記載の粘着剤組成物が挙げられる。
冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、表1に示す組成(表1の数値は質量部である)の単量体を酢酸エチル80部、アセトン40部、アゾビスイソブチロニトリル0.012部と混合して得られた溶液を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を上昇させて還流温度で3.5時間反応させた後、酢酸エチルを加えて重合体の濃度が20%となるように調整し、(メタ)アクリル系樹脂(A-1)の酢酸エチル/アセトン溶液を得た。得られた(メタ)アクリル系樹脂(A-1)の重量平均分子量Mwは139万、重量平均分子量Mwと数平均分子量Mnとの比(Mw/Mn)は3.9であった。
単量体の組成を、表1に示す組成にしたこと以外は、製造例1と同様にして、(メタ)アクリル系樹脂(A-2~14)の酢酸エチル/アセトン溶液を得た(樹脂濃度:20%)。得られた(メタ)アクリル系樹脂(A-2~14)の重量平均分子量Mwはいずれも130万~150万の範囲であり、Mw/Mnは3~6の範囲であった。
BA:ノルマルブチルアクリレート(ホモポリマーのガラス転移温度:-54℃)
MA:メチルアクリレート(ホモポリマーのガラス転移温度:10℃)
AAEM:アセトアセトキシエチルメタクリレート(a1)
HEA:2-ヒドロキシエチルアクリレート(a2)
PEA:フェノキシエチルアクリレート
PEA2:フェノキシジエチレングリコールアクリレート
BMAA:ブトキシメチルアクリルアミド
AA:アクリル酸
(1)粘着剤組成物の調製
上記製造例で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(樹脂濃度:20%)に、該溶液の固形分100部に対して、表2に示す量(質量部)の架橋剤(B)及びシラン化合物(C)を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物を得た。表2に示す各配合成分の配合量は、使用した商品が溶剤等を含む場合は、そこに含まれる有効成分としての質量部数である。
(架橋剤)
B-1:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、東ソー(株)から入手した商品名「コロネートL」。
C-1:1,6-ビス(トリメトキシシリル)ヘキサン。
上記(1)で調製した各粘着剤組成物を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔リンテック(株)から入手した商品名「PLR-382051」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが20μmとなるように塗布し、100℃で1分間乾燥して粘着剤層(粘着剤シート)を作製した。
平均重合度約2400、ケン化度99.9モル%、厚み60μmのポリビニルアルコールフィルム〔(株)クラレ製の商品名「クラレビニロン VF-PE♯6000」〕を、37℃の純水に浸漬した後、ヨウ素とヨウ化カリウムとを含む水溶液(ヨウ素/ヨウ化カリウム/水(質量比)=0.04/1.5/100)に30℃で浸漬した。その後、ヨウ化カリウムとホウ酸とを含む水溶液(ヨウ化カリウム/ホウ酸/水(質量比)=12/3.6/100)に56.5℃で浸漬した。フィルムを10℃の純水で洗浄した後、85℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み約23μmの偏光子を得た。延伸は、主に、ヨウ素染色及びホウ酸処理の工程で行い、トータルの延伸倍率は5.3倍であった。
上記(3)で作製した粘着剤層付光学フィルム(P-1)を、偏光板の延伸軸方向が長辺となるように300mm×220mmの大きさに裁断してセパレートフィルムを剥離し、露出した粘着剤層面をガラス基板に貼合した。得られたガラス基板が貼り付けられた試験片(ガラス基板が貼り付けられた粘着剤層付光学フィルム)を、オートクレーブ中、温度50℃、圧力5kg/cm2(490.3kPa)で、20分間加圧した。ガラス基板には、コーニング社製の無アルカリガラス 商品名「Eagle XG」を使用した。
得られた光学積層体について、温度105℃の乾燥条件下で250時間保持する耐熱試験を実施した。
4:浮き、剥れ、発泡等の外観変化がほとんどみられない、
3:浮き、剥れ、発泡等の外観変化がやや目立つ、
2:浮き、剥れ、発泡等の外観変化が目立つ、
1:浮き、剥れ、発泡等の外観変化が顕著に認められる。
上記(3)で作製した粘着剤層付光学フィルム(P-1)を、25mm×150mmの大きさの試験片に裁断した。試験片からセパレーターを剥がし、その粘着剤面をガラス基板に貼り付けた。得られたガラス基板が貼り付けられた試験片(ガラス基板が貼り付けられた粘着剤層付光学フィルム)を、オートクレーブ中、温度50℃、圧力5kg/cm2(490.3kPa)で、20分間加圧した。温度23℃、相対湿度50%の雰囲気中で24時間保管したのちに、試験片から光学フィルムを粘着剤層とともに300mm/分の速度で180°方向に剥離した。剥離時の平均剥離力を粘着力として表3に示す。粘着力が15N以下である場合にはリワーク性に優れ、また0.5N以上である場合には、偏光板端部から衝撃を受けた際にも剥がれが生じにくい。
ITO層付きガラス基板のITO層の表面の表面抵抗(試験前表面抵抗値)を低抵抗率計〔三菱化学アナリテック(株)製の商品名「ロレスタ―AX」〕で測定した。次に、上記(3)で作製した粘着剤層が形成された偏光板を、20mm×40mmの大きさの試験片に裁断した。得られた試験片からセパレーターを剥がし、ガラス基板のITO層側に、粘着剤層を介して貼着した。得られた光学積層体を、温度60℃、相対湿度90%のオーブン中で500時間保管した後、温度23℃、相対湿度50%の雰囲気下で、ITO層と粘着剤層との間で剥離した。剥離後のITO層の表面抵抗(試験後表面抵抗値)を測定した。試験前後の抵抗変化率を、下記式により算出し、以下の基準で評価した。抵抗変化率が小さいほど、ITO腐食性が低い。結果を表3に示す。
抵抗変化率(%)=[(試験後表面抵抗値)-(試験前表面抵抗値)]/[試験前表面抵抗値]×100
○:抵抗変化率が50%未満であり、ITO腐食性が良好な光学積層体である。
×:抵抗変化率が50%以上であり、光学積層体のITO腐食性は不良である。
本発明の粘着剤シートのゲル分率評価方法を示す。ゲル分率が大きいほど粘着剤中で多くの架橋反応が進行していることになり、架橋密度の目安とすることができる。ゲル分率は、以下の(a)~(d)に従って測定される値である。
(b)上記(1)で得られた貼合物を秤量して、その質量をWs とし、次に粘着剤シートを包み込むように4回折りたたんでホッチキス(ステープラー)で留めた後秤量し、その質量をWb とする。
(c)上記(2)でホッチキス留めしたメッシュをガラス容器に入れ、酢酸エチル60mLを加えて浸漬した後、このガラス容器を室温で3日間保管する。
(d)ガラス容器からメッシュを取り出し、120℃で24時間乾燥した後秤量し、その質量をWa とし、次式に基づいてゲル分率を計算する。
ゲル分率(質量%)=〔{Wa-(Wb-Ws)-Wm}/(Ws-Wm)〕×100
単量体の組成を、表4に示す組成にしたこと以外は、製造例1と同様にして、(メタ)アクリル系樹脂(A-15)~(A-17)の酢酸エチル/アセトン溶液を得た(樹脂濃度:20%)。得られた(メタ)アクリル系樹脂(A-15)~(A-17)の重量平均分子量Mwはいずれも110万~150万の範囲であり、Mw/Mnは3~6の範囲であった。重量平均分子量Mw及び数平均分子量Mnは、上記に記載の方法で測定した。
BA:ノルマルブチルアクリレート(ホモポリマーのガラス転移温度:-54℃)
MA:メチルアクリレート(ホモポリマーのガラス転移温度:10℃)
AAEM:アセトアセトキシエチルメタクリレート(a1)
HEA:2-ヒドロキシエチルアクリレート(a2)
PEA:フェノキシエチルアクリレート
PEA2:フェノキシジエチレングリコールアクリレート
BMAA:ブトキシメチルアクリルアミド
AA:アクリル酸
(6)粘着剤組成物の調製
上記製造例15-17で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(樹脂濃度:20%)に、該溶液の固形分100部に対して、表5に示す量(質量部)の架橋剤(B)及びシラン化合物(C)を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物を得た。表5に示す各配合成分の配合量は、使用した商品が溶剤等を含む場合は、そこに含まれる有効成分としての質量部数である。
(架橋剤)
B-1:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、東ソー(株)から入手した商品名「コロネートL」。
(シラン化合物)
C-1:1,6-ビス(トリメトキシシリル)ヘキサン。
粘着剤組成物を上記(6)で調製した各粘着剤組成物に代えた以外、上記“(2)粘着剤層の作製”と同様の方法で粘着剤層(粘着剤シート)を作製した。
粘着剤層を上記(7)で作製した粘着剤層に代えた以外、上記“(3)粘着剤層付光学フィルム(P-1)の作製”と同様の方法で粘着剤層付光学フィルム(P-2)を作製した。
上記(8)で作製した粘着剤層付光学フィルム(P-2)を、偏光板の延伸軸方向が長辺となるように300mm×220mmの大きさに裁断してセパレートフィルムを剥離し、露出した粘着剤層面をガラス基板に貼合した。得られたガラス基板が貼り付けられた試験片(ガラス基板が貼り付けられた粘着剤層付光学フィルム)を、オートクレーブ中、温度50℃、圧力5kg/cm2(490.3kPa)で、20分間加圧した。ガラス基板には、コーニング社製の無アルカリガラス 商品名「Eagle XG」を使用した。
得られた光学積層体について、温度105℃の乾燥条件下で500時間保持する耐熱試験を実施した。
各試験後の光学積層体を目視観察し、粘着剤層の浮き、剥れ、発泡等の外観変化の有無を目視で観察し、評価基準に従って耐久性を評価した。結果を表6に示す。
4:浮き、剥れ、発泡等の外観変化がほとんどみられない、
3:浮き、剥れ、発泡等の外観変化がやや目立つ、
2:浮き、剥れ、発泡等の外観変化が目立つ、
1:浮き、剥れ、発泡等の外観変化が顕著に認められる。
粘着剤層付光学フィルムを上記(8)で作製した粘着剤層付光学フィルム(P-2)に代えた以外は、上記“(5)粘着剤層付光学フィルムの粘着力評価”と同様の方法で粘着剤層付光学フィルム(P-2)の粘着力評価を行った。結果を表6に示す。
粘着剤層付光学フィルムを上記(8)で作製した粘着剤層付光学フィルム(P-2)に代えた以外は、上記に記載の方法と同じ方法でITOが積層された光学積層体を作製し、上記に記載の方法で得られた光学積層体のITO腐食性評価を行った。結果を表6に示す。なお、評価基準も上記と同じである。
上記(7)で作製した粘着剤シートのゲル分率を上記に記載の方法で測定した。結果を表6に示す。
(11)粘着剤組成物の調製
上記製造例2-4、13で得られた(メタ)アクリル系樹脂の酢酸エチル溶液(樹脂濃度:20%)に、該溶液の固形分100部に対して、表7に示す量(質量部)の架橋剤(B)、シラン化合物(C)及びイオン性化合物(D)を混合し、さらに固形分濃度が14%となるように酢酸エチルを添加して粘着剤組成物を得た。表7に示す各配合成分の配合量は、使用した商品が溶剤等を含む場合は、そこに含まれる有効成分としての質量部数である。
(架橋剤)
B-1:トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液(固形分濃度75%)、東ソー(株)から入手した商品名「コロネートL」。
(シラン化合物)
C-1:1,6-ビス(トリメトキシシリル)ヘキサン。
(イオン性化合物)
D-1:N-デシルピリジニウム ビス(フロオロスルホニル)イミド
粘着剤組成物を上記(11)で調製した各粘着剤組成物に代えた以外は、上記“(2)
粘着剤層の作製”と同様の方法で粘着剤層を作製した。
平均重合度2400、ケン化度99.9モル%、厚み30μmのポリビニルアルコールフィルム((株)クラレ製の商品名〔クラレポバールフィルム VF-PE♯3000〕)を、37℃の純水に浸漬した後、ヨウ素とヨウ化カリウムとを含む水溶液(ヨウ素/ヨウ化カリウム/水(重量比)=0.04/1.5/100)に30℃で浸漬した。その後、ヨウ化カリウムとホウ酸とを含む水溶液(ヨウ化カリウム/ホウ酸/水(重量比)=12/3.6/100)に56.5℃で浸漬した。次いで、フィルムを10℃の純水で洗浄した後、85℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚さ約12μmの偏光子Aを得た。延伸は、主に、ヨウ素染色およびホウ酸処理の工程で行い、トータルの延伸倍率は5.3倍であった。
粘着剤層付光学フィルムを上記(13)で作製した粘着剤層付光学フィルム(P-3)に代えた以外は、上記“(4)粘着剤層付光学フィルムの耐久性評価”と同様の方法で粘着剤層付光学フィルムの耐久性評価を行った。結果を表8に示す。なお、評価基準も上記と同じである。
粘着剤層付光学フィルムを上記(13)で作製した粘着剤層付光学フィルム(P-3)に代えた以外は、上記“(5)粘着剤層付光学フィルムの粘着力評価”と同様の方法で粘着剤層付光学フィルム(P-3)の粘着力評価を行った。結果を表8に示す。
粘着剤層付光学フィルムを上記(13)で作製した粘着剤層付光学フィルム(P-3)に代えた以外は、上記に記載の方法と同じ方法でITOが積層された光学積層体を作製し、上記に記載の方法で得られた光学積層体のITO腐食性評価を行った。結果を表8に示す。なお、評価基準も上記と同じである。
上記(12)で作製した粘着剤シートのゲル分率を上記に記載の方法で測定した。結果を表8に示す。
Claims (23)
- (メタ)アクリル系樹脂(A)、架橋剤(B)及びシラン化合物(C)を含む粘着剤組成物であって、
前記(メタ)アクリル系樹脂(A)は、アセトアセチル基含有(メタ)アクリレート(a1)由来の構成単位とヒドロキシ基含有(メタ)アクリレート(a2)由来の構成単位とを含み、前記構成単位の質量比(a2)/(a1)は0.5~5である、粘着剤組成物。 - (メタ)アクリル系樹脂(A)の重量平均分子量は、ポリスチレン換算で、100万以上である、請求項1に記載の粘着剤組成物。
- (メタ)アクリル系樹脂(A)は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位とをさらに含む、請求項1又は2に記載の粘着剤組成物。
- ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位との質量比(a3)/(a4)は0.1~4である、請求項1~3のいずれかに記載の粘着剤組成物。
- (メタ)アクリル系樹脂(A)に含まれるカルボキシル基含有(メタ)アクリレート由来の構成単位の割合は、(メタ)アクリル系樹脂(A)を構成する全構成単位100質量部に対して1.0質量部以下である、請求項1~4のいずれかに記載の粘着剤組成物。
- (メタ)アクリル系樹脂(A)は、(メタ)アクリルアミド系単量体由来の構成単位をさらに含む、請求項1~5のいずれかに記載の粘着剤組成物。
- 架橋剤(B)は、イソシアネート系化合物である、請求項1~6のいずれかに記載の粘着剤組成物。
- 架橋剤(B)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して、0.01~10質量部である、請求項1~7のいずれかに記載の粘着剤組成物。
- シラン化合物(C)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して、0.01~10質量部である、請求項1~9のいずれかに記載の粘着剤組成物。
- 光重合開始剤及びその分解物を実質的に含有しない、請求項1~10のいずれかに記載の粘着剤組成物。
- さらに、イオン性化合物(D)を含む、請求項1~11のいずれかに記載の粘着剤組成物。
- イオン性化合物(D)の割合は、(メタ)アクリル系樹脂(A)100質量部に対して0.01~10質量部である、請求項12に記載の粘着剤組成物。
- イオン性化合物(D)を構成するアニオンは、ビス(トリフルオロメタンスルホニル)イミドアニオン、ビス(フルオロスルホニル)イミドアニオン、及びテトラ(ペンタフルオロフェニル)ボレートアニオンからなる群から選択される少なくとも1種である、請求項12又は13に記載の粘着剤組成物。
- 請求項1~14のいずれかに記載の粘着剤組成物からなる粘着剤層。
- 前記粘着剤層のゲル分率が70~90%である、請求項15に記載の粘着剤層。
- 光学フィルムと、該光学フィルムの少なくとも一方の面に積層された粘着剤層とを含む粘着剤層付光学フィルムであって、該粘着剤層は、請求項15又は16に記載の粘着剤層である、粘着剤層付光学フィルム。
- 請求項17に記載の粘着剤層付光学フィルムと、該粘着剤層付光学フィルムの粘着剤層側に積層された基材とを含む、光学積層体。
- アセトアセチル基含有(メタ)アクリレート(a1)由来の構成単位とヒドロキシ基含有(メタ)アクリレート(a2)由来の構成単位とを含み、前記構成単位の質量比(a2)/(a1)は0.5~5であり、かつ重量平均分子量は、ポリスチレン換算で、100万以上である、粘着剤組成物用(メタ)アクリル系樹脂(A)。
- (メタ)アクリル系樹脂(A)は、ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位とをさらに含む、請求項19に記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
- ホモポリマーのガラス転移温度が0℃未満のアルキルアクリレート(a3)由来の構成単位と、ホモポリマーのガラス転移温度が0℃以上のアルキルアクリレート(a4)由来の構成単位との質量比(a3)/(a4)は0.1~4である、請求項19又は20に記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
- (メタ)アクリル系樹脂(A)に含まれるカルボキシル基含有(メタ)アクリレート由来の構成単位の割合は、(メタ)アクリル系樹脂(A)を構成する全構成単位100質量部に対して1.0質量部以下である、請求項19~21のいずれかに記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
- (メタ)アクリル系樹脂(A)は、(メタ)アクリルアミド系単量体由来の構成単位をさらに含む、請求項19~22のいずれかに記載の粘着剤組成物用(メタ)アクリル系樹脂(A)。
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JP2020114903A (ja) * | 2019-01-17 | 2020-07-30 | リンテック株式会社 | 粘着性組成物、粘着剤、粘着シートおよび表示体 |
CN113214764A (zh) * | 2020-01-21 | 2021-08-06 | 日本电石工业株式会社 | 耐热性粘合片用粘合剂组合物和耐热性粘合剂 |
JP7369887B2 (ja) | 2021-11-15 | 2023-10-26 | 日東電工株式会社 | 粘着剤組成物、粘着シート、光学積層体、画像表示パネル及び画像表示装置 |
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JP7369887B2 (ja) | 2021-11-15 | 2023-10-26 | 日東電工株式会社 | 粘着剤組成物、粘着シート、光学積層体、画像表示パネル及び画像表示装置 |
JP7369886B2 (ja) | 2021-11-15 | 2023-10-26 | 日東電工株式会社 | 粘着剤組成物、粘着シート、光学積層体、画像表示パネル及び画像表示装置 |
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