WO2020116395A1 - Layered body and method for manufacturing layered body - Google Patents
Layered body and method for manufacturing layered body Download PDFInfo
- Publication number
- WO2020116395A1 WO2020116395A1 PCT/JP2019/047040 JP2019047040W WO2020116395A1 WO 2020116395 A1 WO2020116395 A1 WO 2020116395A1 JP 2019047040 W JP2019047040 W JP 2019047040W WO 2020116395 A1 WO2020116395 A1 WO 2020116395A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- adherend
- adhesive layer
- pressure
- sensitive adhesive
- laminate
- Prior art date
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Images
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
Definitions
- the present invention relates to a laminate and a method for manufacturing the laminate.
- LCD liquid crystal displays
- touch panels display devices
- a transparent adhesive sheet is used for bonding optical members, and a transparent adhesive sheet is also used for bonding the display device and the input device. ..
- Adhesive sheets used for such applications require various properties in addition to adhesive performance.
- a resin plate such as a polycarbonate base material is often used as an optical member because it has excellent transparency and heat resistance, but when an adhesive sheet is attached to the resin plate and placed in a high temperature environment, Bubbles may be generated in the pressure-sensitive adhesive layer, which may affect optical performance. Therefore, excellent outgas resistance may be required depending on the application of the pressure-sensitive adhesive sheet.
- Patent Documents 1 to 3 disclose optical laminated bodies including an adhesive layer.
- Patent Document 1 discloses an optical laminate in which a resin plate made of polycarbonate or acrylic is attached to an adherend via a transparent adhesive.
- Patent Document 2 discloses a laminated body including a laminated unit having a transparent resin layer and a glass layer arranged via an adhesive layer.
- Patent Document 3 a first layer and a second layer which are made of a material capable of generating outgas and have an adherend surface, and a phase difference which is arranged between the first layer and the second layer
- An optical laminate comprising a layer and a first adhesive layer and a second adhesive layer is disclosed.
- JP, 2017-222085 A Japanese Patent Laid-Open No. 2018-1615 Japanese Patent Laid-Open No. 2018-45567
- the present inventors have found that when a resin plate, particularly when a pressure-sensitive adhesive sheet is attached to polycarbonate, the water content of the resin plate is vaporized and expanded by heating, and the pressure due to the expansion. It was found that bubbles and the like are generated by the above. Therefore, as a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, as a result of a durability test of a laminate obtained by laminating a first adherend, an adhesive layer and a second adherend in this order.
- the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at that temperature can be calculated.
- the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer is Fi
- the interface adhesion between the second adherend and the pressure-sensitive adhesive layer is Fb. It has been found that by setting Fb>Fv, it is possible to obtain a laminate that can exhibit excellent outgas resistance against any outgas generation mode.
- the present invention has the following configurations.
- the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (b) is defined as Fi, When the interface adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C.
- the stress when peeling between the first adherend and the pressure-sensitive adhesive layer in the opposite direction is measured as the interfacial adhesion (Ft); when the first adherend and the pressure-sensitive adhesive layer do not peel.
- the interfacial adhesion (Ft) shall be greater than the maximum tensile stress;
- the elastic modulus G′ is measured and the value of the shear storage elastic modulus G′ at 85° C.
- Adhesive is applied to the surface of the second adherend of the laminate having a size of 10 mm ⁇ 10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm ⁇ a width of 30 mm ⁇ a length of 50 mm; on the adhesive layer side.
- a glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of °C, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%.
- the stress when peeling between the second adherend and the adhesive layer is measured in the opposite direction, and the stress is measured as the interfacial adhesion force (Fb); when the second adherend and the adhesive layer do not peel.
- Fb interfacial adhesion force
- the interfacial adhesion (Fb) is assumed to be larger than the maximum tensile stress.
- the first adherend is the laminate according to [1] or [2], which contains a polycarbonate resin.
- the pressure-sensitive adhesive layer used in the step of laminating is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition
- the method for producing a laminate according to [5] wherein the pressure-sensitive adhesive composition contains a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
- FIG. 1 is a cross-sectional view illustrating the structure of a laminate including the adhesive sheet of the present invention.
- FIG. 2 is a diagram illustrating a method for measuring the cross adhesive force of the double-sided adhesive sheet.
- FIG. 3 is a cross-sectional view illustrating how outgas is generated in the laminated body.
- the present invention relates to a laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order.
- the laminate 1 of the present invention has a first adherend 2, an adhesive layer 4, and a second adherend 6 in this order.
- the first adherend 2 and the pressure-sensitive adhesive layer 4 are laminated so as to be in direct contact with each other, and the pressure-sensitive adhesive layer 4 and the second adherend 6 are also in direct contact with each other. It is stacked.
- the saturated water vapor pressure at 85° C. is Fv
- the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by Fi is Fi, and the interfacial adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (c). Is Fb, the conditions of Ft>Fv, Fi>Fv, and Fb>Fv are satisfied.
- the stress when the glass plate is pulled in the opposite direction in the thickness direction and peeled between the first adherend and the pressure-sensitive adhesive layer is measured as the interfacial adhesion (Ft).
- the interfacial adhesion (Ft) is set to be larger than the maximum tensile stress.
- an adhesive is applied on the pressure-sensitive adhesive layer exposed by removing the second adherend,
- the adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the second adherend and the adhesive may be attached via the adhesive.
- the stacking order in the measurement sample is appropriately changed depending on each case in procedures 1 to 3 described later.
- the elastic modulus G′ is measured, and the value of the shear storage elastic modulus G′ at 85° C. is defined as Fi.
- the adhesive used at this time preferably has a glass transition temperature (Tg) of 120° C. or higher so that the measured shear storage elastic modulus is not affected.
- Tg glass transition temperature
- Aron Alpha Quick Attack Versatile EXTRA manufactured by Konishi Co., Ltd. can be used.
- a glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is bonded to the pressure-sensitive adhesive layer side via an adhesive so that the two glass plates have a cross-shaped positional relationship with each other, to obtain a measurement sample. After the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours, the measurement sample was placed in an environment of 85° C.
- the interfacial adhesion (Fb) is set to be larger than the maximum tensile stress.
- an adhesive is applied to the pressure-sensitive adhesive layer exposed by removing the first adherend, and the adhesive is
- the adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the first adherend and the adhesive may be attached via the adhesive.
- the stacking order in the measurement sample is appropriately changed depending on each case in procedures 1 to 3 described later.
- the measuring method (a) and the measuring method (c) are performed by sequentially performing the following procedures 1 to 3.
- (Procedure 1) After cutting the laminated body into a size of 10 mm ⁇ 10 mm, an adhesive is thinly applied to one surface (the surface on the first adherend side) of the laminated body, and the thickness is 4.0 mm ⁇ width 30 mm ⁇ length 50 mm. The laminated body is fixed to the central part of the glass A of FIG. Next, an adhesive is similarly applied to the other surface side (the surface on the side of the second adherend) of the laminated body, and the laminated body is provided on the central portion of the glass B having a thickness of 4.0 mm ⁇ a width of 30 mm ⁇ a length of 50 mm. To fix.
- the two glasses A and B are laminated so as to have a cross-shaped positional relationship with each other.
- the upper diagram of FIG. 2 is a view of the measurement sample viewed from the plane direction
- the lower diagram of FIG. 2 is a view of the side surface of the measurement sample viewed from the cross-sectional direction.
- a measurement sample is formed by bonding glass A10 and glass B20 on each surface of the laminate 1 so as to have a cross-shaped positional relationship with each other.
- the measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Leave for 3 hours.
- the adhesive is not particularly limited as long as the adhesive force (maximum stress in the above measurement) between each adherend and glass is larger than the saturated vapor pressure (Fv) at 85°C.
- the glass used for measurement is preferably alkali glass, and for example, float plate glass manufactured by Standard Test Piece Co., Ltd. can be used.
- the saturated water vapor pressure Fv at 85° C. in the present specification is 0.058 MPa.
- the saturated vapor pressure at 85°C the value described in JIS Z 8806 Appendix Table 1.1 Saturated vapor pressure of water can be adopted.
- the saturated vapor pressure (Fv) at 85° C. the interfacial adhesion (Ft) between the first adherend and the pressure-sensitive adhesive layer measured by the method described above, and the shear storage of the pressure-sensitive adhesive layer.
- the relationship between the elastic modulus (Fi) and the interfacial adhesion (Fb) between the second adherend and the pressure-sensitive adhesive layer satisfies the following conditions. Ft>Fv, Fi>Fv, and Fb>Fv
- Ft>Fv, Fi>Fv, and Fb>Fv In the present invention, by satisfying the above conditions for Fv, Ft, Fi and Fb, it is possible to exhibit excellent outgas resistance against any outgas generation mode.
- FIG. 3 there are three error modes as shown in Fig. 3 as the mode of outgas generation.
- An error mode 1 is shown in FIG. 3A.
- this error mode bubbles R are generated at the interface between the first adherend 2 and the pressure-sensitive adhesive layer 4.
- 3B shows an error mode 2.
- bubbles R are generated in the pressure-sensitive adhesive layer 4.
- 3C shows an error mode 3.
- bubbles R are generated at the interface between the second adherend 6 and the adhesive layer 4.
- Fv, Ft, Fi and Fb as predetermined conditions, it is possible to suppress the generation of various outgases as shown in FIGS. 3(a) to 3(c).
- the pressure-sensitive adhesive layer is prevented from floating or peeling from the adherend even under high temperature conditions, and the adhesion of the constituent members of the laminate is improved.
- the interfacial adhesion (Ft) between the first adherend and the pressure-sensitive adhesive layer may be larger than 0.058 MPa, more preferably 0.10 MPa or more, and more preferably 0.15 MPa or more. More preferably, it is more preferably 0.20 MPa or more, and particularly preferably 0.25 MPa or more.
- the shear storage elastic modulus (Fi) of the pressure-sensitive adhesive layer may be larger than 0.058 MPa, more preferably 0.10 MPa or more, and further preferably 0.15 MPa or more.
- the interface adhesion force (Fb) between the second adherend and the pressure-sensitive adhesive layer may be greater than 0.058 MPa, more preferably 0.10 MPa or more, and preferably 0.15 MPa or more. More preferably, it is more preferably 0.20 MPa or more, and particularly preferably 0.25 MPa or more.
- the laminate of the present invention is preferably used as an optical member. That is, the laminate of the present invention is preferably an optical laminate.
- the layered product of the present invention is preferably used as a constituent member of parts for electric and electronic devices such as home electric appliances and game machines, and decorative parts such as automobiles, in addition to image display devices.
- the laminated body of the present invention since the laminated body of the present invention has excellent outgas resistance even under high temperature conditions, it is also preferably used as an in-vehicle optical member such as an in-vehicle display.
- the laminate of the present invention includes a first adherend and a second adherend that are bonded together via an adhesive layer.
- the first adherend and the second adherend may be the same kind of adherend, but may be different adherends.
- at least one of the first adherend and the second adherend may be an adherend that generates outgas. Even in such a case, the laminate of the present invention can exhibit excellent outgas resistance.
- the first adherend is preferably a resin plate.
- the resin constituting the resin plate include polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polystyrene, polycarbonate, polyetherimide, polyimide, fluororesin, polyamide, (meth)acrylic resin, polymethylmethacrylate resin. , Copolymers of acrylonitrile and styrene, copolymers of acrylonitrile, butadiene and styrene, and the like, and a mixed resin thereof may be used.
- the resin plate is preferably a (meth)acrylic resin plate and a polycarbonate resin plate, and more preferably a polycarbonate resin plate.
- the first adherend contains a polycarbonate resin.
- the polycarbonate resin includes only a composite material of a polycarbonate resin and other components (for example, a laminate of a methyl methacrylate base material and a polycarbonate resin plate or a polycarbonate resin plate with a hard coat layer), or a polycarbonate resin alone. Includes materials such as The polycarbonate resin plate is a member that is apt to generate outgas particularly under high temperature conditions. However, in the present invention, by setting the relationship of Fv, Ft, Fi, and Fb to a predetermined condition, polycarbonate is used as the first adherend. Using a resin plate, outgassing can be suppressed even when the laminate is placed under high temperature conditions.
- the first adherend can function as a cover film or a protect film in the optical laminate.
- the first adherend is a polycarbonate resin plate
- examples of the polycarbonate resin plate include Panlite PC-1151 manufactured by Teijin Chemicals Ltd. and Iupilon NF2000 manufactured by Mitsubishi Gas Chemical Co., Inc. Can be mentioned.
- a laminated base material in which a hard coat layer is laminated on at least one surface of a polycarbonate resin plate, or polymethylmethacrylate (PMMA) on at least one surface of the polycarbonate resin plate You may use the laminated base material with which the base material was laminated
- the second adherend preferably contains at least one selected from a glass plate and a resin plate.
- the second adherend is preferably an optical member, for example, a touch panel, an ITO film, or a polarizing plate.
- a glass plate and a resin plate are mentioned as a member which comprises these optical members.
- the bonding surface of the second adherend with the pressure-sensitive adhesive layer is preferably a glass plate or a resin plate.
- the thickness of each of the first adherend and the second adherend is preferably 0.5 mm or more, more preferably 0.7 mm or more, and further preferably 1 mm or more. Further, the thickness of each of the first adherend and the second adherend is preferably 5 mm or less, more preferably 4 mm or less, and further preferably 3 mm or less.
- the laminate of the present invention includes a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer may be a single pressure-sensitive adhesive layer or a multi-layer pressure-sensitive adhesive layer formed by laminating a plurality of pressure-sensitive adhesive layers.
- the thickness of the pressure-sensitive adhesive layer can be appropriately set depending on the application and is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more. Moreover, the thickness of the pressure-sensitive adhesive layer is preferably 1000 ⁇ m or less, more preferably 750 ⁇ m or less, and further preferably 500 ⁇ m or less. By setting the thickness of the pressure-sensitive adhesive layer within the above range, the outgas resistance of the laminate can be more effectively enhanced. Further, by setting the thickness of the pressure-sensitive adhesive layer within the above range, it is possible to sufficiently secure the step followability when the adherend is a member having a step. Furthermore, when the thickness of the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive layer can be easily manufactured.
- the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the above-mentioned measurement method (b) may be larger than 0.058 MPa, and is more preferably 0.10 MPa or more. , 0.15 MPa or more is more preferable.
- the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer is the shear storage elastic modulus G′ of the pressure-sensitive adhesive layer in the temperature range from 20° C. to 120° C. under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0%. Is measured and the value of the shear storage elastic modulus G′ at 85° C. is calculated.
- the adhesive layer is preferably an acrylic adhesive layer.
- the acrylic pressure-sensitive adhesive layer preferably contains an acrylic copolymer.
- a "unit” is a repeating unit (monomer unit) which comprises a polymer.
- (Meth)acrylic acid represents both acrylic acid and methacrylic acid, or either.
- the pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer having a post-curing property before being attached to the first adherend and the second adherend. That is, it is preferable that the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition in a state before being bonded to the first adherend and the second adherend.
- the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer
- the pressure-sensitive adhesive composition contains at least an acrylic copolymer.
- the pressure-sensitive adhesive composition is a crosslinkable acrylic copolymer, It preferably contains a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
- the acrylic copolymer preferably contains a non-crosslinkable (meth)acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group. That is, the acrylic copolymer is preferably a crosslinkable acrylic copolymer.
- the crosslinkable acrylic copolymer is preferably one having transparency to the extent that visibility of a display device or the like is not deteriorated.
- the non-crosslinkable (meth)acrylic acid ester unit (a1) is a repeating unit derived from a (meth)acrylic acid alkyl ester.
- alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate.
- (meth)acrylic acid alkyl esters at least one selected from methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate since it has high adhesiveness. preferable.
- acrylic monomer unit (a2) having a crosslinkable functional group examples include a hydroxy group-containing monomer unit, an amino group-containing monomer unit, a glycidyl group-containing monomer unit and a carboxy group-containing monomer unit. Can be mentioned. These monomer units may be of one type or of two or more types.
- the hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer.
- Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Examples thereof include (meth)acrylic acid [(mono-, di- or poly)alkylene glycol] such as (meth)acrylic acid mono(diethylene glycol), and (meth)acrylic acid lactone such as (meth)acrylic acid monocaprolactone.
- Examples of the amino group-containing monomer unit include repeating units derived from amino group-containing monomers such as (meth)acrylamide and allylamine.
- Examples of the glycidyl group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth)acrylate.
- Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
- the content of the crosslinkable acrylic monomer unit (a2) in the acrylic copolymer is preferably 0.01% by mass or more and 40% by mass or less, and more preferably 0.5% by mass or more and 35% by mass or less. preferable.
- the acrylic copolymer preferably contains a hydroxy group-containing monomer unit.
- the content of the hydroxy group-containing monomer unit is preferably 0.01% by mass or more and 40% by mass or less, and 0.5% by mass or more and 35% by mass or less, based on the total mass of the acrylic copolymer. More preferably.
- the acrylic copolymer may further include units derived from a nitrogen-containing monomer.
- the nitrogen-containing monomer is a monomer containing a nitrogen element in one molecule.
- Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam and N-vinyl-2-. Pyrrolidone, dimethylaminoethyl (meth)acrylate, N-vinylformamide and the like can be mentioned.
- the nitrogen-containing monomer is preferably at least one selected from acrylamide derivatives, amino group-containing monomers and nitrogen-containing heterocycle-containing monomers, and more preferably acrylamide derivatives.
- the acrylamide derivative is more preferably at least one selected from dimethylacrylamide, diethylacrylamide and acryloylmorpholine, and particularly preferably dimethylacrylamide.
- the content of units derived from the nitrogen-containing monomer is preferably 1% by mass or more, and more preferably 3% by mass or more, based on the total mass of the acrylic copolymer.
- the content of units derived from the nitrogen-containing monomer is preferably 20% by mass or less based on the total mass of the acrylic copolymer.
- the acrylic copolymer may contain (meth)acrylic acid alkoxyalkyl ester units or (meth)acrylic acid ester having an alicyclic structure, if necessary. Further, the acrylic copolymer may have a monomer unit other than the above monomer units. Any other monomer may be used as long as it can be copolymerized with the above monomer unit, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, and vinylpyridine.
- the weight average molecular weight of the acrylic copolymer is preferably 100,000 or more, more preferably 300,000 or more, further preferably 500,000 or more, particularly preferably 600,000 or more.
- the weight average molecular weight of the acrylic copolymer is preferably 2,000,000 or less, more preferably 1.8 million or less, and further preferably 1.6 million or less. When the weight average molecular weight of the acrylic copolymer is within the above range, the coatability is excellent, and the pressure-sensitive adhesive layer is likely to exhibit excellent outgas resistance.
- the weight average molecular weight of the acrylic copolymer is a value measured by gel permeation chromatography (GPC) and determined on a polystyrene basis.
- the measurement conditions of gel permeation chromatography (GPC) are as follows. Solvent: Tetrahydrofuran (THF) Column: Shodex KF801, KF803L, KF800L, KF800D (four Showa Denko KK were used by connecting) Column temperature: 40°C Sample concentration: 0.5% by mass Detector: RI-2031plus (made by JASCO) Pump: RI-2080plus (made by JASCO) Flow rate (flow velocity): 0.8 ml/min Injection volume: 10 ⁇ l
- the content of the acrylic copolymer is preferably 75% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more based on the total mass of the pressure-sensitive adhesive composition. ..
- the pressure-sensitive adhesive composition preferably contains a crosslinking agent.
- the cross-linking agent can be appropriately selected in consideration of the reactivity with the cross-linkable functional group of the acrylic copolymer.
- it can be selected from known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound and a butylated melamine compound.
- isocyanate compounds and epoxy compounds are preferable because they can easily crosslink the acrylic monomer unit (a2) having a crosslinkable functional group.
- an isocyanate compound is more preferably used because of the reactivity of the hydroxy group.
- Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like.
- Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polygly
- the content of the crosslinking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired pressure-sensitive adhesive properties and the like, but is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. It is preferably 0.1 part by mass or more and 3 parts by mass or less.
- the crosslinking agent one kind may be used alone, or two or more kinds may be used in combination, and when two kinds or more are used in combination, the total mass is preferably within the above range.
- the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator.
- the photopolymerization initiator is used for polymerizing the acrylic copolymer.
- the photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-enyl propanone, 1-[4-( 2-Hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1- Alkylphenone photoinitiators such as propanone, acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl)phenylphosphine
- the content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.4 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. preferable.
- the photopolymerization initiator one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.
- the pressure-sensitive adhesive composition preferably contains a monofunctional monomer having one reactive double bond in the molecule.
- the monofunctional monomer examples include lauryl acrylate, isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N,N-dimethyl. Examples thereof include acrylamide, N,N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone and the like. Among them, the monofunctional monomer is preferably lauryl acrylate. Examples of commercially available monofunctional monomers include lauryl acrylate (LA) manufactured by Osaka Organic Chemical Industry Co., Ltd. and the like.
- the content of the monofunctional monomer is preferably 1 to 20 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
- the monofunctional monomers may be used alone or in combination of two or more, and when two or more are used in combination, the total mass is preferably within the above range.
- the pressure-sensitive adhesive composition preferably contains a polyfunctional monomer having two or more reactive double bonds in the molecule.
- the polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more and less than five reactive double bonds, and preferably two. More preferably, it has less than four.
- polyfunctional monomer examples include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, di(meth)acrylic acid 1, 4-butylene glycol, 1,9-nonanediol di(meth)acrylic acid, 1,6-hexanediol diacrylic acid, polybutylene glycol di(meth)acrylic acid, neopentyl glycol di(meth)acrylic acid, di(meth)acrylic acid ) Tetraethylene glycol acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, diacrylate of bisphenol A diglycidyl ether, trimethylolpropane tri(meth)acrylate, tri(meth)acrylic
- examples thereof include (meth)acrylic acid esters of polyhydric alcohols such as acid pentaerythritol and pentaerythr
- the polyfunctional monomer is preferably a polyfunctional monomer having a bisphenol skeleton in one molecule.
- the hardness of the pressure-sensitive adhesive layer after post-curing can be more effectively increased.
- the outgas resistance of the pressure-sensitive adhesive layer after post-curing can be more effectively enhanced.
- polyfunctional monomers having a bisphenol skeleton in one molecule include diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and diacrylate of bisphenol F diglycidyl ether.
- polyfunctional monomer can be used as the polyfunctional monomer.
- bifunctional monomer M211B bisphenol A ethylene oxide modified diacrylate
- Toagosei Co., Ltd. bifunctional monomer M08 (bisphenol F ethylene oxide modified diacrylate)
- Shin Nakamura Chemical Co., Ltd. Bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate) and the like.
- the content of the polyfunctional monomer is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
- the polyfunctional monomers may be used alone or in combination of two or more, and when two or more are used in combination, the total mass is preferably within the above range.
- the pressure-sensitive adhesive composition may contain a solvent. That is, the pressure-sensitive adhesive composition may be a solvent-type pressure-sensitive adhesive composition.
- the solvent examples include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane; methanol, ethanol, Alcohols such as propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate , Ethyl acetate, butyl acetate
- the solvent may be used alone or in combination of two or more.
- the content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but can be 25 parts by mass or more and 500 parts by mass or less, and 30 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. can do.
- the pressure-sensitive adhesive composition may contain components other than the above components as long as the effects of the present invention are not impaired.
- other components include components known as additives for pressure-sensitive adhesives.
- a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, and a light stabilizer such as a hindered amine compound can be selected as necessary.
- a dye or a pigment may be added for the purpose of coloring.
- plasticizer examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoic acid.
- carboxylic acid vinyl esters such as vinyl acid salt and styrene.
- antioxidant examples include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like. These antioxidants may be used alone or in combination of two or more.
- a benzotriazole resin can be mentioned as a preferable example because of the compatibility of the pressure-sensitive adhesive and the high effect.
- the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin and the like.
- the silane coupling agent include a mercaptoalkoxysilane compound (eg, a mercapto group-substituted alkoxy oligomer).
- the ultraviolet absorber include benzotriazole compounds and benzophenone compounds. However, when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them in a range that does not inhibit the polymerization reaction.
- the present invention also relates to a method for manufacturing the above-mentioned laminated body.
- the method for manufacturing a laminate comprises a step of laminating a first adherend and a second adherend to a pressure-sensitive adhesive layer having a post-curing property, and a first adherend or a second adherend. It is preferable to include a step of irradiating the active energy ray from the side.
- the post-curing pressure-sensitive adhesive layer can be manufactured, for example, as follows.
- the step of producing a pressure-sensitive adhesive layer having post-curability preferably includes a step of applying the above-mentioned pressure-sensitive adhesive composition to form a coating film and heating the coating film.
- the reaction of the acrylic copolymer and the crosslinking agent proceeds to form a semi-cured pressure-sensitive adhesive layer.
- the coating of the pressure-sensitive adhesive composition can be carried out using a known coating device.
- the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, and a curtain coater.
- the coating amount after drying is preferably 10 ⁇ m/m 2 or more, and more preferably 20 ⁇ m/m 2 or more. In addition, it is preferable that the coating amount after drying be 500 ⁇ m/m 2 or less, and more preferable that the coating amount be 300 ⁇ m/m 2 or less.
- the heating and drying process of the coating film can be carried out using a known heating device such as a heating furnace or an infrared lamp. For example, it is dried for 10 seconds or more and 10 minutes or less in an air circulation type constant temperature oven at 50° C. or more and 150° C. or less.
- a known heating device such as a heating furnace or an infrared lamp. For example, it is dried for 10 seconds or more and 10 minutes or less in an air circulation type constant temperature oven at 50° C. or more and 150° C. or less.
- an aging treatment step in which the pressure-sensitive adhesive sheet is allowed to stand at a certain temperature for a certain period.
- the aging treatment step can be performed by standing for 7 days under the conditions of 23° C. and 50% relative humidity.
- the first layer and the second layer are formed on each surface of the post-curing pressure-sensitive adhesive layer obtained by the method described above.
- the first adherend and the second adherend are attached to each other. After laminating, you may perform an autoclave process in order to improve adhesiveness.
- a step of irradiating active energy rays from the first adherend or the second adherent side is provided.
- the pressure-sensitive adhesive layer in the semi-cured state is completely cured (post-cured). This increases the cohesive force of the pressure-sensitive adhesive layer, and improves the adhesiveness to each adherend. Further, by post-curing the pressure-sensitive adhesive layer, the outgas resistance of the entire laminate can be more effectively enhanced.
- the resin plate is preferably a transparent substrate, and when irradiated with active energy rays, the first It is preferable to irradiate active energy rays from the adherend side.
- Examples of active energy rays include ultraviolet rays, electron rays, visible rays, X rays, and ion rays, and can be appropriately selected according to the polymerization initiator contained in the pressure-sensitive adhesive layer. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
- the ultraviolet light source for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used.
- the electron beam for example, an electron beam emitted from each type of electron beam accelerator such as Cockloft Wald type, Bande-Craft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. is used. it can.
- Radiation output of the UV light it is preferable that the integrated quantity of light is made to be a 100 ⁇ 10000mJ / cm 2, and more preferably made to be 500 ⁇ 5000mJ / cm 2.
- the pressure-sensitive adhesive layer having the post-curing property is used as described above, the adhesive layer is semi-cured and is adhered in a good wettability state, so that the adhesion to the first and second adherends is enhanced and Ft and Fb are enhanced. It is possible to increase the Fi by further post-curing.
- the weight average molecular weight of the crosslinkable acrylic copolymer (A-1) was 540,000.
- the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
- the measurement conditions of gel permeation chromatography (GPC) are as follows.
- a xylylene diisocyanate compound Takenate D-110N, manufactured by Mitsui Chemicals, Inc.
- ⁇ Preparation of adhesive layer (A-1)> A 100 ⁇ m thick polyethylene terephthalate film (first release sheet) having a release agent layer treated with a silicone-based release agent (heavy separator film, the pressure-sensitive adhesive composition (A-1) produced as described above, The surface of a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Co., Ltd.) was uniformly coated with an applicator so that the coating amount after drying was 150 ⁇ m/m 2 . Then, it was dried in an air-circulating constant temperature oven at 100° C. for 3 minutes to form an adhesive layer (A-1) on the surface of the first release sheet.
- a second release sheet (light separator film, manufactured by Teijin DuPont Films Co., Ltd., having a thickness of 75 ⁇ m, which has been subjected to a release treatment having a higher release property than the first release sheet on the surface of this adhesive layer
- a first release sheet/adhesive layer (A-1), which is laminated to a treated polyethylene terephthalate film) and the adhesive layer (A-1) is sandwiched between a pair of release sheets having different release forces.
- a pressure-sensitive adhesive sheet with a release sheet having the configuration of the second release sheet was obtained. This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under conditions of 23° C. and 50% relative humidity for aging treatment.
- a laminate (A-1G) was produced by the following method using the pressure-sensitive adhesive sheet with a release sheet obtained above.
- the second release sheet which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K.
- the first release sheet which is a heavy separator film
- the exposed pressure-sensitive adhesive layer (A-1) was attached to the entire surface of a glass plate having a size of 100 mm ⁇ 200 mm, which was a second adherend.
- a sample having a structure of PC plate/adhesive layer/glass plate was autoclaved (40° C., 0.5 MPa, 30 min), and then, ultraviolet rays were irradiated from the glass plate side so that the integrated light amount was 3000 mJ/cm 2 .
- a laminate sample having a size of 100 mm ⁇ 200 mm was obtained.
- Example 2 ⁇ Production of Laminate (A-1P)> A laminate (A-1P) was produced in the same manner as in Example 1 except that the second adherend was changed to Cosmo Shine A4300 (PET) manufactured by Toyobo Co., Ltd. having a thickness of 100 ⁇ m and the ultraviolet ray was irradiated from the PET side. ..
- Example 3 ⁇ Preparation of crosslinkable acrylic copolymer (A-2)> 75 mass% of n-butyl acrylate (BA) and 25 mass% of 2-hydroxyethyl acrylate (2HEA) were mixed, and 2,2′-azobis(2,4-dimethylvaleronitrile) was used as a radical polymerization initiator. ) was dissolved in the solution. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic copolymer (A-2). The weight average molecular weight of the crosslinkable acrylic copolymer (A-2) was 510,000.
- ⁇ Preparation of adhesive layer (A-2)> A pressure-sensitive adhesive sheet with a release sheet having a pressure-sensitive adhesive layer (A-2) having a thickness of 150 ⁇ m in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (A-1) was changed to the pressure-sensitive adhesive composition (A-2).
- This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
- a laminate (A-2G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
- Example 4 ⁇ Production of laminated body (A-2P)> A laminate (A-2P) was produced in the same manner as in Example 2 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
- a laminate (A-3G) was produced by the following method using the pressure-sensitive adhesive layer (A-2) produced above.
- the second release sheet which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, is peeled off, and the exposed pressure-sensitive adhesive layer (A-2) is formed on a second adherend, a glass plate having a size of 100 mm ⁇ 200 mm. Pasted With the glass plate/adhesive layer (A-2)/first release sheet laminated, ultraviolet irradiated from the glass side so that the integrated light amount would be 3000 mJ/cm 2, and then the first release sheet.
- the exposed pressure-sensitive adhesive layer was attached to the entire surface of a 1 mm-thick PC plate (Panlite Sheet PC-1151 manufactured by Teijin Ltd.) which is the first adherend.
- the laminate of PC plate/adhesive layer (A-3)/glass plate was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-3G).
- (Comparative example 2) ⁇ Preparation of adhesive composition (A-4)> 0.05 parts by mass of a toluene diisocyanate compound (Coronate L55 manufactured by Tosoh Corporation) was blended with 100 parts by mass of the crosslinkable acrylic copolymer (A-1) to prepare lauryl acrylate, bisphenol A ethylene oxide-modified diacrylate.
- a pressure-sensitive adhesive composition (A-4) was obtained in the same manner as in Example 1 except that bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide was not added.
- This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
- a laminate (A-4G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-4) and the ultraviolet irradiation was not performed.
- a laminate (A-5P) was produced by the following method using the pressure-sensitive adhesive layer (A-1) produced above.
- the second release sheet which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K.
- the accumulated light amount of ultraviolet rays from the first release sheet side becomes 3000 mJ/cm 2.
- the first release sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to the entire surface of a PET film having a size of 100 mm ⁇ 200 mm, which was the second adherend.
- the laminate having the structure of PC plate/adhesive layer (A-5)/PET was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-5P).
- EXTRA EXTRA
- the laminate was fixed to the center of glass A having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm.
- an instantaneous adhesive is similarly applied to the other surface side (the surface of the second adherend side) of the laminated body, and laminated on the central portion of the glass B having a thickness of 4.0 mm ⁇ a width of 30 mm ⁇ a length of 50 mm.
- the two glasses A and B were laminated so as to have a cross positional relationship with each other.
- the measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C.
- Step 2 In the measurement of Step 1, the instant adhesive was thinly applied to the exposed pressure-sensitive adhesive layer surface due to peeling at the interface between the first adherend and the pressure-sensitive adhesive layer, and the thickness was 4.0 mm x width 30 mm x length 50 mm. It was fixed to the center of a new glass C of. At that time, as in the above, the two glasses B and C were laminated so as to have a cross-shaped positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the instant adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Left for 3 hours.
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Abstract
The problem to be solved by the present invention is to provide a layered body that can exhibit outstanding anti-outgassing properties with respect to any form of occurrence of outgassing. The present invention relates to a layered body, formed by layering a first adherend, an adhesive layer, and a second adherend in that order, wherein, the conditions Ft > Fv, Fi > Fv, and Fb > Fv are fulfilled if: the saturation water vapor pressure at 85°C is Fv; the interface adhesion of the first adherend and the adhesive layer at 85°C, measured by a measurement method (a), is Ft; the shear storage elastic modulus (G') of the adhesive layer at 85°C, measured by a measurement method (b), is Fi; and the interface adhesion of the second adherend and the adhesive layer at 85°C, measured by a measurement method (c), is Fb.
Description
本発明は、積層体及び積層体の製造方法に関する。
The present invention relates to a laminate and a method for manufacturing the laminate.
近年、様々な分野で、液晶ディスプレイ(LCD)などの表示装置や、タッチパネルなどの表示装置と組み合わせて用いられる入力装置が広く用いられるようになってきている。これらの表示装置や入力装置の製造等においては、光学部材を貼り合せる用途に透明な粘着シートが使用されており、表示装置と入力装置との貼合にも透明な粘着シートが使用されている。
In recent years, input devices used in combination with display devices such as liquid crystal displays (LCD) and display devices such as touch panels have been widely used in various fields. In the production of these display devices and input devices, a transparent adhesive sheet is used for bonding optical members, and a transparent adhesive sheet is also used for bonding the display device and the input device. ..
このような用途に用いられる粘着シートには、粘着性能以外にも様々な特性が要求される。例えば、ポリカーボネート基材等の樹脂板は、透明性や耐熱性などに優れているため、光学部材として多用されているが、樹脂板に粘着シートを貼合し、高温環境下に置いた場合、粘着剤層に気泡が生じ、光学性能に影響を及ぼすことがある。このため、粘着シートの用途によっては、優れた耐アウトガス性が要求される場合がある。
❖ Adhesive sheets used for such applications require various properties in addition to adhesive performance. For example, a resin plate such as a polycarbonate base material is often used as an optical member because it has excellent transparency and heat resistance, but when an adhesive sheet is attached to the resin plate and placed in a high temperature environment, Bubbles may be generated in the pressure-sensitive adhesive layer, which may affect optical performance. Therefore, excellent outgas resistance may be required depending on the application of the pressure-sensitive adhesive sheet.
例えば、特許文献1~3には、粘着剤層を備える光学積層体が開示されている。特許文献1では、透明粘着剤を介してポリカーボネート又はアクリルからなる樹脂板が被着体に貼付された光学積層体が開示されている。特許文献2では、粘着剤層を介して配置される透明樹脂層及びガラス層を有する積層単位を備える積層体が開示されている。また、特許文献3には、アウトガスを発生可能な素材で構成されており且つ被着面を有する第1層及び第2層と、第1層と第2層との間に配置される位相差層と、第1粘着層及び第2粘着層とを備えている光学積層体が開示されている。
For example, Patent Documents 1 to 3 disclose optical laminated bodies including an adhesive layer. Patent Document 1 discloses an optical laminate in which a resin plate made of polycarbonate or acrylic is attached to an adherend via a transparent adhesive. Patent Document 2 discloses a laminated body including a laminated unit having a transparent resin layer and a glass layer arranged via an adhesive layer. Further, in Patent Document 3, a first layer and a second layer which are made of a material capable of generating outgas and have an adherend surface, and a phase difference which is arranged between the first layer and the second layer An optical laminate comprising a layer and a first adhesive layer and a second adhesive layer is disclosed.
粘着シートを、アウトガスを発生させ得る樹脂板等に貼合する場合においては、粘着シートと樹脂板の界面に気泡が発生する場合もあるが、粘着シート中に気泡が発生する場合もある。このように、アウトガスの発生様式は1パターンではないため、いかなる発生様式に対しても優れた耐アウトガス性を発揮できる積層体の開発が求められていた。
そこで本発明者らは、このような従来技術の課題を解決するために、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮できる積層体を提供することを目的として検討を進めた。 When the pressure-sensitive adhesive sheet is attached to a resin plate or the like capable of generating outgas, air bubbles may be generated at the interface between the pressure-sensitive adhesive sheet and the resin plate, but air bubbles may be generated in the pressure-sensitive adhesive sheet. As described above, since the outgassing mode is not one pattern, there has been a demand for the development of a laminate capable of exhibiting excellent outgas resistance against any generation mode.
Therefore, in order to solve the problems of the prior art, the present inventors have conducted studies for the purpose of providing a laminate capable of exhibiting excellent outgas resistance against any outgas generation mode. ..
そこで本発明者らは、このような従来技術の課題を解決するために、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮できる積層体を提供することを目的として検討を進めた。 When the pressure-sensitive adhesive sheet is attached to a resin plate or the like capable of generating outgas, air bubbles may be generated at the interface between the pressure-sensitive adhesive sheet and the resin plate, but air bubbles may be generated in the pressure-sensitive adhesive sheet. As described above, since the outgassing mode is not one pattern, there has been a demand for the development of a laminate capable of exhibiting excellent outgas resistance against any generation mode.
Therefore, in order to solve the problems of the prior art, the present inventors have conducted studies for the purpose of providing a laminate capable of exhibiting excellent outgas resistance against any outgas generation mode. ..
上記の課題を検討する中で、本発明者らは、樹脂板、特にポリカーボネートに粘着シートを貼合した場合は、樹脂板の水分が加熱されることで気化して膨張し、その膨張による圧力によって気泡などが発生することを見出した。そこで本発明者らが上記課題を解決するために鋭意検討を行った結果、第1の被着材、粘着剤層及び第2の被着材をこの順で積層した積層体において、耐久試験の条件下における温度(例えば85℃)または実際に使用される過酷な環境下での温度の飽和水蒸気圧をFvとした時に、その温度における第1の被着材と粘着剤層の界面密着力をFtとし、粘着剤層の剪断貯蔵弾性率(G’)をFiとし、第2の被着材と粘着剤層の界面密着力をFbとした場合に、Ft>Fv、Fi>Fv、及び、Fb>Fvとすることにより、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮できる積層体が得られることを見出した。
具体的に、本発明は、以下の構成を有する。 In the consideration of the above problems, the present inventors have found that when a resin plate, particularly when a pressure-sensitive adhesive sheet is attached to polycarbonate, the water content of the resin plate is vaporized and expanded by heating, and the pressure due to the expansion. It was found that bubbles and the like are generated by the above. Therefore, as a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, as a result of a durability test of a laminate obtained by laminating a first adherend, an adhesive layer and a second adherend in this order. When the saturated steam pressure at the temperature under the conditions (for example, 85° C.) or the temperature in the harsh environment actually used is Fv, the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at that temperature can be calculated. Ft>Fv, Fi>Fv, and Ft, the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer is Fi, and the interface adhesion between the second adherend and the pressure-sensitive adhesive layer is Fb. It has been found that by setting Fb>Fv, it is possible to obtain a laminate that can exhibit excellent outgas resistance against any outgas generation mode.
Specifically, the present invention has the following configurations.
具体的に、本発明は、以下の構成を有する。 In the consideration of the above problems, the present inventors have found that when a resin plate, particularly when a pressure-sensitive adhesive sheet is attached to polycarbonate, the water content of the resin plate is vaporized and expanded by heating, and the pressure due to the expansion. It was found that bubbles and the like are generated by the above. Therefore, as a result of intensive investigations by the present inventors in order to solve the above-mentioned problems, as a result of a durability test of a laminate obtained by laminating a first adherend, an adhesive layer and a second adherend in this order. When the saturated steam pressure at the temperature under the conditions (for example, 85° C.) or the temperature in the harsh environment actually used is Fv, the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at that temperature can be calculated. Ft>Fv, Fi>Fv, and Ft, the shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer is Fi, and the interface adhesion between the second adherend and the pressure-sensitive adhesive layer is Fb. It has been found that by setting Fb>Fv, it is possible to obtain a laminate that can exhibit excellent outgas resistance against any outgas generation mode.
Specifically, the present invention has the following configurations.
[1] 第1の被着材、粘着剤層及び第2の被着材をこの順で積層した積層体であって、
85℃における飽和水蒸気圧をFvとし、
下記測定方法(a)で測定される85℃における第1の被着材と粘着剤層の界面密着力をFtとし、
下記測定方法(b)で測定される85℃における粘着剤層の剪断貯蔵弾性率(G’)をFiとし、
下記測定方法(c)で測定される85℃における第2の被着材と粘着剤層の界面密着力をFbとした場合、
Ft>Fv、Fi>Fv、及び、Fb>Fvの条件を満たす積層体;
測定方法(a):
10mm×10mmのサイズの積層体の第1の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第1の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Ft)として測定する;第1の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Ft)は引張最大応力よりも大きいものとする;
測定方法(b):
積層体を固体剪断試験用治具に接着剤を用いて固定し、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとする;
測定方法(c):
10mm×10mmのサイズの積層体の第2の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第2の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Fb)として測定する;第2の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Fb)は引張最大応力よりも大きいものとする。
[2] 第1の被着材は、樹脂板である[1]に記載の積層体。
[3] 第1の被着材は、ポリカーボネート系樹脂を含む[1]又は[2]に記載の積層体。
[4] 第2の被着材は、ガラス板及び樹脂板から選択される少なくとも1種を含む[1]~[3]のいずれかに記載の積層体。
[5] [1]~[4]のいずれかに記載の積層体の製造方法であって、
後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程と、
第1の被着材もしくは第2の被着材側から活性エネルギー線を照射する工程とを含む積層体の製造方法。
[6] 貼合する工程で用いられる粘着剤層は、粘着剤組成物を半硬化状態とした粘着剤層であり、
粘着剤組成物は、架橋性アクリル共重合体、架橋剤、光重合開始剤、単官能単量体及び多官能単量体を含む、[5]に記載の積層体の製造方法。
[7] 単官能単量体は、ラウリルアクリレートである[6]に記載の積層体の製造方法。
[8] 多官能単量体は、1分子内にビスフェノール骨格を有する単量体である[6]又は[7]に記載の積層体の製造方法。 [1] A laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order,
Saturated water vapor pressure at 85°C is Fv,
Ft is the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (a),
The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (b) is defined as Fi,
When the interface adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (c) is Fb,
A laminate satisfying the conditions of Ft>Fv, Fi>Fv, and Fb>Fv;
Measuring method (a):
Adhesive is applied to the surface of the first adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the first adherend and the pressure-sensitive adhesive layer in the opposite direction is measured as the interfacial adhesion (Ft); when the first adherend and the pressure-sensitive adhesive layer do not peel. , The interfacial adhesion (Ft) shall be greater than the maximum tensile stress;
Measuring method (b):
The laminate is fixed to a jig for solid shear test with an adhesive, and the shear storage of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C under the conditions of solid shear mode,frequency 1 Hz, and strain 1.0%. The elastic modulus G′ is measured and the value of the shear storage elastic modulus G′ at 85° C. is defined as Fi;
Measuring method (c):
Adhesive is applied to the surface of the second adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; on the adhesive layer side. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the second adherend and the adhesive layer is measured in the opposite direction, and the stress is measured as the interfacial adhesion force (Fb); when the second adherend and the adhesive layer do not peel. In addition, the interfacial adhesion (Fb) is assumed to be larger than the maximum tensile stress.
[2] The laminated body according to [1], wherein the first adherend is a resin plate.
[3] The first adherend is the laminate according to [1] or [2], which contains a polycarbonate resin.
[4] The laminated body according to any one of [1] to [3], wherein the second adherend contains at least one selected from a glass plate and a resin plate.
[5] The method for producing a laminate according to any one of [1] to [4],
A step of laminating the first adherend and the second adherend to the pressure-sensitive adhesive layer having a post-curing property,
And a step of irradiating an active energy ray from the side of the first adherend or the second adherend.
[6] The pressure-sensitive adhesive layer used in the step of laminating is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition,
The method for producing a laminate according to [5], wherein the pressure-sensitive adhesive composition contains a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
[7] The method for producing a laminate according to [6], wherein the monofunctional monomer is lauryl acrylate.
[8] The method for producing a laminate according to [6] or [7], wherein the polyfunctional monomer is a monomer having a bisphenol skeleton in one molecule.
85℃における飽和水蒸気圧をFvとし、
下記測定方法(a)で測定される85℃における第1の被着材と粘着剤層の界面密着力をFtとし、
下記測定方法(b)で測定される85℃における粘着剤層の剪断貯蔵弾性率(G’)をFiとし、
下記測定方法(c)で測定される85℃における第2の被着材と粘着剤層の界面密着力をFbとした場合、
Ft>Fv、Fi>Fv、及び、Fb>Fvの条件を満たす積層体;
測定方法(a):
10mm×10mmのサイズの積層体の第1の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第1の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Ft)として測定する;第1の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Ft)は引張最大応力よりも大きいものとする;
測定方法(b):
積層体を固体剪断試験用治具に接着剤を用いて固定し、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとする;
測定方法(c):
10mm×10mmのサイズの積層体の第2の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第2の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Fb)として測定する;第2の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Fb)は引張最大応力よりも大きいものとする。
[2] 第1の被着材は、樹脂板である[1]に記載の積層体。
[3] 第1の被着材は、ポリカーボネート系樹脂を含む[1]又は[2]に記載の積層体。
[4] 第2の被着材は、ガラス板及び樹脂板から選択される少なくとも1種を含む[1]~[3]のいずれかに記載の積層体。
[5] [1]~[4]のいずれかに記載の積層体の製造方法であって、
後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程と、
第1の被着材もしくは第2の被着材側から活性エネルギー線を照射する工程とを含む積層体の製造方法。
[6] 貼合する工程で用いられる粘着剤層は、粘着剤組成物を半硬化状態とした粘着剤層であり、
粘着剤組成物は、架橋性アクリル共重合体、架橋剤、光重合開始剤、単官能単量体及び多官能単量体を含む、[5]に記載の積層体の製造方法。
[7] 単官能単量体は、ラウリルアクリレートである[6]に記載の積層体の製造方法。
[8] 多官能単量体は、1分子内にビスフェノール骨格を有する単量体である[6]又は[7]に記載の積層体の製造方法。 [1] A laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order,
Saturated water vapor pressure at 85°C is Fv,
Ft is the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (a),
The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (b) is defined as Fi,
When the interface adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (c) is Fb,
A laminate satisfying the conditions of Ft>Fv, Fi>Fv, and Fb>Fv;
Measuring method (a):
Adhesive is applied to the surface of the first adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the first adherend and the pressure-sensitive adhesive layer in the opposite direction is measured as the interfacial adhesion (Ft); when the first adherend and the pressure-sensitive adhesive layer do not peel. , The interfacial adhesion (Ft) shall be greater than the maximum tensile stress;
Measuring method (b):
The laminate is fixed to a jig for solid shear test with an adhesive, and the shear storage of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C under the conditions of solid shear mode,
Measuring method (c):
Adhesive is applied to the surface of the second adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; on the adhesive layer side. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the second adherend and the adhesive layer is measured in the opposite direction, and the stress is measured as the interfacial adhesion force (Fb); when the second adherend and the adhesive layer do not peel. In addition, the interfacial adhesion (Fb) is assumed to be larger than the maximum tensile stress.
[2] The laminated body according to [1], wherein the first adherend is a resin plate.
[3] The first adherend is the laminate according to [1] or [2], which contains a polycarbonate resin.
[4] The laminated body according to any one of [1] to [3], wherein the second adherend contains at least one selected from a glass plate and a resin plate.
[5] The method for producing a laminate according to any one of [1] to [4],
A step of laminating the first adherend and the second adherend to the pressure-sensitive adhesive layer having a post-curing property,
And a step of irradiating an active energy ray from the side of the first adherend or the second adherend.
[6] The pressure-sensitive adhesive layer used in the step of laminating is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition,
The method for producing a laminate according to [5], wherein the pressure-sensitive adhesive composition contains a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
[7] The method for producing a laminate according to [6], wherein the monofunctional monomer is lauryl acrylate.
[8] The method for producing a laminate according to [6] or [7], wherein the polyfunctional monomer is a monomer having a bisphenol skeleton in one molecule.
本発明によれば、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮できる積層体を得ることができる。
According to the present invention, it is possible to obtain a laminate capable of exhibiting excellent outgas resistance against any outgas generation mode.
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
The present invention will be described in detail below. The description of the constituent requirements described below may be made based on typical embodiments or specific examples, but the present invention is not limited to such embodiments.
(積層体)
本発明は、第1の被着材、粘着剤層及び第2の被着材をこの順で積層した積層体に関する。図1に示されるように、本発明の積層体1は、第1の被着材2と、粘着剤層4と、第2の被着材6をこの順で有する。なお、本発明の積層体1においては、第1の被着材2と粘着剤層4は直接接するように積層されており、粘着剤層4と第2の被着材6も直接接するように積層されている。ここで、85℃における飽和水蒸気圧をFvとし、下記測定方法(a)で測定される85℃における第1の被着材と粘着剤層の界面密着力をFtとし、下記測定方法(b)で測定される85℃における粘着剤層の剪断貯蔵弾性率(G’)をFiとし、下記測定方法(c)で測定される85℃における第2の被着材と粘着剤層の界面密着力をFbとした場合、Ft>Fv、Fi>Fv、及び、Fb>Fvの条件を満たす。 (Laminate)
The present invention relates to a laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order. As shown in FIG. 1, thelaminate 1 of the present invention has a first adherend 2, an adhesive layer 4, and a second adherend 6 in this order. In the laminated body 1 of the present invention, the first adherend 2 and the pressure-sensitive adhesive layer 4 are laminated so as to be in direct contact with each other, and the pressure-sensitive adhesive layer 4 and the second adherend 6 are also in direct contact with each other. It is stacked. Here, the saturated water vapor pressure at 85° C. is Fv, the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (a) is Ft, and the following measurement method (b) The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by Fi is Fi, and the interfacial adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (c). Is Fb, the conditions of Ft>Fv, Fi>Fv, and Fb>Fv are satisfied.
本発明は、第1の被着材、粘着剤層及び第2の被着材をこの順で積層した積層体に関する。図1に示されるように、本発明の積層体1は、第1の被着材2と、粘着剤層4と、第2の被着材6をこの順で有する。なお、本発明の積層体1においては、第1の被着材2と粘着剤層4は直接接するように積層されており、粘着剤層4と第2の被着材6も直接接するように積層されている。ここで、85℃における飽和水蒸気圧をFvとし、下記測定方法(a)で測定される85℃における第1の被着材と粘着剤層の界面密着力をFtとし、下記測定方法(b)で測定される85℃における粘着剤層の剪断貯蔵弾性率(G’)をFiとし、下記測定方法(c)で測定される85℃における第2の被着材と粘着剤層の界面密着力をFbとした場合、Ft>Fv、Fi>Fv、及び、Fb>Fvの条件を満たす。 (Laminate)
The present invention relates to a laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order. As shown in FIG. 1, the
測定方法(a):
10mm×10mmのサイズの積層体の第1の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する。粘着剤層側に、厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする。測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第1の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Ft)として測定する。第1の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Ft)は引張最大応力よりも大きいものとする。
ここで、測定方法(a)において、粘着剤層側に貼合されるガラス板は、第2の被着材を除去することで露出した粘着剤層上に接着剤を塗布し、この接着剤を介して貼合されるものであってもよく、第2の被着材表面に接着剤を塗布し、この接着剤を介して貼合されるものであってもよい。測定用サンプルにおける積層順序については、後述する手順1~3における各場合によって適宜変更されるものである。 Measuring method (a):
An adhesive is applied to the surface of the first adherend of the laminated body having a size of 10 mm×10 mm, and the laminated body is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is bonded to the pressure-sensitive adhesive layer side via an adhesive so that the two glass plates have a cross-shaped positional relationship with each other, to obtain a measurement sample. After the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours, the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% at a speed of 5 mm/min using a tensile tester. The stress when the glass plate is pulled in the opposite direction in the thickness direction and peeled between the first adherend and the pressure-sensitive adhesive layer is measured as the interfacial adhesion (Ft). When the first adherend and the pressure-sensitive adhesive layer are not separated from each other, the interfacial adhesion (Ft) is set to be larger than the maximum tensile stress.
Here, in the measuring method (a), for the glass plate to be bonded to the pressure-sensitive adhesive layer side, an adhesive is applied on the pressure-sensitive adhesive layer exposed by removing the second adherend, The adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the second adherend and the adhesive may be attached via the adhesive. The stacking order in the measurement sample is appropriately changed depending on each case inprocedures 1 to 3 described later.
10mm×10mmのサイズの積層体の第1の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する。粘着剤層側に、厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする。測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第1の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Ft)として測定する。第1の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Ft)は引張最大応力よりも大きいものとする。
ここで、測定方法(a)において、粘着剤層側に貼合されるガラス板は、第2の被着材を除去することで露出した粘着剤層上に接着剤を塗布し、この接着剤を介して貼合されるものであってもよく、第2の被着材表面に接着剤を塗布し、この接着剤を介して貼合されるものであってもよい。測定用サンプルにおける積層順序については、後述する手順1~3における各場合によって適宜変更されるものである。 Measuring method (a):
An adhesive is applied to the surface of the first adherend of the laminated body having a size of 10 mm×10 mm, and the laminated body is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is bonded to the pressure-sensitive adhesive layer side via an adhesive so that the two glass plates have a cross-shaped positional relationship with each other, to obtain a measurement sample. After the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours, the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% at a speed of 5 mm/min using a tensile tester. The stress when the glass plate is pulled in the opposite direction in the thickness direction and peeled between the first adherend and the pressure-sensitive adhesive layer is measured as the interfacial adhesion (Ft). When the first adherend and the pressure-sensitive adhesive layer are not separated from each other, the interfacial adhesion (Ft) is set to be larger than the maximum tensile stress.
Here, in the measuring method (a), for the glass plate to be bonded to the pressure-sensitive adhesive layer side, an adhesive is applied on the pressure-sensitive adhesive layer exposed by removing the second adherend, The adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the second adherend and the adhesive may be attached via the adhesive. The stacking order in the measurement sample is appropriately changed depending on each case in
測定方法(b):
積層体を固体剪断試験用治具に接着剤を用いて固定し、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとする。この際に用いる接着剤は、測定する剪断貯蔵弾性率に影響が出ないようにガラス転移温度(Tg)が120℃以上であることが好ましい。接着剤としては、例えば、コニシ社製のアロンアルフア 速攻多用途EXTRAを用いることができる。 Measuring method (b):
The laminate is fixed to a jig for solid shear test with an adhesive, and the shear storage of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C under the conditions of solid shear mode,frequency 1 Hz, and strain 1.0%. The elastic modulus G′ is measured, and the value of the shear storage elastic modulus G′ at 85° C. is defined as Fi. The adhesive used at this time preferably has a glass transition temperature (Tg) of 120° C. or higher so that the measured shear storage elastic modulus is not affected. As the adhesive, for example, Aron Alpha Quick Attack Versatile EXTRA manufactured by Konishi Co., Ltd. can be used.
積層体を固体剪断試験用治具に接着剤を用いて固定し、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとする。この際に用いる接着剤は、測定する剪断貯蔵弾性率に影響が出ないようにガラス転移温度(Tg)が120℃以上であることが好ましい。接着剤としては、例えば、コニシ社製のアロンアルフア 速攻多用途EXTRAを用いることができる。 Measuring method (b):
The laminate is fixed to a jig for solid shear test with an adhesive, and the shear storage of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C under the conditions of solid shear mode,
測定方法(c):
10mm×10mmのサイズの積層体の第2の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する。粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする。測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第2の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Fb)として測定する。第2の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Fb)は引張最大応力よりも大きいものとする。
ここで、測定方法(c)において、粘着剤層側に貼合されるガラス板は、第1の被着材を除去することで露出した粘着剤層上に接着剤を塗布し、この接着剤を介して貼合されるものであってもよく、第1の被着材表面に接着剤を塗布し、この接着剤を介して貼合されるものであってもよい。測定用サンプルにおける積層順序については、後述する手順1~3における各場合によって適宜変更されるものである。 Measuring method (c):
An adhesive is applied to the surface of the second adherend of the laminated body having a size of 10 mm×10 mm, and the laminated body is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is bonded to the pressure-sensitive adhesive layer side via an adhesive so that the two glass plates have a cross-shaped positional relationship with each other, to obtain a measurement sample. After the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours, the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% at a speed of 5 mm/min using a tensile tester. The stress when the glass plate is pulled in the opposite direction in the thickness direction and peeled between the second adherend and the pressure-sensitive adhesive layer is measured as the interfacial adhesion (Fb). When the second adherend and the pressure-sensitive adhesive layer are not separated from each other, the interfacial adhesion (Fb) is set to be larger than the maximum tensile stress.
Here, in the measurement method (c), for the glass plate to be bonded to the pressure-sensitive adhesive layer side, an adhesive is applied to the pressure-sensitive adhesive layer exposed by removing the first adherend, and the adhesive is The adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the first adherend and the adhesive may be attached via the adhesive. The stacking order in the measurement sample is appropriately changed depending on each case inprocedures 1 to 3 described later.
10mm×10mmのサイズの積層体の第2の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する。粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする。測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第2の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Fb)として測定する。第2の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Fb)は引張最大応力よりも大きいものとする。
ここで、測定方法(c)において、粘着剤層側に貼合されるガラス板は、第1の被着材を除去することで露出した粘着剤層上に接着剤を塗布し、この接着剤を介して貼合されるものであってもよく、第1の被着材表面に接着剤を塗布し、この接着剤を介して貼合されるものであってもよい。測定用サンプルにおける積層順序については、後述する手順1~3における各場合によって適宜変更されるものである。 Measuring method (c):
An adhesive is applied to the surface of the second adherend of the laminated body having a size of 10 mm×10 mm, and the laminated body is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is bonded to the pressure-sensitive adhesive layer side via an adhesive so that the two glass plates have a cross-shaped positional relationship with each other, to obtain a measurement sample. After the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% for 3 hours, the measurement sample was placed in an environment of 85° C. and a relative humidity of less than 20% at a speed of 5 mm/min using a tensile tester. The stress when the glass plate is pulled in the opposite direction in the thickness direction and peeled between the second adherend and the pressure-sensitive adhesive layer is measured as the interfacial adhesion (Fb). When the second adherend and the pressure-sensitive adhesive layer are not separated from each other, the interfacial adhesion (Fb) is set to be larger than the maximum tensile stress.
Here, in the measurement method (c), for the glass plate to be bonded to the pressure-sensitive adhesive layer side, an adhesive is applied to the pressure-sensitive adhesive layer exposed by removing the first adherend, and the adhesive is The adhesive layer may be attached via the adhesive, or the adhesive may be applied to the surface of the first adherend and the adhesive may be attached via the adhesive. The stacking order in the measurement sample is appropriately changed depending on each case in
測定方法(a)と測定方法(c)は具体的には以下の手順1~3を順に行うことでなされる。
(手順1)
積層体を10mm×10mmのサイズに切り出した後、積層体の一方の面(第1の被着材側の面)に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスAの中央部に積層体を固定する。次いで積層体のもう一方の面側(第2の被着材側の面)に同様に接着剤を塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスBの中央部に積層体を固定する。その際、図2に示されるように、2つのガラスA、Bが互いに十字の位置関係になるよう貼合する。なお、図2の上図は測定用サンプルを平面方向から見た図であり、図2の下図は測定用サンプルの側面を断面方向から見た図である。図2に示されるように、積層体1の各面に、ガラスA10及びガラスB20を互いに十字の位置関係になるよう貼合することで測定用サンプルが構成される。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ1の測定と剥離界面の観察を行い、以下の基準でFt及びFbを決定する。
(1)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ1として手順2の試験を実施してFbを測定する。
(2)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ1とし手順3の試験を実施してFtを測定する。
(3)接着剤とガラス(又は被着材)の界面で剥離した場合、Ft、Fb>σ1とする。すなわち、(3)の場合のように被着材と粘着剤層の界面で剥離せずに、ガラスと積層体が分離した場合には、界面密着力(Ft)と界面密着力(Fb)は、その際の引張最大応力よりも大きいものとする。
なお、ガラスと積層体の接着に用いられる接着剤としては、例えば、瞬間接着剤を用いることができ、具体的には、コニシ社製のアロンアルフア 速攻多用途EXTRA等を用いることができる。ここで、接着剤は各被着材とガラスの接着力(上記の測定での最大応力)が85℃における飽和水蒸気圧(Fv)より大きいものであれば特に限定されるものではない。また、測定に用いられるガラスはアルカリガラスであることが好ましく、例えば、(株)スタンダードテストピース社製のフロート板ガラスを用いることができる。 Specifically, the measuring method (a) and the measuring method (c) are performed by sequentially performing the followingprocedures 1 to 3.
(Procedure 1)
After cutting the laminated body into a size of 10 mm×10 mm, an adhesive is thinly applied to one surface (the surface on the first adherend side) of the laminated body, and the thickness is 4.0 mm×width 30 mm×length 50 mm. The laminated body is fixed to the central part of the glass A of FIG. Next, an adhesive is similarly applied to the other surface side (the surface on the side of the second adherend) of the laminated body, and the laminated body is provided on the central portion of the glass B having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. To fix. At that time, as shown in FIG. 2, the two glasses A and B are laminated so as to have a cross-shaped positional relationship with each other. Note that the upper diagram of FIG. 2 is a view of the measurement sample viewed from the plane direction, and the lower diagram of FIG. 2 is a view of the side surface of the measurement sample viewed from the cross-sectional direction. As shown in FIG. 2, a measurement sample is formed by bonding glass A10 and glass B20 on each surface of thelaminate 1 so as to have a cross-shaped positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Leave for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ1 is measured and the peeling interface is observed, and Ft and Fb are determined according to the following criteria.
(1) When peeling off at the interface between the first adherend and the pressure-sensitive adhesive layer, the test ofprocedure 2 is performed with Ft=σ1 to measure Fb.
(2) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ1 is set and the test of step 3 is performed to measure Ft.
(3) When peeled at the interface between the adhesive and the glass (or the adherend), Ft and Fb>σ1. That is, when the glass and the laminate are separated without peeling at the interface between the adherend and the pressure-sensitive adhesive layer as in the case of (3), the interface adhesion force (Ft) and the interface adhesion force (Fb) are , Which is larger than the maximum tensile stress at that time.
As the adhesive used for bonding the glass and the laminated body, for example, an instant adhesive can be used, and specifically, Aron Alpha Quick Launch Multipurpose EXTRA manufactured by Konishi Co., Ltd. can be used. Here, the adhesive is not particularly limited as long as the adhesive force (maximum stress in the above measurement) between each adherend and glass is larger than the saturated vapor pressure (Fv) at 85°C. The glass used for measurement is preferably alkali glass, and for example, float plate glass manufactured by Standard Test Piece Co., Ltd. can be used.
(手順1)
積層体を10mm×10mmのサイズに切り出した後、積層体の一方の面(第1の被着材側の面)に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスAの中央部に積層体を固定する。次いで積層体のもう一方の面側(第2の被着材側の面)に同様に接着剤を塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスBの中央部に積層体を固定する。その際、図2に示されるように、2つのガラスA、Bが互いに十字の位置関係になるよう貼合する。なお、図2の上図は測定用サンプルを平面方向から見た図であり、図2の下図は測定用サンプルの側面を断面方向から見た図である。図2に示されるように、積層体1の各面に、ガラスA10及びガラスB20を互いに十字の位置関係になるよう貼合することで測定用サンプルが構成される。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ1の測定と剥離界面の観察を行い、以下の基準でFt及びFbを決定する。
(1)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ1として手順2の試験を実施してFbを測定する。
(2)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ1とし手順3の試験を実施してFtを測定する。
(3)接着剤とガラス(又は被着材)の界面で剥離した場合、Ft、Fb>σ1とする。すなわち、(3)の場合のように被着材と粘着剤層の界面で剥離せずに、ガラスと積層体が分離した場合には、界面密着力(Ft)と界面密着力(Fb)は、その際の引張最大応力よりも大きいものとする。
なお、ガラスと積層体の接着に用いられる接着剤としては、例えば、瞬間接着剤を用いることができ、具体的には、コニシ社製のアロンアルフア 速攻多用途EXTRA等を用いることができる。ここで、接着剤は各被着材とガラスの接着力(上記の測定での最大応力)が85℃における飽和水蒸気圧(Fv)より大きいものであれば特に限定されるものではない。また、測定に用いられるガラスはアルカリガラスであることが好ましく、例えば、(株)スタンダードテストピース社製のフロート板ガラスを用いることができる。 Specifically, the measuring method (a) and the measuring method (c) are performed by sequentially performing the following
(Procedure 1)
After cutting the laminated body into a size of 10 mm×10 mm, an adhesive is thinly applied to one surface (the surface on the first adherend side) of the laminated body, and the thickness is 4.0 mm×width 30 mm×length 50 mm. The laminated body is fixed to the central part of the glass A of FIG. Next, an adhesive is similarly applied to the other surface side (the surface on the side of the second adherend) of the laminated body, and the laminated body is provided on the central portion of the glass B having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. To fix. At that time, as shown in FIG. 2, the two glasses A and B are laminated so as to have a cross-shaped positional relationship with each other. Note that the upper diagram of FIG. 2 is a view of the measurement sample viewed from the plane direction, and the lower diagram of FIG. 2 is a view of the side surface of the measurement sample viewed from the cross-sectional direction. As shown in FIG. 2, a measurement sample is formed by bonding glass A10 and glass B20 on each surface of the
(1) When peeling off at the interface between the first adherend and the pressure-sensitive adhesive layer, the test of
(2) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ1 is set and the test of step 3 is performed to measure Ft.
(3) When peeled at the interface between the adhesive and the glass (or the adherend), Ft and Fb>σ1. That is, when the glass and the laminate are separated without peeling at the interface between the adherend and the pressure-sensitive adhesive layer as in the case of (3), the interface adhesion force (Ft) and the interface adhesion force (Fb) are , Which is larger than the maximum tensile stress at that time.
As the adhesive used for bonding the glass and the laminated body, for example, an instant adhesive can be used, and specifically, Aron Alpha Quick Launch Multipurpose EXTRA manufactured by Konishi Co., Ltd. can be used. Here, the adhesive is not particularly limited as long as the adhesive force (maximum stress in the above measurement) between each adherend and glass is larger than the saturated vapor pressure (Fv) at 85°C. The glass used for measurement is preferably alkali glass, and for example, float plate glass manufactured by Standard Test Piece Co., Ltd. can be used.
(手順2)
手順1の測定で第1の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスCの中央に固定する。その際、上記と同様に2つのガラスB、Cが互いに十字の位置関係になるよう貼合する。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ2の測定と剥離界面の観察を行い、以下の基準でFbを決定する。
(4)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ2とする。
(5)接着剤とガラス、又は、接着剤と粘着剤層の界面で剥離した場合、Fb>σ2とする。 (Procedure 2)
The adhesive was thinly applied to the surface of the pressure-sensitive adhesive layer that was exposed by peeling at the interface between the first adherend and the pressure-sensitive adhesive layer in the measurement ofstep 1, and the thickness was 4.0 mm × width 30 mm × length 50 mm. Fix in the center of a new glass C. At that time, the two glasses B and C are laminated so as to have a cross-shaped positional relationship with each other as in the above. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Leave for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ2 is measured and the peeling interface is observed, and Fb is determined according to the following criteria.
(4) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ2.
(5) When peeled at the interface between the adhesive and the glass or the adhesive and the pressure-sensitive adhesive layer, Fb>σ2.
手順1の測定で第1の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスCの中央に固定する。その際、上記と同様に2つのガラスB、Cが互いに十字の位置関係になるよう貼合する。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ2の測定と剥離界面の観察を行い、以下の基準でFbを決定する。
(4)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ2とする。
(5)接着剤とガラス、又は、接着剤と粘着剤層の界面で剥離した場合、Fb>σ2とする。 (Procedure 2)
The adhesive was thinly applied to the surface of the pressure-sensitive adhesive layer that was exposed by peeling at the interface between the first adherend and the pressure-sensitive adhesive layer in the measurement of
(4) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ2.
(5) When peeled at the interface between the adhesive and the glass or the adhesive and the pressure-sensitive adhesive layer, Fb>σ2.
(手順3)
手順1の測定で第2の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスDの中央に固定する。その際、上記と同様に2つのガラスA、Dが互いに十字の位置関係になるよう貼合する。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ3の測定と剥離界面の観察を行い、以下の基準でFtを決定する。
(6)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ3とする。
(7)接着剤とガラス、又は、接着剤と粘着剤層の界面で剥離した場合、Ft>σ3とする。 (Procedure 3)
The adhesive was thinly applied to the exposed surface of the pressure-sensitive adhesive layer, which was peeled off at the interface between the second adherend and the pressure-sensitive adhesive layer in the measurement ofStep 1, and the thickness was 4.0 mm×width 30 mm×length 50 mm. Fix it in the center of a new glass D. At that time, the two glasses A and D are laminated so as to have a cross-shaped positional relationship with each other as in the above. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Leave for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ3 is measured and the peeling interface is observed, and Ft is determined according to the following criteria.
(6) When peeling off at the interface between the first adherend and the pressure-sensitive adhesive layer, Ft=σ3.
(7) When peeled at the interface between the adhesive and the glass, or the adhesive and the pressure-sensitive adhesive layer, Ft>σ3.
手順1の測定で第2の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスDの中央に固定する。その際、上記と同様に2つのガラスA、Dが互いに十字の位置関係になるよう貼合する。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置く。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ3の測定と剥離界面の観察を行い、以下の基準でFtを決定する。
(6)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ3とする。
(7)接着剤とガラス、又は、接着剤と粘着剤層の界面で剥離した場合、Ft>σ3とする。 (Procedure 3)
The adhesive was thinly applied to the exposed surface of the pressure-sensitive adhesive layer, which was peeled off at the interface between the second adherend and the pressure-sensitive adhesive layer in the measurement of
(6) When peeling off at the interface between the first adherend and the pressure-sensitive adhesive layer, Ft=σ3.
(7) When peeled at the interface between the adhesive and the glass, or the adhesive and the pressure-sensitive adhesive layer, Ft>σ3.
本明細書における85℃における飽和水蒸気圧Fvは、0.058MPaである。なお、85℃における飽和水蒸気圧は、JIS Z 8806付表1.1 水の飽和蒸気圧に記載された値を採用できる。
The saturated water vapor pressure Fv at 85° C. in the present specification is 0.058 MPa. As the saturated vapor pressure at 85°C, the value described in JIS Z 8806 Appendix Table 1.1 Saturated vapor pressure of water can be adopted.
本発明の積層体においては、85℃における飽和水蒸気圧(Fv)と、上述した方法で測定される第1の被着材と粘着剤層の界面密着力(Ft)、粘着剤層の剪断貯蔵弾性率(Fi)及び第2の被着材と粘着剤層の界面密着力(Fb)の関係が以下の条件を満たす。
Ft>Fv、Fi>Fv、及び、Fb>Fv
本発明においては、Fv、Ft、Fi及びFbが上記条件を満たすことにより、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮することができる。 In the laminate of the present invention, the saturated vapor pressure (Fv) at 85° C., the interfacial adhesion (Ft) between the first adherend and the pressure-sensitive adhesive layer measured by the method described above, and the shear storage of the pressure-sensitive adhesive layer. The relationship between the elastic modulus (Fi) and the interfacial adhesion (Fb) between the second adherend and the pressure-sensitive adhesive layer satisfies the following conditions.
Ft>Fv, Fi>Fv, and Fb>Fv
In the present invention, by satisfying the above conditions for Fv, Ft, Fi and Fb, it is possible to exhibit excellent outgas resistance against any outgas generation mode.
Ft>Fv、Fi>Fv、及び、Fb>Fv
本発明においては、Fv、Ft、Fi及びFbが上記条件を満たすことにより、いかなるアウトガスの発生様式に対しても優れた耐アウトガス性を発揮することができる。 In the laminate of the present invention, the saturated vapor pressure (Fv) at 85° C., the interfacial adhesion (Ft) between the first adherend and the pressure-sensitive adhesive layer measured by the method described above, and the shear storage of the pressure-sensitive adhesive layer. The relationship between the elastic modulus (Fi) and the interfacial adhesion (Fb) between the second adherend and the pressure-sensitive adhesive layer satisfies the following conditions.
Ft>Fv, Fi>Fv, and Fb>Fv
In the present invention, by satisfying the above conditions for Fv, Ft, Fi and Fb, it is possible to exhibit excellent outgas resistance against any outgas generation mode.
ここで、アウトガスの発生様式としては、図3に示されるような3つのエラーモードが挙げられる。図3(a)にはエラーモード1が示されており、このエラーモードでは、第1の被着材2と粘着剤層4の界面に気泡Rが発生する。図3(b)にはエラーモード2が示されており、このエラーモードでは、粘着剤層4中に気泡Rが発生する。図3(c)には、エラーモード3が示されており、このエラーモードでは、第2の被着材6と粘着剤層4の界面に気泡Rが発生する。本発明においては、Fv、Ft、Fi及びFbを所定条件とすることにより、図3(a)~(c)に示されたような種々のアウトガスの発生を抑制することができる。これにより、本発明の積層体においては、高温条件下においても粘着剤層が被着材から浮いたり、剥がれたりすることが抑制され、積層体の構成部材の密着性が高められる。
▽Here, there are three error modes as shown in Fig. 3 as the mode of outgas generation. An error mode 1 is shown in FIG. 3A. In this error mode, bubbles R are generated at the interface between the first adherend 2 and the pressure-sensitive adhesive layer 4. 3B shows an error mode 2. In this error mode, bubbles R are generated in the pressure-sensitive adhesive layer 4. 3C shows an error mode 3. In this error mode, bubbles R are generated at the interface between the second adherend 6 and the adhesive layer 4. In the present invention, by setting Fv, Ft, Fi and Fb as predetermined conditions, it is possible to suppress the generation of various outgases as shown in FIGS. 3(a) to 3(c). As a result, in the laminate of the present invention, the pressure-sensitive adhesive layer is prevented from floating or peeling from the adherend even under high temperature conditions, and the adhesion of the constituent members of the laminate is improved.
第1の被着材と粘着剤層の界面密着力(Ft)は、0.058MPaよりも大きいものであればよく、0.10MPa以上であることがより好ましく、0.15MPa以上であることがさらに好ましく、0.20MPa以上であることが一層好ましく、0.25MPa以上であることが特に好ましい。
The interfacial adhesion (Ft) between the first adherend and the pressure-sensitive adhesive layer may be larger than 0.058 MPa, more preferably 0.10 MPa or more, and more preferably 0.15 MPa or more. More preferably, it is more preferably 0.20 MPa or more, and particularly preferably 0.25 MPa or more.
粘着剤層の剪断貯蔵弾性率(Fi)は、0.058MPaよりも大きいものであればよく、0.10MPa以上であることがより好ましく、0.15MPa以上であることがさらに好ましい。
The shear storage elastic modulus (Fi) of the pressure-sensitive adhesive layer may be larger than 0.058 MPa, more preferably 0.10 MPa or more, and further preferably 0.15 MPa or more.
第2の被着材と粘着剤層の界面密着力(Fb)は、0.058MPaよりも大きいものであればよく、0.10MPa以上であることがより好ましく、0.15MPa以上であることがさらに好ましく、0.20MPa以上であることが一層好ましく、0.25MPa以上であることが特に好ましい。
The interface adhesion force (Fb) between the second adherend and the pressure-sensitive adhesive layer may be greater than 0.058 MPa, more preferably 0.10 MPa or more, and preferably 0.15 MPa or more. More preferably, it is more preferably 0.20 MPa or more, and particularly preferably 0.25 MPa or more.
本発明の積層体は、光学部材として用いられることが好ましい。すなわち、本発明の積層体は光学積層体であることが好ましい。例えば、本発明の積層体は、画像表示装置の他、家電品やゲーム機等の電気電子機器のパーツ、自動車等の加飾部の構成部材として用いられることが好ましい。また、本発明の積層体は、高温条件下においても優れた耐アウトガス性を有しているため、車載ディスプレイ等の車載光学部材として用いられることも好ましい。
The laminate of the present invention is preferably used as an optical member. That is, the laminate of the present invention is preferably an optical laminate. For example, the layered product of the present invention is preferably used as a constituent member of parts for electric and electronic devices such as home electric appliances and game machines, and decorative parts such as automobiles, in addition to image display devices. Moreover, since the laminated body of the present invention has excellent outgas resistance even under high temperature conditions, it is also preferably used as an in-vehicle optical member such as an in-vehicle display.
(被着材)
本発明の積層体は、粘着剤層を介して貼合される、第1の被着材と第2の被着材を備える。なお、第1の被着材と第2の被着材は同種の被着材であってもよいが、異なる被着材であってもよい。なお、本発明においては、第1の被着材と第2の被着材の少なくとも一方がアウトガスを発生する被着材であってもよい。このような場合であっても、本発明の積層体は優れた耐アウトガス性を発揮することができる。 (Substrate)
The laminate of the present invention includes a first adherend and a second adherend that are bonded together via an adhesive layer. The first adherend and the second adherend may be the same kind of adherend, but may be different adherends. In the present invention, at least one of the first adherend and the second adherend may be an adherend that generates outgas. Even in such a case, the laminate of the present invention can exhibit excellent outgas resistance.
本発明の積層体は、粘着剤層を介して貼合される、第1の被着材と第2の被着材を備える。なお、第1の被着材と第2の被着材は同種の被着材であってもよいが、異なる被着材であってもよい。なお、本発明においては、第1の被着材と第2の被着材の少なくとも一方がアウトガスを発生する被着材であってもよい。このような場合であっても、本発明の積層体は優れた耐アウトガス性を発揮することができる。 (Substrate)
The laminate of the present invention includes a first adherend and a second adherend that are bonded together via an adhesive layer. The first adherend and the second adherend may be the same kind of adherend, but may be different adherends. In the present invention, at least one of the first adherend and the second adherend may be an adherend that generates outgas. Even in such a case, the laminate of the present invention can exhibit excellent outgas resistance.
第1の被着材は、樹脂板であることが好ましい。樹脂板を構成する樹脂としては、例えば、ポリエステル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリビニルアルコール、ポリスチレン、ポリカーボネート、ポリエーテルイミド、ポリイミド、フッ素樹脂、ポリアミド、(メタ)アクリル樹脂、ポリメタクリル酸メチル樹脂、アクリロニトリルとスチレンの共重合体、アクリロニトリルとブタジエンとスチレンの共重合体などが挙げられ、これらの混合樹脂が用いられてもよい。中でも樹脂板は、(メタ)アクリル樹脂板及びポリカーボネート樹脂板であることが好ましく、ポリカーボネート樹脂板であることがより好ましい。すなわち、第1の被着材はポリカーボネート系樹脂を含むものであることが好ましい。ここで、ポリカーボネート系樹脂には、ポリカーボネート樹脂と他の成分の複合素材(例えば、メタクリル酸メチル基材とポリカーボネート系樹脂板の積層体やハードコート層付ポリカーボネート系樹脂板)や、ポリカーボネート樹脂のみからなる素材等が含まれる。ポリカーボネート樹脂板は、特に高温条件下においてアウトガスを発生しやすい部材であるが、本発明においては、Fv、Ft、Fi及びFbの関係を所定条件とすることにより、第1の被着材としてポリカーボネート樹脂板を用い、積層体を高温条件下においた場合であってもアウトガスの発生を抑制することができる。なお、第1の被着材は、光学積層体において、カバーフィルムやプロテクトフィルムとして機能し得る。
The first adherend is preferably a resin plate. Examples of the resin constituting the resin plate include polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polystyrene, polycarbonate, polyetherimide, polyimide, fluororesin, polyamide, (meth)acrylic resin, polymethylmethacrylate resin. , Copolymers of acrylonitrile and styrene, copolymers of acrylonitrile, butadiene and styrene, and the like, and a mixed resin thereof may be used. Above all, the resin plate is preferably a (meth)acrylic resin plate and a polycarbonate resin plate, and more preferably a polycarbonate resin plate. That is, it is preferable that the first adherend contains a polycarbonate resin. Here, the polycarbonate resin includes only a composite material of a polycarbonate resin and other components (for example, a laminate of a methyl methacrylate base material and a polycarbonate resin plate or a polycarbonate resin plate with a hard coat layer), or a polycarbonate resin alone. Includes materials such as The polycarbonate resin plate is a member that is apt to generate outgas particularly under high temperature conditions. However, in the present invention, by setting the relationship of Fv, Ft, Fi, and Fb to a predetermined condition, polycarbonate is used as the first adherend. Using a resin plate, outgassing can be suppressed even when the laminate is placed under high temperature conditions. The first adherend can function as a cover film or a protect film in the optical laminate.
なお、第1の被着材が、ポリカーボネート樹脂板である場合、ポリカーボネート樹脂板としては、例えば、帝人化成(株)製のパンライトPC-1151、三菱ガス化学(株)製のユーピロンNF2000等を挙げることができる。また、第1の被着材としては、ポリカーボネート樹脂板の少なくとも一方の面上にハードコート層が積層された積層基材や、ポリカーボネート樹脂板の少なくとも一方の面上にポリメタクリル酸メチル(PMMA)基材が積層された積層基材を用いてもよい。
When the first adherend is a polycarbonate resin plate, examples of the polycarbonate resin plate include Panlite PC-1151 manufactured by Teijin Chemicals Ltd. and Iupilon NF2000 manufactured by Mitsubishi Gas Chemical Co., Inc. Can be mentioned. As the first adherend, a laminated base material in which a hard coat layer is laminated on at least one surface of a polycarbonate resin plate, or polymethylmethacrylate (PMMA) on at least one surface of the polycarbonate resin plate You may use the laminated base material with which the base material was laminated|stacked.
第2の被着材は、ガラス板及び樹脂板から選択される少なくとも1種を含むことが好ましい。第2の被着材は、光学部材であることが好ましく、例えば、タッチパネルやITOフィルム、偏光板であることが好ましい。なお、これらの光学部材を構成する部材として、ガラス板及び樹脂板が挙げられる。第2の被着材における粘着剤層との貼合面は、ガラス板及び樹脂板であることが好ましい。
The second adherend preferably contains at least one selected from a glass plate and a resin plate. The second adherend is preferably an optical member, for example, a touch panel, an ITO film, or a polarizing plate. In addition, a glass plate and a resin plate are mentioned as a member which comprises these optical members. The bonding surface of the second adherend with the pressure-sensitive adhesive layer is preferably a glass plate or a resin plate.
第1の被着材及び第2の被着材の各々の厚みは、0.5mm以上であることが好ましく、0.7mm以上であることがより好ましく、1mm以上であることがさらに好ましい。また、第1の被着材及び第2の被着材の各々の厚みは、5mm以下であることが好ましく、4mm以下であることがより好ましく、3mm以下であることがさらに好ましい。
The thickness of each of the first adherend and the second adherend is preferably 0.5 mm or more, more preferably 0.7 mm or more, and further preferably 1 mm or more. Further, the thickness of each of the first adherend and the second adherend is preferably 5 mm or less, more preferably 4 mm or less, and further preferably 3 mm or less.
(粘着剤層)
本発明の積層体は、粘着剤層を備える。粘着剤層は、単層の粘着剤層であってもよく、粘着剤層が複数層積層されてなる多層の粘着剤層であってもよい。 (Adhesive layer)
The laminate of the present invention includes a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer may be a single pressure-sensitive adhesive layer or a multi-layer pressure-sensitive adhesive layer formed by laminating a plurality of pressure-sensitive adhesive layers.
本発明の積層体は、粘着剤層を備える。粘着剤層は、単層の粘着剤層であってもよく、粘着剤層が複数層積層されてなる多層の粘着剤層であってもよい。 (Adhesive layer)
The laminate of the present invention includes a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer may be a single pressure-sensitive adhesive layer or a multi-layer pressure-sensitive adhesive layer formed by laminating a plurality of pressure-sensitive adhesive layers.
粘着剤層の厚みは、用途に応じて適宜設定でき、特に限定されないが、10μm以上であることが好ましく、20μm以上であることがより好ましい。また、粘着剤層の厚みは、1000μm以下であることが好ましく、750μm以下であることがより好ましく、500μm以下であることがさらに好ましい。粘着剤層の厚みを上記範囲内とすることにより、積層体の耐アウトガス性をより効果的に高めることができる。また、粘着剤層の厚みを上記範囲内とすることにより、被着体が段差を有する部材である場合に段差追従性を十分に確保することができる。さらに、粘着剤層の厚さを上記範囲内とすることにより、粘着剤層の製造が容易となる。
The thickness of the pressure-sensitive adhesive layer can be appropriately set depending on the application and is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more. Moreover, the thickness of the pressure-sensitive adhesive layer is preferably 1000 μm or less, more preferably 750 μm or less, and further preferably 500 μm or less. By setting the thickness of the pressure-sensitive adhesive layer within the above range, the outgas resistance of the laminate can be more effectively enhanced. Further, by setting the thickness of the pressure-sensitive adhesive layer within the above range, it is possible to sufficiently secure the step followability when the adherend is a member having a step. Furthermore, when the thickness of the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive layer can be easily manufactured.
上述した測定方法(b)で測定される85℃における粘着剤層の剪断貯蔵弾性率(G’)は、0.058MPaよりも大きいものであればよく、0.10MPa以上であることがより好ましく、0.15MPa以上であることがさらに好ましい。粘着剤層の剪断貯蔵弾性率(G’)は、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値を算出したものである。
The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the above-mentioned measurement method (b) may be larger than 0.058 MPa, and is more preferably 0.10 MPa or more. , 0.15 MPa or more is more preferable. The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer is the shear storage elastic modulus G′ of the pressure-sensitive adhesive layer in the temperature range from 20° C. to 120° C. under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0%. Is measured and the value of the shear storage elastic modulus G′ at 85° C. is calculated.
粘着剤層は、アクリル系粘着剤層であることが好ましい。アクリル系粘着剤層は、アクリル共重合体を含むものであることが好ましい。なお、本明細書において、「単位」は重合体を構成する繰り返し単位(単量体単位)である。「(メタ)アクリル酸」はアクリル酸およびメタクリル酸の双方、または、いずれかを表す。
The adhesive layer is preferably an acrylic adhesive layer. The acrylic pressure-sensitive adhesive layer preferably contains an acrylic copolymer. In addition, in this specification, a "unit" is a repeating unit (monomer unit) which comprises a polymer. "(Meth)acrylic acid" represents both acrylic acid and methacrylic acid, or either.
(粘着剤組成物)
粘着剤層は、第1の被着材及び第2の被着材に貼合される前の段階では、後硬化性を有する粘着剤層であることが好ましい。すなわち、第1の被着材及び第2の被着材に貼合される前の状態では、粘着剤層は粘着剤組成物を半硬化状態とした粘着剤層であることが好ましい。なお、粘着剤層がアクリル系粘着剤層である場合、粘着剤組成物は少なくともアクリル共重合体を含む。また、第1の被着材及び第2の被着材に貼合される前の粘着剤層が半硬化状態の粘着剤層である場合、粘着剤組成物は、架橋性アクリル共重合体、架橋剤、光重合開始剤、単官能単量体及び多官能単量体を含むことが好ましい。 (Adhesive composition)
The pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer having a post-curing property before being attached to the first adherend and the second adherend. That is, it is preferable that the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition in a state before being bonded to the first adherend and the second adherend. When the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition contains at least an acrylic copolymer. When the pressure-sensitive adhesive layer before being bonded to the first adherend and the second adherend is a semi-cured pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition is a crosslinkable acrylic copolymer, It preferably contains a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
粘着剤層は、第1の被着材及び第2の被着材に貼合される前の段階では、後硬化性を有する粘着剤層であることが好ましい。すなわち、第1の被着材及び第2の被着材に貼合される前の状態では、粘着剤層は粘着剤組成物を半硬化状態とした粘着剤層であることが好ましい。なお、粘着剤層がアクリル系粘着剤層である場合、粘着剤組成物は少なくともアクリル共重合体を含む。また、第1の被着材及び第2の被着材に貼合される前の粘着剤層が半硬化状態の粘着剤層である場合、粘着剤組成物は、架橋性アクリル共重合体、架橋剤、光重合開始剤、単官能単量体及び多官能単量体を含むことが好ましい。 (Adhesive composition)
The pressure-sensitive adhesive layer is preferably a pressure-sensitive adhesive layer having a post-curing property before being attached to the first adherend and the second adherend. That is, it is preferable that the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition in a state before being bonded to the first adherend and the second adherend. When the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition contains at least an acrylic copolymer. When the pressure-sensitive adhesive layer before being bonded to the first adherend and the second adherend is a semi-cured pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition is a crosslinkable acrylic copolymer, It preferably contains a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer.
(アクリル共重合体)
アクリル共重合体は、非架橋性(メタ)アクリル酸エステル単位(a1)と、架橋性官能基を有するアクリル単量体単位(a2)を含有するものであることが好ましい。すなわち、アクリル共重合体は、架橋性アクリル共重合体であることが好ましい。架橋性アクリル共重合体は、表示装置等の視認性を低下させない程度の透明性を有するものが好ましい。 (Acrylic copolymer)
The acrylic copolymer preferably contains a non-crosslinkable (meth)acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group. That is, the acrylic copolymer is preferably a crosslinkable acrylic copolymer. The crosslinkable acrylic copolymer is preferably one having transparency to the extent that visibility of a display device or the like is not deteriorated.
アクリル共重合体は、非架橋性(メタ)アクリル酸エステル単位(a1)と、架橋性官能基を有するアクリル単量体単位(a2)を含有するものであることが好ましい。すなわち、アクリル共重合体は、架橋性アクリル共重合体であることが好ましい。架橋性アクリル共重合体は、表示装置等の視認性を低下させない程度の透明性を有するものが好ましい。 (Acrylic copolymer)
The acrylic copolymer preferably contains a non-crosslinkable (meth)acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group. That is, the acrylic copolymer is preferably a crosslinkable acrylic copolymer. The crosslinkable acrylic copolymer is preferably one having transparency to the extent that visibility of a display device or the like is not deteriorated.
非架橋性(メタ)アクリル酸エステル単位(a1)は、(メタ)アクリル酸アルキルエステルに由来する繰り返し単位である。(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸n-ウンデシル、(メタ)アクリル酸n-ドデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ベンジル等が挙げられる。これらは1種を単独で使用してもよいし、2種以上を併用してもよい。
上記(メタ)アクリル酸アルキルエステルの中でも、粘着性が高くなることから、(メタ)アクリル酸メチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシルから選ばれる少なくとも1種が好ましい。 The non-crosslinkable (meth)acrylic acid ester unit (a1) is a repeating unit derived from a (meth)acrylic acid alkyl ester. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Isobutyl acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, ( Isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, (meth) Examples thereof include n-dodecyl acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. These may be used alone or in combination of two or more.
Among the above-mentioned (meth)acrylic acid alkyl esters, at least one selected from methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate since it has high adhesiveness. preferable.
上記(メタ)アクリル酸アルキルエステルの中でも、粘着性が高くなることから、(メタ)アクリル酸メチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸2-エチルヘキシルから選ばれる少なくとも1種が好ましい。 The non-crosslinkable (meth)acrylic acid ester unit (a1) is a repeating unit derived from a (meth)acrylic acid alkyl ester. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. Isobutyl acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, ( Isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, (meth) Examples thereof include n-dodecyl acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. These may be used alone or in combination of two or more.
Among the above-mentioned (meth)acrylic acid alkyl esters, at least one selected from methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate since it has high adhesiveness. preferable.
架橋性官能基を有するアクリル単量体単位(a2)としては、ヒドロキシ基含有単量体単位、アミノ基含有単量体単位、グリシジル基含有単量体単位、カルボキシ基含有単量体単位等が挙げられる。これら単量体単位は1種でもよいし、2種以上でもよい。
ヒドロキシ基含有単量体単位は、ヒドロキシ基含有単量体に由来する繰り返し単位である。ヒドロキシ基含有単量体としては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシプロピルなどの(メタ)アクリル酸ヒドロキシアルキル、(メタ)アクリル酸モノ(ジエチレングリコール)などの(メタ)アクリル酸[(モノ、ジ又はポリ)アルキレングリコール]、(メタ)アクリル酸モノカプロラクトンなどの(メタ)アクリル酸ラクトンが挙げられる。
アミノ基含有単量体単位としては、例えば、(メタ)アクリルアミド、アリルアミン等のアミノ基含有単量体に由来する繰り返し単位が挙げられる。
グリシジル基含有単量体単位としては、(メタ)アクリル酸グリシジル等のグリシジル基含有単量体に由来する繰り返し単位が挙げられる。
カルボキシ基含有単量体単位としては、アクリル酸、メタクリル酸が挙げられる。 Examples of the acrylic monomer unit (a2) having a crosslinkable functional group include a hydroxy group-containing monomer unit, an amino group-containing monomer unit, a glycidyl group-containing monomer unit and a carboxy group-containing monomer unit. Can be mentioned. These monomer units may be of one type or of two or more types.
The hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer. Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Examples thereof include (meth)acrylic acid [(mono-, di- or poly)alkylene glycol] such as (meth)acrylic acid mono(diethylene glycol), and (meth)acrylic acid lactone such as (meth)acrylic acid monocaprolactone.
Examples of the amino group-containing monomer unit include repeating units derived from amino group-containing monomers such as (meth)acrylamide and allylamine.
Examples of the glycidyl group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth)acrylate.
Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
ヒドロキシ基含有単量体単位は、ヒドロキシ基含有単量体に由来する繰り返し単位である。ヒドロキシ基含有単量体としては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシプロピルなどの(メタ)アクリル酸ヒドロキシアルキル、(メタ)アクリル酸モノ(ジエチレングリコール)などの(メタ)アクリル酸[(モノ、ジ又はポリ)アルキレングリコール]、(メタ)アクリル酸モノカプロラクトンなどの(メタ)アクリル酸ラクトンが挙げられる。
アミノ基含有単量体単位としては、例えば、(メタ)アクリルアミド、アリルアミン等のアミノ基含有単量体に由来する繰り返し単位が挙げられる。
グリシジル基含有単量体単位としては、(メタ)アクリル酸グリシジル等のグリシジル基含有単量体に由来する繰り返し単位が挙げられる。
カルボキシ基含有単量体単位としては、アクリル酸、メタクリル酸が挙げられる。 Examples of the acrylic monomer unit (a2) having a crosslinkable functional group include a hydroxy group-containing monomer unit, an amino group-containing monomer unit, a glycidyl group-containing monomer unit and a carboxy group-containing monomer unit. Can be mentioned. These monomer units may be of one type or of two or more types.
The hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer. Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; Examples thereof include (meth)acrylic acid [(mono-, di- or poly)alkylene glycol] such as (meth)acrylic acid mono(diethylene glycol), and (meth)acrylic acid lactone such as (meth)acrylic acid monocaprolactone.
Examples of the amino group-containing monomer unit include repeating units derived from amino group-containing monomers such as (meth)acrylamide and allylamine.
Examples of the glycidyl group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth)acrylate.
Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
アクリル共重合体における架橋性アクリル単量体単位(a2)の含有量は0.01質量%以上40質量%以下であることが好ましく、0.5質量%以上35質量%以下であることがより好ましい。
The content of the crosslinkable acrylic monomer unit (a2) in the acrylic copolymer is preferably 0.01% by mass or more and 40% by mass or less, and more preferably 0.5% by mass or more and 35% by mass or less. preferable.
なお、アクリル共重合体は、ヒドロキシ基含有単量体単位を含むものであることが好ましい。ヒドロキシ基含有単量体単位の含有量は、アクリル共重合体の全質量に対して、0.01質量%以上40質量%以下であることが好ましく、0.5質量%以上35質量%以下であることがより好ましい。なお、ヒドロキシ基含有単量体単位の含有量を上記範囲内とすることにより、均一な架橋構造が発現するため粘着性能が向上し、高温条件下における弾性率をより高めることができる。
The acrylic copolymer preferably contains a hydroxy group-containing monomer unit. The content of the hydroxy group-containing monomer unit is preferably 0.01% by mass or more and 40% by mass or less, and 0.5% by mass or more and 35% by mass or less, based on the total mass of the acrylic copolymer. More preferably. By setting the content of the hydroxy group-containing monomer unit within the above range, a uniform cross-linked structure is developed, so that the adhesive performance is improved and the elastic modulus under high temperature conditions can be further increased.
アクリル共重合体は、窒素含有単量体に由来する単位をさらに含んでもよい。窒素含有単量体は、1分子内に窒素元素を含有する単量体である。窒素含有単量体としては、例えば、ジメチルアクリルアミド、ジエチルアクリルアミド、アクリロイルモルホリン、ヒドロキシエチルアクリルアミド、メチロールアクリルアミド、メトキシメチルアクリルアミド、エトキシメチルアクリルアミド、ジメチルアミノエチルアクリルアミド、N-ビニルカプロラクタム、N-ビニル-2-ピロリドン、ジメチルアミノエチル(メタ)アクリレート、N-ビニルホルムアミド等を挙げることができる。中でも、窒素含有単量体は、アクリルアミド誘導体、アミノ基含有モノマー及び含窒素複素環含有モノマーから選択される少なくとも1種であることが好ましく、アクリルアミド誘導体であることがより好ましい。アクリルアミド誘導体は、ジメチルアクリルアミド、ジエチルアクリルアミド及びアクリロイルモルホリンから選択される少なくとも1種であることがさらに好ましく、ジメチルアクリルアミドであることが特に好ましい。
The acrylic copolymer may further include units derived from a nitrogen-containing monomer. The nitrogen-containing monomer is a monomer containing a nitrogen element in one molecule. Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam and N-vinyl-2-. Pyrrolidone, dimethylaminoethyl (meth)acrylate, N-vinylformamide and the like can be mentioned. Among them, the nitrogen-containing monomer is preferably at least one selected from acrylamide derivatives, amino group-containing monomers and nitrogen-containing heterocycle-containing monomers, and more preferably acrylamide derivatives. The acrylamide derivative is more preferably at least one selected from dimethylacrylamide, diethylacrylamide and acryloylmorpholine, and particularly preferably dimethylacrylamide.
窒素含有単量体に由来する単位の含有量は、アクリル共重合体の全質量に対して、1質量%以上であることが好ましく、3質量%以上であることがより好ましい。また、窒素含有単量体に由来する単位の含有量は、アクリル共重合体の全質量に対して、20質量%以下であることが好ましい。
The content of units derived from the nitrogen-containing monomer is preferably 1% by mass or more, and more preferably 3% by mass or more, based on the total mass of the acrylic copolymer. The content of units derived from the nitrogen-containing monomer is preferably 20% by mass or less based on the total mass of the acrylic copolymer.
アクリル共重合体は、必要に応じて、(メタ)アクリル酸アルコキシアルキルエステル単位や、脂環構造を有する(メタ)アクリル酸エステルを含有してもよい。また、アクリル共重合体は、上記単量体単位以外の他の単量体単位を有してもよい。他の単量体は、上記単量体単位と共重合可能なものであればよく、例えば(メタ)アクリロニトリル、酢酸ビニル、スチレン、塩化ビニル、ビニルピロリドン、ビニルピリジン等が挙げられる。
The acrylic copolymer may contain (meth)acrylic acid alkoxyalkyl ester units or (meth)acrylic acid ester having an alicyclic structure, if necessary. Further, the acrylic copolymer may have a monomer unit other than the above monomer units. Any other monomer may be used as long as it can be copolymerized with the above monomer unit, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, and vinylpyridine.
アクリル共重合体の重量平均分子量は、10万以上であることが好ましく、30万以上であることがより好ましく、50万以上であることがさらに好ましく、60万以上であることが特に好ましい。また、アクリル共重合体の重量平均分子量は、200万以下であることが好ましく、180万以下であることがより好ましく、160万以下であることがさらに好ましい。アクリル共重合体の重量平均分子量を上記範囲内とすることにより塗工性に優れ、粘着剤層は優れた耐アウトガス性を発揮しやすくなる。
The weight average molecular weight of the acrylic copolymer is preferably 100,000 or more, more preferably 300,000 or more, further preferably 500,000 or more, particularly preferably 600,000 or more. The weight average molecular weight of the acrylic copolymer is preferably 2,000,000 or less, more preferably 1.8 million or less, and further preferably 1.6 million or less. When the weight average molecular weight of the acrylic copolymer is within the above range, the coatability is excellent, and the pressure-sensitive adhesive layer is likely to exhibit excellent outgas resistance.
アクリル共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフイー(GPC)により測定し、ポリスチレン基準で求めた値である。ゲルパーミエーションクロマトグラフイー(GPC)の測定条件は以下のとおりである。
溶媒:テトラヒドロフラン(THF)
カラム:Shodex KF801、KF803L、KF800L、KF800D(昭和電工(株)製を4本接続して使用した)
カラム温度:40℃
試料濃度:0.5質量%
検出器:RI-2031plus(JASCO製)
ポンプ:RI-2080plus(JASCO製)
流量(流速):0.8ml/min
注入量:10μl
校正曲線:標準ポリスチレンShodex standard ポリスチレン(昭和電工(株)製)Mw=1320~2,500,000迄の10サンプルによる校正曲線を使用した。 The weight average molecular weight of the acrylic copolymer is a value measured by gel permeation chromatography (GPC) and determined on a polystyrene basis. The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran (THF)
Column: Shodex KF801, KF803L, KF800L, KF800D (four Showa Denko KK were used by connecting)
Column temperature: 40°C
Sample concentration: 0.5% by mass
Detector: RI-2031plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow velocity): 0.8 ml/min
Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko KK) Mw = 1320 to a calibration curve of 10 samples from 2,500,000 was used.
溶媒:テトラヒドロフラン(THF)
カラム:Shodex KF801、KF803L、KF800L、KF800D(昭和電工(株)製を4本接続して使用した)
カラム温度:40℃
試料濃度:0.5質量%
検出器:RI-2031plus(JASCO製)
ポンプ:RI-2080plus(JASCO製)
流量(流速):0.8ml/min
注入量:10μl
校正曲線:標準ポリスチレンShodex standard ポリスチレン(昭和電工(株)製)Mw=1320~2,500,000迄の10サンプルによる校正曲線を使用した。 The weight average molecular weight of the acrylic copolymer is a value measured by gel permeation chromatography (GPC) and determined on a polystyrene basis. The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran (THF)
Column: Shodex KF801, KF803L, KF800L, KF800D (four Showa Denko KK were used by connecting)
Column temperature: 40°C
Sample concentration: 0.5% by mass
Detector: RI-2031plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow velocity): 0.8 ml/min
Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko KK) Mw = 1320 to a calibration curve of 10 samples from 2,500,000 was used.
アクリル共重合体の含有量は、粘着剤組成物の全質量に対し、75質量%以上であることが好ましく、80質量%以上であることがより好ましく、85質量%以上であることがさらに好ましい。
The content of the acrylic copolymer is preferably 75% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more based on the total mass of the pressure-sensitive adhesive composition. ..
(架橋剤)
粘着剤組成物は、架橋剤を含むものであることが好ましい。架橋剤は、アクリル共重合体が有する架橋性官能基との反応性を考慮して適宜選択できる。例えばイソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物などの公知の架橋剤の中から選択できる。これらの中でも、架橋性官能基を有するアクリル単量体単位(a2)を容易に架橋できることから、イソシアネート化合物やエポキシ化合物が好ましい。例えば、架橋性官能基としてヒドロキシ基を含む場合は、ヒドロキシ基の反応性から、イソシアネート化合物を用いることがより好ましい。 (Crosslinking agent)
The pressure-sensitive adhesive composition preferably contains a crosslinking agent. The cross-linking agent can be appropriately selected in consideration of the reactivity with the cross-linkable functional group of the acrylic copolymer. For example, it can be selected from known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound and a butylated melamine compound. Among these, isocyanate compounds and epoxy compounds are preferable because they can easily crosslink the acrylic monomer unit (a2) having a crosslinkable functional group. For example, when a hydroxyl group is included as the crosslinkable functional group, an isocyanate compound is more preferably used because of the reactivity of the hydroxy group.
粘着剤組成物は、架橋剤を含むものであることが好ましい。架橋剤は、アクリル共重合体が有する架橋性官能基との反応性を考慮して適宜選択できる。例えばイソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物などの公知の架橋剤の中から選択できる。これらの中でも、架橋性官能基を有するアクリル単量体単位(a2)を容易に架橋できることから、イソシアネート化合物やエポキシ化合物が好ましい。例えば、架橋性官能基としてヒドロキシ基を含む場合は、ヒドロキシ基の反応性から、イソシアネート化合物を用いることがより好ましい。 (Crosslinking agent)
The pressure-sensitive adhesive composition preferably contains a crosslinking agent. The cross-linking agent can be appropriately selected in consideration of the reactivity with the cross-linkable functional group of the acrylic copolymer. For example, it can be selected from known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound and a butylated melamine compound. Among these, isocyanate compounds and epoxy compounds are preferable because they can easily crosslink the acrylic monomer unit (a2) having a crosslinkable functional group. For example, when a hydroxyl group is included as the crosslinkable functional group, an isocyanate compound is more preferably used because of the reactivity of the hydroxy group.
イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート等が挙げられる。
エポキシ化合物としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、テトラグリシジルキシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。 Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned.
エポキシ化合物としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、テトラグリシジルキシレンジアミン、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。 Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned.
粘着剤組成物中の架橋剤の含有量は、所望とする粘着物性等に応じて適宜選択されるが、アクリル共重合体100質量部に対し、0.01質量部以上5質量部以下であることが好ましく、0.1質量部以上3質量部以下であることがより好ましい。架橋剤としては1種を単独で用いても2種以上を併用してもよく、2種以上を併用する場合は、合計質量が上記範囲内であることが好ましい。
The content of the crosslinking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired pressure-sensitive adhesive properties and the like, but is 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. It is preferably 0.1 part by mass or more and 3 parts by mass or less. As the crosslinking agent, one kind may be used alone, or two or more kinds may be used in combination, and when two kinds or more are used in combination, the total mass is preferably within the above range.
(光重合開始剤)
粘着剤層が後硬化性を有するものである場合、粘着剤組成物は光重合開始剤を含むものであることが好ましい。光重合開始剤は、アクリル共重合体の重合に用いられる。光重合開始剤としては、特に限定されないが、例えば、2,2-ジメトキシー2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシル-フェニルケトン、2-ヒドロキシ-2-メチル-1-ヘニルプロパノン、1-[4-(2-ヒドロキシエトキシル)-フェニル]-2-ヒドロキシ-メチルプロパノン、2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル)フェニル)-2-メチル-1-プロパノン等のアルキルフェノン系光重合開始剤、2,4,6-トリメチルベンゾイル-ジフェニルフォスフィンオキサイドや2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド系重合開始剤、ベンゾイルギ酸メチルや4メチルベンゾフェノン等の分子内水素引き抜き型光重合開始剤のほか、オキシムエステル系重合光開始剤やカチオン系重合光開始剤などの油溶性重合開始剤を挙げることができる。 (Photopolymerization initiator)
When the pressure-sensitive adhesive layer has post-curability, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator. The photopolymerization initiator is used for polymerizing the acrylic copolymer. The photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-enyl propanone, 1-[4-( 2-Hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1- Alkylphenone photoinitiators such as propanone, acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzoyl In addition to intramolecular hydrogen abstraction type photopolymerization initiators such as methyl formate and 4-methylbenzophenone, oil-soluble polymerization initiators such as oxime ester polymerization photoinitiators and cationic polymerization photoinitiators can be mentioned.
粘着剤層が後硬化性を有するものである場合、粘着剤組成物は光重合開始剤を含むものであることが好ましい。光重合開始剤は、アクリル共重合体の重合に用いられる。光重合開始剤としては、特に限定されないが、例えば、2,2-ジメトキシー2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシル-フェニルケトン、2-ヒドロキシ-2-メチル-1-ヘニルプロパノン、1-[4-(2-ヒドロキシエトキシル)-フェニル]-2-ヒドロキシ-メチルプロパノン、2-ヒドロキシ-1-(4-(4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル)フェニル)-2-メチル-1-プロパノン等のアルキルフェノン系光重合開始剤、2,4,6-トリメチルベンゾイル-ジフェニルフォスフィンオキサイドや2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド系重合開始剤、ベンゾイルギ酸メチルや4メチルベンゾフェノン等の分子内水素引き抜き型光重合開始剤のほか、オキシムエステル系重合光開始剤やカチオン系重合光開始剤などの油溶性重合開始剤を挙げることができる。 (Photopolymerization initiator)
When the pressure-sensitive adhesive layer has post-curability, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator. The photopolymerization initiator is used for polymerizing the acrylic copolymer. The photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-enyl propanone, 1-[4-( 2-Hydroxyethoxyl)-phenyl]-2-hydroxy-methylpropanone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methyl-1- Alkylphenone photoinitiators such as propanone, acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzoyl In addition to intramolecular hydrogen abstraction type photopolymerization initiators such as methyl formate and 4-methylbenzophenone, oil-soluble polymerization initiators such as oxime ester polymerization photoinitiators and cationic polymerization photoinitiators can be mentioned.
光重合開始剤の含有量は、アクリル共重合体100質量部に対し、0.1質量部以上10質量部以下であることが好ましく、0.4質量部以上5質量部以下であることがより好ましい。光重合開始剤としては1種を単独で用いても2種以上を併用してもよく、2種以上を併用する場合は、合計質量が上記範囲内であることが好ましい。
The content of the photopolymerization initiator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.4 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. preferable. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.
(単官能単量体)
粘着剤組成物は、分子内に反応性二重結合を1つ有する単官能単量体を含有することが好ましい。 (Monofunctional monomer)
The pressure-sensitive adhesive composition preferably contains a monofunctional monomer having one reactive double bond in the molecule.
粘着剤組成物は、分子内に反応性二重結合を1つ有する単官能単量体を含有することが好ましい。 (Monofunctional monomer)
The pressure-sensitive adhesive composition preferably contains a monofunctional monomer having one reactive double bond in the molecule.
単官能単量体としては、例えば、ラウリルアクリレート、イソボルニルアクリレート、イソステアリルアクリレート、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、ベンジルメタクリレート、N-アクリロイルオキシエチルヘキサヒドロフタルイミド、アクリルアミド、N,N-ジメチルアクリルアミド、N,N-ジエチルアクリルアミド、アクリロイルモルホリン、ビニルピロリドンなどを挙げることができる。中でも、単官能単量体は、ラウリルアクリレートであることが好ましい。単官能単量体の市販品の例としては、大阪有機化学工業(株)社製のラウリルアクリレート(LA)等が挙げられる。
Examples of the monofunctional monomer include lauryl acrylate, isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N,N-dimethyl. Examples thereof include acrylamide, N,N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone and the like. Among them, the monofunctional monomer is preferably lauryl acrylate. Examples of commercially available monofunctional monomers include lauryl acrylate (LA) manufactured by Osaka Organic Chemical Industry Co., Ltd. and the like.
単官能単量体の含有量はアクリル共重合体100質量部に対して、1~20質量部であることが好ましく、2~20質量部であることがより好ましい。上記単官能単量体は1種類を単独で用いても2種類以上を併用してもよく、2種類以上を併用する場合は、合計質量が上記範囲内であることが好ましい。
The content of the monofunctional monomer is preferably 1 to 20 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer. The monofunctional monomers may be used alone or in combination of two or more, and when two or more are used in combination, the total mass is preferably within the above range.
(多官能単量体)
粘着剤組成物は、分子内に反応性二重結合を2つ以上有する多官能単量体を含有することが好ましい。多官能単量体は反応性二重結合を2つ以上有するものであり、中でも、多官能単量体は反応性二重結合を2つ以上5つ未満有するものであることが好ましく、2つ以上4つ未満有するものであることがより好ましい。 (Polyfunctional monomer)
The pressure-sensitive adhesive composition preferably contains a polyfunctional monomer having two or more reactive double bonds in the molecule. The polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more and less than five reactive double bonds, and preferably two. More preferably, it has less than four.
粘着剤組成物は、分子内に反応性二重結合を2つ以上有する多官能単量体を含有することが好ましい。多官能単量体は反応性二重結合を2つ以上有するものであり、中でも、多官能単量体は反応性二重結合を2つ以上5つ未満有するものであることが好ましく、2つ以上4つ未満有するものであることがより好ましい。 (Polyfunctional monomer)
The pressure-sensitive adhesive composition preferably contains a polyfunctional monomer having two or more reactive double bonds in the molecule. The polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more and less than five reactive double bonds, and preferably two. More preferably, it has less than four.
多官能単量体としては、例えば、ジ(メタ)アクリル酸エチレングリコール、ジ(メタ)アクリル酸トリエチレングリコール、ジ(メタ)アクリル酸1,3-ブチレングリコール、ジ(メタ)アクリル酸1,4-ブチレングリコール、ジ(メタ)アクリル酸1,9-ノナンジオール、ジアクリル酸1,6-ヘキサンジオール、ジ(メタ)アクリル酸ポリブチレングリコール、ジ(メタ)アクリル酸ネオペンチルグリコール、ジ(メタ)アクリル酸テトラエチレングリコール、ジ(メタ)アクリル酸トリプロピレングリコール、ジ(メタ)アクリル酸ポリプロピレングリコール、ビスフェノールAジグリシジルエーテルのジアクリレート、トリ(メタ)アクリル酸トリメチロールプロパン、トリ(メタ)アクリル酸ペンタエリスリトール、テトラ(メタ)アクリル酸ペンタエリスリトール等の多価アルコールの(メタ)アクリル酸エステル類、メタクリル酸ビニル等が挙げられる。
Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, di(meth)acrylic acid 1, 4-butylene glycol, 1,9-nonanediol di(meth)acrylic acid, 1,6-hexanediol diacrylic acid, polybutylene glycol di(meth)acrylic acid, neopentyl glycol di(meth)acrylic acid, di(meth)acrylic acid ) Tetraethylene glycol acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, diacrylate of bisphenol A diglycidyl ether, trimethylolpropane tri(meth)acrylate, tri(meth)acrylic Examples thereof include (meth)acrylic acid esters of polyhydric alcohols such as acid pentaerythritol and pentaerythritol tetra(meth)acrylate, vinyl methacrylate and the like.
中でも、多官能単量体は、1分子内にビスフェノール骨格を有する多官能単量体であることが好ましい。1分子内にビスフェノール骨格を有する多官能単量体を用いることにより、後硬化後の粘着剤層の硬度をより効果的に高めることができる。これにより、後硬化後の粘着剤層の耐アウトガス性をより効果的に高めることができる。
Among them, the polyfunctional monomer is preferably a polyfunctional monomer having a bisphenol skeleton in one molecule. By using a polyfunctional monomer having a bisphenol skeleton in one molecule, the hardness of the pressure-sensitive adhesive layer after post-curing can be more effectively increased. Thereby, the outgas resistance of the pressure-sensitive adhesive layer after post-curing can be more effectively enhanced.
1分子内にビスフェノール骨格を有する多官能単量体としては、例えば、ビスフェノールAジグリシジルエーテルのジアクリレート、プロポキシ化ビスフェノールAのジアクリレート、ビスフェノールFジグリシジルエーテルのジアクリレート等が挙げられる。
Examples of polyfunctional monomers having a bisphenol skeleton in one molecule include diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and diacrylate of bisphenol F diglycidyl ether.
多官能単量体として、市販品を使用できる。市販品の例としては、東亞合成社製、二官能モノマーM211B(ビスフェノールA エチレンオキサイド変性ジアクリレート)、東亞合成社製、二官能モノマーM08(ビスフェノールF エチレンオキサイド変性ジアクリレート)、新中村化学社製、二官能モノマーA-BPP-3(プロポキシ化ビスフェノールAジアクリレート)等が挙げられる。
Commercial products can be used as the polyfunctional monomer. As examples of commercially available products, Toagosei Co., Ltd., bifunctional monomer M211B (bisphenol A ethylene oxide modified diacrylate), Toagosei Co., Ltd., bifunctional monomer M08 (bisphenol F ethylene oxide modified diacrylate), Shin Nakamura Chemical Co., Ltd. , Bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate) and the like.
多官能単量体の含有量はアクリル共重合体100質量部に対して、1~30質量部であることが好ましく、5~30質量部であることがより好ましい。上記多官能単量体は1種類を単独で用いても2種類以上を併用してもよく、2種類以上を併用する場合は、合計質量が上記範囲内であることが好ましい。多官能単量体の含有量を上記範囲内とすることにより、後硬化後の粘着剤層の硬度をより効果的に高めることができ、粘着剤層の耐アウトガス性をより効果的に高めることができる。
The content of the polyfunctional monomer is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer. The polyfunctional monomers may be used alone or in combination of two or more, and when two or more are used in combination, the total mass is preferably within the above range. By setting the content of the polyfunctional monomer within the above range, the hardness of the pressure-sensitive adhesive layer after post-curing can be more effectively increased, and the outgas resistance of the pressure-sensitive adhesive layer can be more effectively increased. You can
(溶剤)
粘着剤組成物は溶剤を含むものであってもよい。すなわち、粘着剤組成物は溶剤型粘着剤組成物であってもよい。 (solvent)
The pressure-sensitive adhesive composition may contain a solvent. That is, the pressure-sensitive adhesive composition may be a solvent-type pressure-sensitive adhesive composition.
粘着剤組成物は溶剤を含むものであってもよい。すなわち、粘着剤組成物は溶剤型粘着剤組成物であってもよい。 (solvent)
The pressure-sensitive adhesive composition may contain a solvent. That is, the pressure-sensitive adhesive composition may be a solvent-type pressure-sensitive adhesive composition.
溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の炭化水素類;ジクロロメタン、トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、ジクロロプロパン等のハロゲン化炭化水素類;メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、ジアセトンアルコール等のアルコール類;ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン等のケトン類;酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酪酸エチル等のエステル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセタート等のポリオール及びその誘導体が挙げられる。
Examples of the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane; methanol, ethanol, Alcohols such as propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate , Ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate, and other esters; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Examples thereof include polyols such as glycol monomethyl ether acetate and derivatives thereof.
溶剤は1種を単独で使用してもよいし、2種以上を併用してもよい。粘着剤組成物中における溶剤の含有量は、特に限定されないが、アクリル共重合体100質量部に対し、25質量部以上500質量部以下とすることができ、30質量部以上400質量部以下とすることができる。
The solvent may be used alone or in combination of two or more. The content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but can be 25 parts by mass or more and 500 parts by mass or less, and 30 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. can do.
(その他の成分)
粘着剤組成物は、本発明の効果を損なわない範囲で、上記以外の他の成分を含有してもよい。他の成分としては、粘着剤用の添加剤として公知の成分を挙げることができる。例えば可塑剤、酸化防止剤、金属腐食防止剤、粘着付与剤、シランカップリング剤、紫外線吸収剤、ヒンダードアミン系化合物等の光安定剤等の中から必要に応じて選択できる。また、着色を目的に染料や顔料を添加してもよい。
可塑剤としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルのようなカルボン酸ビニルエステル類やスチレン等が挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は1種類を単独で使用してもよいし、2種類以上を併用してもよい。
金属腐食防止剤としては、粘着剤の相溶性や効果の高さから、ベンゾリアゾール系樹脂を好ましい例として挙げることができる。
粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
シランカップリング剤としては、例えば、メルカプトアルコキシシラン化合物(例えば、メルカプト基置換アルコキシオリゴマー等)などが挙げられる。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。ただし、後硬化時の活性エネルギー線に紫外線を用いる場合は、重合反応を阻害しない範囲で添加することが好ましい。 (Other ingredients)
The pressure-sensitive adhesive composition may contain components other than the above components as long as the effects of the present invention are not impaired. Examples of other components include components known as additives for pressure-sensitive adhesives. For example, a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, and a light stabilizer such as a hindered amine compound can be selected as necessary. Further, a dye or a pigment may be added for the purpose of coloring.
Examples of the plasticizer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoic acid. Examples thereof include carboxylic acid vinyl esters such as vinyl acid salt and styrene.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like. These antioxidants may be used alone or in combination of two or more.
As the metal corrosion inhibitor, a benzotriazole resin can be mentioned as a preferable example because of the compatibility of the pressure-sensitive adhesive and the high effect.
Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin and the like.
Examples of the silane coupling agent include a mercaptoalkoxysilane compound (eg, a mercapto group-substituted alkoxy oligomer).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds. However, when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them in a range that does not inhibit the polymerization reaction.
粘着剤組成物は、本発明の効果を損なわない範囲で、上記以外の他の成分を含有してもよい。他の成分としては、粘着剤用の添加剤として公知の成分を挙げることができる。例えば可塑剤、酸化防止剤、金属腐食防止剤、粘着付与剤、シランカップリング剤、紫外線吸収剤、ヒンダードアミン系化合物等の光安定剤等の中から必要に応じて選択できる。また、着色を目的に染料や顔料を添加してもよい。
可塑剤としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルのようなカルボン酸ビニルエステル類やスチレン等が挙げられる。
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は1種類を単独で使用してもよいし、2種類以上を併用してもよい。
金属腐食防止剤としては、粘着剤の相溶性や効果の高さから、ベンゾリアゾール系樹脂を好ましい例として挙げることができる。
粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
シランカップリング剤としては、例えば、メルカプトアルコキシシラン化合物(例えば、メルカプト基置換アルコキシオリゴマー等)などが挙げられる。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。ただし、後硬化時の活性エネルギー線に紫外線を用いる場合は、重合反応を阻害しない範囲で添加することが好ましい。 (Other ingredients)
The pressure-sensitive adhesive composition may contain components other than the above components as long as the effects of the present invention are not impaired. Examples of other components include components known as additives for pressure-sensitive adhesives. For example, a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, and a light stabilizer such as a hindered amine compound can be selected as necessary. Further, a dye or a pigment may be added for the purpose of coloring.
Examples of the plasticizer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoic acid. Examples thereof include carboxylic acid vinyl esters such as vinyl acid salt and styrene.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like. These antioxidants may be used alone or in combination of two or more.
As the metal corrosion inhibitor, a benzotriazole resin can be mentioned as a preferable example because of the compatibility of the pressure-sensitive adhesive and the high effect.
Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin and the like.
Examples of the silane coupling agent include a mercaptoalkoxysilane compound (eg, a mercapto group-substituted alkoxy oligomer).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds. However, when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them in a range that does not inhibit the polymerization reaction.
(積層体の製造方法)
本発明は、上述した積層体の製造方法に関するものでもある。積層体の製造方法は、後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程と、第1の被着材もしくは第2の被着材側から活性エネルギー線を照射する工程とを含むことが好ましい。 (Method for manufacturing laminated body)
The present invention also relates to a method for manufacturing the above-mentioned laminated body. The method for manufacturing a laminate comprises a step of laminating a first adherend and a second adherend to a pressure-sensitive adhesive layer having a post-curing property, and a first adherend or a second adherend. It is preferable to include a step of irradiating the active energy ray from the side.
本発明は、上述した積層体の製造方法に関するものでもある。積層体の製造方法は、後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程と、第1の被着材もしくは第2の被着材側から活性エネルギー線を照射する工程とを含むことが好ましい。 (Method for manufacturing laminated body)
The present invention also relates to a method for manufacturing the above-mentioned laminated body. The method for manufacturing a laminate comprises a step of laminating a first adherend and a second adherend to a pressure-sensitive adhesive layer having a post-curing property, and a first adherend or a second adherend. It is preferable to include a step of irradiating the active energy ray from the side.
後硬化性を有する粘着剤層は、例えば、以下のようにして製造することができる。後硬化性を有する粘着剤層を製造する工程では、上述した粘着剤組成物を塗工して塗膜を形成し、該塗膜を加熱する工程を含むことが好ましい。例えば、剥離シート上に粘着剤組成物を塗工して塗膜を形成し、該塗膜を加熱して半硬化状態の硬化物とすることが好ましい。塗膜の加熱により、アクリル共重合体及び架橋剤の反応が進行して半硬化状態の粘着剤層が形成される。
The post-curing pressure-sensitive adhesive layer can be manufactured, for example, as follows. The step of producing a pressure-sensitive adhesive layer having post-curability preferably includes a step of applying the above-mentioned pressure-sensitive adhesive composition to form a coating film and heating the coating film. For example, it is preferable to apply a pressure-sensitive adhesive composition on a release sheet to form a coating film, and heat the coating film to obtain a semi-cured cured product. By heating the coating film, the reaction of the acrylic copolymer and the crosslinking agent proceeds to form a semi-cured pressure-sensitive adhesive layer.
粘着剤組成物の塗工は、公知の塗工装置を用いて実施できる。塗工装置としては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、マイクログラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター等が挙げられる。
The coating of the pressure-sensitive adhesive composition can be carried out using a known coating device. Examples of the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, and a curtain coater.
塗工工程では、乾燥後の塗工量が10μm/m2以上となるように塗工することが好ましく、20μm/m2以上となるように塗工することがより好ましい。また、乾燥後の塗工量が500μm/m2以下となるように塗工することが好ましく、300μm/m2以下となるように塗工することがより好ましい。
In the coating step, the coating amount after drying is preferably 10 μm/m 2 or more, and more preferably 20 μm/m 2 or more. In addition, it is preferable that the coating amount after drying be 500 μm/m 2 or less, and more preferable that the coating amount be 300 μm/m 2 or less.
塗膜の加熱乾燥工程は、加熱炉、赤外線ランプ等の公知の加熱装置を用いて実施できる。例えば、50℃以上150℃以下の空気循環式恒温オーブンで10秒以上10分以下乾燥させる。
The heating and drying process of the coating film can be carried out using a known heating device such as a heating furnace or an infrared lamp. For example, it is dried for 10 seconds or more and 10 minutes or less in an air circulation type constant temperature oven at 50° C. or more and 150° C. or less.
加熱乾燥工程の後には、一定温度で一定期間粘着シートを静置するエージング処理工程を設けることが好ましい。エージング処理工程は例えば、23℃、相対湿度50%の条件下で7日間静置して行うことができる。
After the heating and drying step, it is preferable to provide an aging treatment step in which the pressure-sensitive adhesive sheet is allowed to stand at a certain temperature for a certain period. The aging treatment step can be performed by standing for 7 days under the conditions of 23° C. and 50% relative humidity.
後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程では、上述した方法で得られた後硬化性を有する粘着剤層の各面に第1の被着材と第2の被着材をそれぞれ貼合する。貼合後には、密着性を高めるためにオートクレーブ処理を施してもよい。
In the step of laminating the first adherend and the second adherend to the pressure-sensitive adhesive layer having a post-curing property, the first layer and the second layer are formed on each surface of the post-curing pressure-sensitive adhesive layer obtained by the method described above. The first adherend and the second adherend are attached to each other. After laminating, you may perform an autoclave process in order to improve adhesiveness.
粘着剤層の両面に第1の被着材と第2の被着材を貼合した後には、第1の被着材もしくは第2の被着材側から活性エネルギー線を照射する工程が設けられることが好ましい。活性エネルギー線が照射されることで、半硬化状態の粘着剤層が完全硬化(後硬化)する。これにより、粘着剤層の凝集力が高まり、各被着材への粘着性が向上する。また、粘着剤層を後硬化することにより、積層体全体の耐アウトガス性をより効果的に高めることができる。なお、積層体において、第1の被着材がポリカーボネート樹脂板等の樹脂板である場合には、樹脂板は透明基材であることが好ましく、活性エネルギー線を照射する際には、第1の被着材側から活性エネルギー線を照射することが好ましい。
After bonding the first adherend and the second adherend to both surfaces of the adhesive layer, a step of irradiating active energy rays from the first adherend or the second adherent side is provided. Preferably. When the active energy ray is irradiated, the pressure-sensitive adhesive layer in the semi-cured state is completely cured (post-cured). This increases the cohesive force of the pressure-sensitive adhesive layer, and improves the adhesiveness to each adherend. Further, by post-curing the pressure-sensitive adhesive layer, the outgas resistance of the entire laminate can be more effectively enhanced. In the laminated body, when the first adherend is a resin plate such as a polycarbonate resin plate, the resin plate is preferably a transparent substrate, and when irradiated with active energy rays, the first It is preferable to irradiate active energy rays from the adherend side.
活性エネルギー線としては、紫外線、電子線、可視光線、X線、イオン線等が挙げられ、粘着剤層に含まれる重合開始剤に応じて適宜選択できる。中でも、汎用性の点から、紫外線または電子線が好ましく、紫外線が特に好ましい。
紫外線の光源としては、例えば、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、無電極紫外線ランプ等を使用できる。
電子線としては、例えば、コックロフトワルト型、バンデクラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の各種類の電子線加速器から放出される電子線を使用できる。
紫外線の照射出力は、積算光量が100~10000mJ/cm2となるようにすることが好ましく、500~5000mJ/cm2となるようにすることがより好ましい。このように後硬化性を有する粘着剤層を用いると半硬化で濡れ性の良い状態で貼合されることにより、第1及び第2の被着材への密着性を高めFtおよびFbを高めることが可能となり、さらに後硬化させることでFiを高めることが可能となる。 Examples of active energy rays include ultraviolet rays, electron rays, visible rays, X rays, and ion rays, and can be appropriately selected according to the polymerization initiator contained in the pressure-sensitive adhesive layer. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
As the ultraviolet light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used.
As the electron beam, for example, an electron beam emitted from each type of electron beam accelerator such as Cockloft Wald type, Bande-Craft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. is used. it can.
Radiation output of the UV light, it is preferable that the integrated quantity of light is made to be a 100 ~ 10000mJ / cm 2, and more preferably made to be 500 ~ 5000mJ / cm 2. When the pressure-sensitive adhesive layer having the post-curing property is used as described above, the adhesive layer is semi-cured and is adhered in a good wettability state, so that the adhesion to the first and second adherends is enhanced and Ft and Fb are enhanced. It is possible to increase the Fi by further post-curing.
紫外線の光源としては、例えば、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、無電極紫外線ランプ等を使用できる。
電子線としては、例えば、コックロフトワルト型、バンデクラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の各種類の電子線加速器から放出される電子線を使用できる。
紫外線の照射出力は、積算光量が100~10000mJ/cm2となるようにすることが好ましく、500~5000mJ/cm2となるようにすることがより好ましい。このように後硬化性を有する粘着剤層を用いると半硬化で濡れ性の良い状態で貼合されることにより、第1及び第2の被着材への密着性を高めFtおよびFbを高めることが可能となり、さらに後硬化させることでFiを高めることが可能となる。 Examples of active energy rays include ultraviolet rays, electron rays, visible rays, X rays, and ion rays, and can be appropriately selected according to the polymerization initiator contained in the pressure-sensitive adhesive layer. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
As the ultraviolet light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used.
As the electron beam, for example, an electron beam emitted from each type of electron beam accelerator such as Cockloft Wald type, Bande-Craft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. is used. it can.
Radiation output of the UV light, it is preferable that the integrated quantity of light is made to be a 100 ~ 10000mJ / cm 2, and more preferably made to be 500 ~ 5000mJ / cm 2. When the pressure-sensitive adhesive layer having the post-curing property is used as described above, the adhesive layer is semi-cured and is adhered in a good wettability state, so that the adhesion to the first and second adherends is enhanced and Ft and Fb are enhanced. It is possible to increase the Fi by further post-curing.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.
(実施例1)
[積層体(A-1G)の作製]
<架橋性アクリル共重合体(A-1)の作製>
2-エチルヘキシルアクリレート(2EHA)を45質量%、エチルアクリレート(EA)を40質量%、4-ヒドロキシブチルアクリレート(4HBA)を2質量%、N,N-ジメチルアクリルアミド(DMAA)13質量%となるように配合し、ラジカル重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)を溶液へ溶解した。溶液を60℃に加熱してランダム共重合させ、架橋性アクリル共重合体(A-1)を得た。架橋性アクリル共重合体(A-1)の重量平均分子量は54万であった。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフイー(GPC)により測定し、ポリスチレン基準で求めた値である。
ゲルパーミエーションクロマトグラフイー(GPC)の測定条件は以下のとおりである。
溶媒:テトラヒドロフラン
カラム:Shodex KF801、KF803L、KF800L、KF800D(昭和電工(株)製を4本接続して使用した)
カラム温度:40℃
試料濃度:0.5質量%
検出器:RI-2031plus(JASCO製)
ポンプ:RI-2080plus(JASCO製)
流量(流速):0.8ml/分
注入量:10μl
校正曲線:標準ポリスチレンShodex standard ポリスチレン(昭和電工(株)製)Mw=1320~2,500,000迄の10サンプルによる校正曲線を使用した。 (Example 1)
[Production of Laminate (A-1G)]
<Preparation of crosslinkable acrylic copolymer (A-1)>
45% by mass of 2-ethylhexyl acrylate (2EHA), 40% by mass of ethyl acrylate (EA), 2% by mass of 4-hydroxybutyl acrylate (4HBA), and 13% by mass of N,N-dimethylacrylamide (DMAA). 2,2′-azobis(2,4-dimethylvaleronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic copolymer (A-1). The weight average molecular weight of the crosslinkable acrylic copolymer (A-1) was 540,000.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran Column: Shodex KF801, KF803L, KF800L, KF800D (4 Showa Denko KK were used by connecting them)
Column temperature: 40°C
Sample concentration: 0.5% by mass
Detector: RI-2031plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow rate): 0.8 ml/min Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko KK) Mw = 1320 to a calibration curve of 10 samples from 2,500,000 was used.
[積層体(A-1G)の作製]
<架橋性アクリル共重合体(A-1)の作製>
2-エチルヘキシルアクリレート(2EHA)を45質量%、エチルアクリレート(EA)を40質量%、4-ヒドロキシブチルアクリレート(4HBA)を2質量%、N,N-ジメチルアクリルアミド(DMAA)13質量%となるように配合し、ラジカル重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)を溶液へ溶解した。溶液を60℃に加熱してランダム共重合させ、架橋性アクリル共重合体(A-1)を得た。架橋性アクリル共重合体(A-1)の重量平均分子量は54万であった。
なお、重量平均分子量は、ゲルパーミエーションクロマトグラフイー(GPC)により測定し、ポリスチレン基準で求めた値である。
ゲルパーミエーションクロマトグラフイー(GPC)の測定条件は以下のとおりである。
溶媒:テトラヒドロフラン
カラム:Shodex KF801、KF803L、KF800L、KF800D(昭和電工(株)製を4本接続して使用した)
カラム温度:40℃
試料濃度:0.5質量%
検出器:RI-2031plus(JASCO製)
ポンプ:RI-2080plus(JASCO製)
流量(流速):0.8ml/分
注入量:10μl
校正曲線:標準ポリスチレンShodex standard ポリスチレン(昭和電工(株)製)Mw=1320~2,500,000迄の10サンプルによる校正曲線を使用した。 (Example 1)
[Production of Laminate (A-1G)]
<Preparation of crosslinkable acrylic copolymer (A-1)>
45% by mass of 2-ethylhexyl acrylate (2EHA), 40% by mass of ethyl acrylate (EA), 2% by mass of 4-hydroxybutyl acrylate (4HBA), and 13% by mass of N,N-dimethylacrylamide (DMAA). 2,2′-azobis(2,4-dimethylvaleronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic copolymer (A-1). The weight average molecular weight of the crosslinkable acrylic copolymer (A-1) was 540,000.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and determined on the basis of polystyrene.
The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran Column: Shodex KF801, KF803L, KF800L, KF800D (4 Showa Denko KK were used by connecting them)
Column temperature: 40°C
Sample concentration: 0.5% by mass
Detector: RI-2031plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow rate): 0.8 ml/min Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard polystyrene (manufactured by Showa Denko KK) Mw = 1320 to a calibration curve of 10 samples from 2,500,000 was used.
<粘着剤組成物(A-1)の作製>
架橋性アクリル共重合体(A-1)100質量部に対して、架橋剤としてキシリレンジイソシアネート化合物(三井化学(株)製、タケネートD-110N)を0.2質量部、単官能単量体としてラウリルアクリレート(LA)を10質量部、多官能単量体としてビスフェノールA エチレンオキサイド変性ジアクリレート(東亞合成(株)社製、アロニックス M211B)を12質量部、重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(BASFジャパン(株)製、IRGACURE819)を1.0質量部添加し、固形分濃度が35質量%となるように溶剤として酢酸エチルを添加して粘着剤組成物(A-1)を得た。 <Preparation of adhesive composition (A-1)>
0.2 parts by mass of a xylylene diisocyanate compound (Takenate D-110N, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent based on 100 parts by mass of the crosslinkable acrylic copolymer (A-1), a monofunctional monomer. 10 parts by mass of lauryl acrylate (LA), 12 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer, and bis(2,4) as a polymerization initiator. ,6-Trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Japan Ltd., IRGACURE819) was added in an amount of 1.0 part by mass, and ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass. A composition (A-1) was obtained.
架橋性アクリル共重合体(A-1)100質量部に対して、架橋剤としてキシリレンジイソシアネート化合物(三井化学(株)製、タケネートD-110N)を0.2質量部、単官能単量体としてラウリルアクリレート(LA)を10質量部、多官能単量体としてビスフェノールA エチレンオキサイド変性ジアクリレート(東亞合成(株)社製、アロニックス M211B)を12質量部、重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(BASFジャパン(株)製、IRGACURE819)を1.0質量部添加し、固形分濃度が35質量%となるように溶剤として酢酸エチルを添加して粘着剤組成物(A-1)を得た。 <Preparation of adhesive composition (A-1)>
0.2 parts by mass of a xylylene diisocyanate compound (Takenate D-110N, manufactured by Mitsui Chemicals, Inc.) as a crosslinking agent based on 100 parts by mass of the crosslinkable acrylic copolymer (A-1), a monofunctional monomer. 10 parts by mass of lauryl acrylate (LA), 12 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer, and bis(2,4) as a polymerization initiator. ,6-Trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF Japan Ltd., IRGACURE819) was added in an amount of 1.0 part by mass, and ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass. A composition (A-1) was obtained.
<粘着剤層(A-1)の作製>
上記のように作製した粘着剤組成物(A-1)を、シリコーン系剥離剤で処理された剥離剤層を備えた厚さ100μmのポリエチレンテレフタレートフィルム(第1の剥離シート)(重セパレータフィルム、帝人デュポンフィルム(株)製、離型処理されたポリエチレンテレフタレートフィルム)の表面に、乾燥後の塗工量が150μm/m2になるようにアプリケーターで均一に塗工した。その後、100℃の空気循環式恒温オーブンで3分間乾燥し、第1の剥離シートの表面に粘着剤層(A-1)を形成した。次いで、この粘着剤層の表面に第1の剥離シートより剥離性の高い離型処理が施された厚さ75μmの第2の剥離シート(軽セパレータフィルム、帝人デュポンフィルム(株)製、離型処理されたポリエチレンテレフタレートフィルム)に貼合して、粘着剤層(A-1)が剥離力差のある1対の剥離シートに挟まれた第1の剥離シート/粘着剤層(A-1)/第2の剥離シートの構成の剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置して、エージング処理を行った。 <Preparation of adhesive layer (A-1)>
A 100 μm thick polyethylene terephthalate film (first release sheet) having a release agent layer treated with a silicone-based release agent (heavy separator film, the pressure-sensitive adhesive composition (A-1) produced as described above, The surface of a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Co., Ltd.) was uniformly coated with an applicator so that the coating amount after drying was 150 μm/m 2 . Then, it was dried in an air-circulating constant temperature oven at 100° C. for 3 minutes to form an adhesive layer (A-1) on the surface of the first release sheet. Then, a second release sheet (light separator film, manufactured by Teijin DuPont Films Co., Ltd., having a thickness of 75 μm, which has been subjected to a release treatment having a higher release property than the first release sheet on the surface of this adhesive layer A first release sheet/adhesive layer (A-1), which is laminated to a treated polyethylene terephthalate film) and the adhesive layer (A-1) is sandwiched between a pair of release sheets having different release forces. / A pressure-sensitive adhesive sheet with a release sheet having the configuration of the second release sheet was obtained. This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under conditions of 23° C. and 50% relative humidity for aging treatment.
上記のように作製した粘着剤組成物(A-1)を、シリコーン系剥離剤で処理された剥離剤層を備えた厚さ100μmのポリエチレンテレフタレートフィルム(第1の剥離シート)(重セパレータフィルム、帝人デュポンフィルム(株)製、離型処理されたポリエチレンテレフタレートフィルム)の表面に、乾燥後の塗工量が150μm/m2になるようにアプリケーターで均一に塗工した。その後、100℃の空気循環式恒温オーブンで3分間乾燥し、第1の剥離シートの表面に粘着剤層(A-1)を形成した。次いで、この粘着剤層の表面に第1の剥離シートより剥離性の高い離型処理が施された厚さ75μmの第2の剥離シート(軽セパレータフィルム、帝人デュポンフィルム(株)製、離型処理されたポリエチレンテレフタレートフィルム)に貼合して、粘着剤層(A-1)が剥離力差のある1対の剥離シートに挟まれた第1の剥離シート/粘着剤層(A-1)/第2の剥離シートの構成の剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置して、エージング処理を行った。 <Preparation of adhesive layer (A-1)>
A 100 μm thick polyethylene terephthalate film (first release sheet) having a release agent layer treated with a silicone-based release agent (heavy separator film, the pressure-sensitive adhesive composition (A-1) produced as described above, The surface of a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Co., Ltd.) was uniformly coated with an applicator so that the coating amount after drying was 150 μm/m 2 . Then, it was dried in an air-circulating constant temperature oven at 100° C. for 3 minutes to form an adhesive layer (A-1) on the surface of the first release sheet. Then, a second release sheet (light separator film, manufactured by Teijin DuPont Films Co., Ltd., having a thickness of 75 μm, which has been subjected to a release treatment having a higher release property than the first release sheet on the surface of this adhesive layer A first release sheet/adhesive layer (A-1), which is laminated to a treated polyethylene terephthalate film) and the adhesive layer (A-1) is sandwiched between a pair of release sheets having different release forces. / A pressure-sensitive adhesive sheet with a release sheet having the configuration of the second release sheet was obtained. This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under conditions of 23° C. and 50% relative humidity for aging treatment.
<積層体(A-1G)の作製>
上記で得られた剥離シート付き粘着シートを用いて以下の方法で積層体(A-1G)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-1)を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)に貼合した。次に重セパレータフィルムである第1の剥離シートを剥がし、露出した粘着剤層(A-1)を第2の被着材である100mm×200mmの大きさのガラス板の全面に貼着した。PC板/粘着剤層/ガラス板の構成のサンプルをオートクレーブ処理(40℃、0.5MPa、30min)し、次いで、ガラス板側より紫外線を積算光量が3000mJ/cm2となるように照射し、100mm×200mmの大きさの積層体サンプルを得た。 <Production of laminated body (A-1G)>
A laminate (A-1G) was produced by the following method using the pressure-sensitive adhesive sheet with a release sheet obtained above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K. Next, the first release sheet, which is a heavy separator film, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was attached to the entire surface of a glass plate having a size of 100 mm×200 mm, which was a second adherend. A sample having a structure of PC plate/adhesive layer/glass plate was autoclaved (40° C., 0.5 MPa, 30 min), and then, ultraviolet rays were irradiated from the glass plate side so that the integrated light amount was 3000 mJ/cm 2 . A laminate sample having a size of 100 mm×200 mm was obtained.
上記で得られた剥離シート付き粘着シートを用いて以下の方法で積層体(A-1G)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-1)を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)に貼合した。次に重セパレータフィルムである第1の剥離シートを剥がし、露出した粘着剤層(A-1)を第2の被着材である100mm×200mmの大きさのガラス板の全面に貼着した。PC板/粘着剤層/ガラス板の構成のサンプルをオートクレーブ処理(40℃、0.5MPa、30min)し、次いで、ガラス板側より紫外線を積算光量が3000mJ/cm2となるように照射し、100mm×200mmの大きさの積層体サンプルを得た。 <Production of laminated body (A-1G)>
A laminate (A-1G) was produced by the following method using the pressure-sensitive adhesive sheet with a release sheet obtained above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K. Next, the first release sheet, which is a heavy separator film, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was attached to the entire surface of a glass plate having a size of 100 mm×200 mm, which was a second adherend. A sample having a structure of PC plate/adhesive layer/glass plate was autoclaved (40° C., 0.5 MPa, 30 min), and then, ultraviolet rays were irradiated from the glass plate side so that the integrated light amount was 3000 mJ/cm 2 . A laminate sample having a size of 100 mm×200 mm was obtained.
(実施例2)
<積層体(A-1P)の作製>
第2の被着材を厚み100μmの東洋紡社製のコスモシャインA4300(PET)に変更しPET側から紫外線を照射した以外は、実施例1と同様にして積層体(A-1P)を作製した。 (Example 2)
<Production of Laminate (A-1P)>
A laminate (A-1P) was produced in the same manner as in Example 1 except that the second adherend was changed to Cosmo Shine A4300 (PET) manufactured by Toyobo Co., Ltd. having a thickness of 100 μm and the ultraviolet ray was irradiated from the PET side. ..
<積層体(A-1P)の作製>
第2の被着材を厚み100μmの東洋紡社製のコスモシャインA4300(PET)に変更しPET側から紫外線を照射した以外は、実施例1と同様にして積層体(A-1P)を作製した。 (Example 2)
<Production of Laminate (A-1P)>
A laminate (A-1P) was produced in the same manner as in Example 1 except that the second adherend was changed to Cosmo Shine A4300 (PET) manufactured by Toyobo Co., Ltd. having a thickness of 100 μm and the ultraviolet ray was irradiated from the PET side. ..
(実施例3)
<架橋性アクリル共重合体(A-2)の作製>
n-ブチルアクリレート(BA)を75質量%、2-ヒドロキシエチルアクリレート(2HEA)を25質量%となるように配合し、ラジカル重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)を溶液へ溶解した。溶液を60℃に加熱してランダム共重合させ、架橋性アクリル共重合体(A-2)を得た。架橋性アクリル共重合体(A-2)の重量平均分子量は51万であった。 (Example 3)
<Preparation of crosslinkable acrylic copolymer (A-2)>
75 mass% of n-butyl acrylate (BA) and 25 mass% of 2-hydroxyethyl acrylate (2HEA) were mixed, and 2,2′-azobis(2,4-dimethylvaleronitrile) was used as a radical polymerization initiator. ) Was dissolved in the solution. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic copolymer (A-2). The weight average molecular weight of the crosslinkable acrylic copolymer (A-2) was 510,000.
<架橋性アクリル共重合体(A-2)の作製>
n-ブチルアクリレート(BA)を75質量%、2-ヒドロキシエチルアクリレート(2HEA)を25質量%となるように配合し、ラジカル重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)を溶液へ溶解した。溶液を60℃に加熱してランダム共重合させ、架橋性アクリル共重合体(A-2)を得た。架橋性アクリル共重合体(A-2)の重量平均分子量は51万であった。 (Example 3)
<Preparation of crosslinkable acrylic copolymer (A-2)>
75 mass% of n-butyl acrylate (BA) and 25 mass% of 2-hydroxyethyl acrylate (2HEA) were mixed, and 2,2′-azobis(2,4-dimethylvaleronitrile) was used as a radical polymerization initiator. ) Was dissolved in the solution. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic copolymer (A-2). The weight average molecular weight of the crosslinkable acrylic copolymer (A-2) was 510,000.
<粘着剤組成物(A-2)の作製>
架橋性アクリル共重合体(A-2)100質量部に対して、架橋剤としてトルエンジイソシアネート化合物(東ソー(株)製、コロネートL55)を0.1質量部、単官能単量体としてラウリルアクリレート(LA)を30質量部、多官能単量体としてビスフェノールA エチレンオキサイド変性ジアクリレート(東亞合成(株)社製、アロニックス M211B)を6質量部、重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(BASFジャパン(株)製、IRGACURE819)を1.12質量部添加し、固形分濃度が35質量%となるように溶剤として酢酸エチルを添加して粘着剤組成物(A-2)を得た。 <Preparation of adhesive composition (A-2)>
With respect to 100 parts by mass of the crosslinkable acrylic copolymer (A-2), 0.1 part by mass of a toluene diisocyanate compound (Coronate L55 manufactured by Tosoh Corporation) as a crosslinker and lauryl acrylate (as a monofunctional monomer) 30 parts by mass of LA), 6 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer, and bis(2,4,6-trimethyl) as a polymerization initiator. 1.12 parts by mass of benzoyl)phenylphosphine oxide (manufactured by BASF Japan Ltd., IRGACURE819) was added, and ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass, and the pressure-sensitive adhesive composition (A -2) was obtained.
架橋性アクリル共重合体(A-2)100質量部に対して、架橋剤としてトルエンジイソシアネート化合物(東ソー(株)製、コロネートL55)を0.1質量部、単官能単量体としてラウリルアクリレート(LA)を30質量部、多官能単量体としてビスフェノールA エチレンオキサイド変性ジアクリレート(東亞合成(株)社製、アロニックス M211B)を6質量部、重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイド(BASFジャパン(株)製、IRGACURE819)を1.12質量部添加し、固形分濃度が35質量%となるように溶剤として酢酸エチルを添加して粘着剤組成物(A-2)を得た。 <Preparation of adhesive composition (A-2)>
With respect to 100 parts by mass of the crosslinkable acrylic copolymer (A-2), 0.1 part by mass of a toluene diisocyanate compound (Coronate L55 manufactured by Tosoh Corporation) as a crosslinker and lauryl acrylate (as a monofunctional monomer) 30 parts by mass of LA), 6 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer, and bis(2,4,6-trimethyl) as a polymerization initiator. 1.12 parts by mass of benzoyl)phenylphosphine oxide (manufactured by BASF Japan Ltd., IRGACURE819) was added, and ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass, and the pressure-sensitive adhesive composition (A -2) was obtained.
<粘着剤層(A-2)の作製>
粘着剤組成物(A-1)を粘着剤組成物(A-2)に変更した以外は実施例1と同様にして150μmの厚みを有する粘着剤層(A-2)有する剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置し、エージング処理を行った。 <Preparation of adhesive layer (A-2)>
A pressure-sensitive adhesive sheet with a release sheet having a pressure-sensitive adhesive layer (A-2) having a thickness of 150 μm in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (A-1) was changed to the pressure-sensitive adhesive composition (A-2). Got This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
粘着剤組成物(A-1)を粘着剤組成物(A-2)に変更した以外は実施例1と同様にして150μmの厚みを有する粘着剤層(A-2)有する剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置し、エージング処理を行った。 <Preparation of adhesive layer (A-2)>
A pressure-sensitive adhesive sheet with a release sheet having a pressure-sensitive adhesive layer (A-2) having a thickness of 150 μm in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (A-1) was changed to the pressure-sensitive adhesive composition (A-2). Got This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
<積層体(A-2G)の作製>
粘着剤層(A-1)を粘着剤層(A-2)に変更した以外は、実施例1と同様にして積層体(A-2G)を作製した。 <Production of laminated body (A-2G)>
A laminate (A-2G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
粘着剤層(A-1)を粘着剤層(A-2)に変更した以外は、実施例1と同様にして積層体(A-2G)を作製した。 <Production of laminated body (A-2G)>
A laminate (A-2G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
(実施例4)
<積層体(A-2P)の作製>
粘着剤層(A-1)を粘着剤層(A-2)に変更した以外は、実施例2と同様にして積層体(A-2P)を作製した。 (Example 4)
<Production of laminated body (A-2P)>
A laminate (A-2P) was produced in the same manner as in Example 2 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
<積層体(A-2P)の作製>
粘着剤層(A-1)を粘着剤層(A-2)に変更した以外は、実施例2と同様にして積層体(A-2P)を作製した。 (Example 4)
<Production of laminated body (A-2P)>
A laminate (A-2P) was produced in the same manner as in Example 2 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-2).
(比較例1)
<積層体(A-3G)の作製>
上記で作製した粘着剤層(A-2)を用いて下記の方法で積層体(A-3G)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-2)を第2の被着材である100mm×200mmの大きさのガラス板に貼合した。ガラス板/粘着剤層(A-2)/第1の剥離シートが積層された状態で、ガラス側より紫外線を積算光量が3000mJ/cm2となるように照射し、その後に第1の剥離シートを剥がし、露出した粘着剤層を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)の全面に貼着した。PC板/粘着剤層(A-3)/ガラス板の構成の積層体をオートクレーブ処理(40℃、0.5MPa、30min)し、積層体(A-3G)とした。 (Comparative Example 1)
<Production of laminated body (A-3G)>
A laminate (A-3G) was produced by the following method using the pressure-sensitive adhesive layer (A-2) produced above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, is peeled off, and the exposed pressure-sensitive adhesive layer (A-2) is formed on a second adherend, a glass plate having a size of 100 mm×200 mm. Pasted With the glass plate/adhesive layer (A-2)/first release sheet laminated, ultraviolet rays were irradiated from the glass side so that the integrated light amount would be 3000 mJ/cm 2, and then the first release sheet. The exposed pressure-sensitive adhesive layer was attached to the entire surface of a 1 mm-thick PC plate (Panlite Sheet PC-1151 manufactured by Teijin Ltd.) which is the first adherend. The laminate of PC plate/adhesive layer (A-3)/glass plate was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-3G).
<積層体(A-3G)の作製>
上記で作製した粘着剤層(A-2)を用いて下記の方法で積層体(A-3G)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-2)を第2の被着材である100mm×200mmの大きさのガラス板に貼合した。ガラス板/粘着剤層(A-2)/第1の剥離シートが積層された状態で、ガラス側より紫外線を積算光量が3000mJ/cm2となるように照射し、その後に第1の剥離シートを剥がし、露出した粘着剤層を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)の全面に貼着した。PC板/粘着剤層(A-3)/ガラス板の構成の積層体をオートクレーブ処理(40℃、0.5MPa、30min)し、積層体(A-3G)とした。 (Comparative Example 1)
<Production of laminated body (A-3G)>
A laminate (A-3G) was produced by the following method using the pressure-sensitive adhesive layer (A-2) produced above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, is peeled off, and the exposed pressure-sensitive adhesive layer (A-2) is formed on a second adherend, a glass plate having a size of 100 mm×200 mm. Pasted With the glass plate/adhesive layer (A-2)/first release sheet laminated, ultraviolet rays were irradiated from the glass side so that the integrated light amount would be 3000 mJ/cm 2, and then the first release sheet. The exposed pressure-sensitive adhesive layer was attached to the entire surface of a 1 mm-thick PC plate (Panlite Sheet PC-1151 manufactured by Teijin Ltd.) which is the first adherend. The laminate of PC plate/adhesive layer (A-3)/glass plate was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-3G).
(比較例2)
<粘着剤組成物(A-4)の作製>
架橋性アクリル共重合体(A-1)100質量部に対して、トルエンジイソシアネート化合物(東ソー(株)製、コロネートL55)を0.05質量部配合し、ラウリルアクリレート、ビスフェノールA エチレンオキサイド変性ジアクリレート及びビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイドを配合しなかった以外は実施例1と同様にして粘着剤組成物(A-4)を得た。 (Comparative example 2)
<Preparation of adhesive composition (A-4)>
0.05 parts by mass of a toluene diisocyanate compound (Coronate L55 manufactured by Tosoh Corporation) was blended with 100 parts by mass of the crosslinkable acrylic copolymer (A-1) to prepare lauryl acrylate, bisphenol A ethylene oxide-modified diacrylate. A pressure-sensitive adhesive composition (A-4) was obtained in the same manner as in Example 1 except that bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide was not added.
<粘着剤組成物(A-4)の作製>
架橋性アクリル共重合体(A-1)100質量部に対して、トルエンジイソシアネート化合物(東ソー(株)製、コロネートL55)を0.05質量部配合し、ラウリルアクリレート、ビスフェノールA エチレンオキサイド変性ジアクリレート及びビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイドを配合しなかった以外は実施例1と同様にして粘着剤組成物(A-4)を得た。 (Comparative example 2)
<Preparation of adhesive composition (A-4)>
0.05 parts by mass of a toluene diisocyanate compound (Coronate L55 manufactured by Tosoh Corporation) was blended with 100 parts by mass of the crosslinkable acrylic copolymer (A-1) to prepare lauryl acrylate, bisphenol A ethylene oxide-modified diacrylate. A pressure-sensitive adhesive composition (A-4) was obtained in the same manner as in Example 1 except that bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide was not added.
<粘着剤層(A-4)の作製>
粘着剤組成物(A-1)を粘着剤組成物(A-4)に変更した以外は実施例1と同様にして150μmの厚みを有する粘着剤層(A-4)を有する剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置し、エージング処理を行った。 <Preparation of adhesive layer (A-4)>
Adhesion with a release sheet having an adhesive layer (A-4) having a thickness of 150 μm in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-4). Got the sheet. This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
粘着剤組成物(A-1)を粘着剤組成物(A-4)に変更した以外は実施例1と同様にして150μmの厚みを有する粘着剤層(A-4)を有する剥離シート付き粘着シートを得た。この剥離シート付き粘着シートを23℃、相対湿度50%の条件で7日間静置し、エージング処理を行った。 <Preparation of adhesive layer (A-4)>
Adhesion with a release sheet having an adhesive layer (A-4) having a thickness of 150 μm in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-4). Got the sheet. This pressure-sensitive adhesive sheet with a release sheet was allowed to stand for 7 days under the conditions of 23° C. and 50% relative humidity for aging treatment.
<積層体(A-4G)の作製>
粘着剤層(A-1)を粘着剤層(A-4)に変更し、さらに紫外線照射を行わなかった以外は、実施例1と同様にして積層体(A-4G)を作製した。 <Production of laminated body (A-4G)>
A laminate (A-4G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-4) and the ultraviolet irradiation was not performed.
粘着剤層(A-1)を粘着剤層(A-4)に変更し、さらに紫外線照射を行わなかった以外は、実施例1と同様にして積層体(A-4G)を作製した。 <Production of laminated body (A-4G)>
A laminate (A-4G) was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A-1) was changed to the pressure-sensitive adhesive layer (A-4) and the ultraviolet irradiation was not performed.
(比較例3)
<積層体(A-5P)の作製>
上記で作製した粘着剤層(A-1)を用いて下記の方法で積層体(A-5P)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-1)を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)に貼合した。ガラス板PC板/粘着剤層(A-1)/第1の剥離シートが積層された状態で、重セパレータフィルムである第1の剥離シート側より紫外線を積算光量が3000mJ/cm2となるように照射し、その後に第1の剥離シートを剥がし、露出した粘着剤層を第2の被着材である100mm×200mmの大きさのPETフィルムの全面に貼着した。PC板/粘着剤層(A-5)/PETの構成の積層体をオートクレーブ処理(40℃、0.5MPa、30min)し、積層体(A-5P)とした。 (Comparative example 3)
<Production of laminated body (A-5P)>
A laminate (A-5P) was produced by the following method using the pressure-sensitive adhesive layer (A-1) produced above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K. With the glass plate PC plate/adhesive layer (A-1)/first release sheet laminated, the accumulated light amount of ultraviolet rays from the first release sheet side, which is a heavy separator film, becomes 3000 mJ/cm 2. Then, the first release sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to the entire surface of a PET film having a size of 100 mm×200 mm, which was the second adherend. The laminate having the structure of PC plate/adhesive layer (A-5)/PET was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-5P).
<積層体(A-5P)の作製>
上記で作製した粘着剤層(A-1)を用いて下記の方法で積層体(A-5P)を作製した。まず、剥離シート付き粘着シートの軽セパレータフィルムである第2の剥離シートを剥がし、露出した粘着剤層(A-1)を第1の被着材である厚み1mmのPC板(帝人(株)製のパンライトシートPC-1151)に貼合した。ガラス板PC板/粘着剤層(A-1)/第1の剥離シートが積層された状態で、重セパレータフィルムである第1の剥離シート側より紫外線を積算光量が3000mJ/cm2となるように照射し、その後に第1の剥離シートを剥がし、露出した粘着剤層を第2の被着材である100mm×200mmの大きさのPETフィルムの全面に貼着した。PC板/粘着剤層(A-5)/PETの構成の積層体をオートクレーブ処理(40℃、0.5MPa、30min)し、積層体(A-5P)とした。 (Comparative example 3)
<Production of laminated body (A-5P)>
A laminate (A-5P) was produced by the following method using the pressure-sensitive adhesive layer (A-1) produced above. First, the second release sheet, which is a light separator film of a pressure-sensitive adhesive sheet with a release sheet, was peeled off, and the exposed pressure-sensitive adhesive layer (A-1) was used as the first adherend, a 1 mm-thick PC plate (Teijin Corp.). It was attached to a Panlite sheet PC-1151) manufactured by K.K. With the glass plate PC plate/adhesive layer (A-1)/first release sheet laminated, the accumulated light amount of ultraviolet rays from the first release sheet side, which is a heavy separator film, becomes 3000 mJ/cm 2. Then, the first release sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to the entire surface of a PET film having a size of 100 mm×200 mm, which was the second adherend. The laminate having the structure of PC plate/adhesive layer (A-5)/PET was autoclaved (40° C., 0.5 MPa, 30 min) to obtain a laminate (A-5P).
(測定及び評価)
<第1の被着材と粘着剤層の界面密着力(Ft)及び粘着剤層と第2の被着材の界面密着力(Fb)の測定>
(手順1)
実施例及び比較例で作製した積層体を10mm×10mmのサイズに切り出した後、積層体の一方の面(第1の被着材側の面)に瞬間接着剤(コニシ社製 アロンアルフア 速攻多用途EXTRA)を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスAの中央部に積層体を固定した。次いで積層体のもう一方の面側(第2の被着材側の面)に同様に瞬間接着剤を塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスBの中央部に積層体を固定した。その際、図2に示されるように、2つのガラスA、Bが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ1の測定と剥離界面の観察を行い、以下の基準でFt及びFbを決定した。
(1)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ1として手順2の試験を実施してFbを測定した。
(2)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ1とし手順3の試験を実施してFtを測定した。
(3)瞬間接着剤とガラス(又は被着材)の界面で剥離した場合、Ft、Fb>σ1とした。 (Measurement and evaluation)
<Measurement of the interfacial adhesion force (Ft) between the first adherend and the pressure-sensitive adhesive layer and the interfacial adhesion force (Fb) between the pressure-sensitive adhesive layer and the second adherend>
(Procedure 1)
After cutting the laminates produced in the examples and comparative examples into a size of 10 mm×10 mm, an instant adhesive (Aron Alpha, quick-release multi-purpose product manufactured by Konishi Co., Ltd.) was applied to one surface (the surface on the first adherend side) of the laminate. EXTRA) was applied thinly, and the laminate was fixed to the center of glass A having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm. Next, an instantaneous adhesive is similarly applied to the other surface side (the surface of the second adherend side) of the laminated body, and laminated on the central portion of the glass B having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. I fixed my body. At that time, as shown in FIG. 2, the two glasses A and B were laminated so as to have a cross positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the instant adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Left for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ1 was measured and the peeling interface was observed, and Ft and Fb were determined according to the following criteria.
(1) When peeled at the interface between the first adherend and the pressure-sensitive adhesive layer, the test ofprocedure 2 was performed with Ft=σ1 to measure Fb.
(2) In the case of peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ1 was set and the test of procedure 3 was performed to measure Ft.
(3) When peeled at the interface between the instant adhesive and the glass (or the adherend), Ft and Fb>σ1.
<第1の被着材と粘着剤層の界面密着力(Ft)及び粘着剤層と第2の被着材の界面密着力(Fb)の測定>
(手順1)
実施例及び比較例で作製した積層体を10mm×10mmのサイズに切り出した後、積層体の一方の面(第1の被着材側の面)に瞬間接着剤(コニシ社製 アロンアルフア 速攻多用途EXTRA)を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスAの中央部に積層体を固定した。次いで積層体のもう一方の面側(第2の被着材側の面)に同様に瞬間接着剤を塗布して、厚み4.0mm×幅30mm×長さ50mmのガラスBの中央部に積層体を固定した。その際、図2に示されるように、2つのガラスA、Bが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ1の測定と剥離界面の観察を行い、以下の基準でFt及びFbを決定した。
(1)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ1として手順2の試験を実施してFbを測定した。
(2)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ1とし手順3の試験を実施してFtを測定した。
(3)瞬間接着剤とガラス(又は被着材)の界面で剥離した場合、Ft、Fb>σ1とした。 (Measurement and evaluation)
<Measurement of the interfacial adhesion force (Ft) between the first adherend and the pressure-sensitive adhesive layer and the interfacial adhesion force (Fb) between the pressure-sensitive adhesive layer and the second adherend>
(Procedure 1)
After cutting the laminates produced in the examples and comparative examples into a size of 10 mm×10 mm, an instant adhesive (Aron Alpha, quick-release multi-purpose product manufactured by Konishi Co., Ltd.) was applied to one surface (the surface on the first adherend side) of the laminate. EXTRA) was applied thinly, and the laminate was fixed to the center of glass A having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm. Next, an instantaneous adhesive is similarly applied to the other surface side (the surface of the second adherend side) of the laminated body, and laminated on the central portion of the glass B having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm. I fixed my body. At that time, as shown in FIG. 2, the two glasses A and B were laminated so as to have a cross positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the instant adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Left for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ1 was measured and the peeling interface was observed, and Ft and Fb were determined according to the following criteria.
(1) When peeled at the interface between the first adherend and the pressure-sensitive adhesive layer, the test of
(2) In the case of peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ1 was set and the test of procedure 3 was performed to measure Ft.
(3) When peeled at the interface between the instant adhesive and the glass (or the adherend), Ft and Fb>σ1.
(手順2)
手順1の測定で第1の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に瞬間接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスCの中央に固定した。その際、上記と同様に2つのガラスB、Cが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ2の測定と剥離界面の観察を行い、以下の基準でFbを決定した。
(4)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ2とした。
(5)瞬間接着剤とガラス、又は、瞬間接着剤と粘着剤層の界面で剥離した場合、Fb>σ2とした。 (Procedure 2)
In the measurement ofStep 1, the instant adhesive was thinly applied to the exposed pressure-sensitive adhesive layer surface due to peeling at the interface between the first adherend and the pressure-sensitive adhesive layer, and the thickness was 4.0 mm x width 30 mm x length 50 mm. It was fixed to the center of a new glass C of. At that time, as in the above, the two glasses B and C were laminated so as to have a cross-shaped positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the instant adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Left for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ2 was measured and the peeling interface was observed, and Fb was determined according to the following criteria.
(4) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ2.
(5) When peeled at the interface between the instant adhesive and the glass or the instant adhesive and the pressure-sensitive adhesive layer, Fb>σ2.
手順1の測定で第1の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に瞬間接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスCの中央に固定した。その際、上記と同様に2つのガラスB、Cが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ2の測定と剥離界面の観察を行い、以下の基準でFbを決定した。
(4)第2の被着材と粘着剤層の界面で剥離した場合、Fb=σ2とした。
(5)瞬間接着剤とガラス、又は、瞬間接着剤と粘着剤層の界面で剥離した場合、Fb>σ2とした。 (Procedure 2)
In the measurement of
(4) When peeling at the interface between the second adherend and the pressure-sensitive adhesive layer, Fb=σ2.
(5) When peeled at the interface between the instant adhesive and the glass or the instant adhesive and the pressure-sensitive adhesive layer, Fb>σ2.
(手順3)
手順1の測定で第2の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に瞬間接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスDの中央に固定した。その際、上記と同様に2つのガラスA、Dが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ3の測定と剥離界面の観察を行い、以下の基準でFtを決定した。
(6)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ3とした。
(7)瞬間接着剤とガラス、又は、瞬間接着剤と粘着剤層の界面で剥離した場合、Ft>σ3とした。 (Procedure 3)
A thin adhesive is applied to the surface of the pressure-sensitive adhesive layer which has been peeled off at the interface between the second adherend and the pressure-sensitive adhesive layer in the measurement ofstep 1, and the thickness is 4.0 mm x width 30 mm x length 50 mm. It was fixed to the center of a new glass D of. At that time, as in the above, the two glasses A and D were laminated so as to have a cross-shaped positional relationship with each other. The measurement sample thus obtained was allowed to stand for 30 minutes in an environment of 23° C. and a relative humidity of 50% to completely cure the instant adhesive, and then in an environment of 85° C. and a relative humidity of less than 20%. Left for 3 hours. Then, using a tensile tester, under an environment of 85° C. and a relative humidity of less than 20%, each glass was pulled at a speed of 5 mm/min in the opposite direction in the thickness direction until each glass separated, and the maximum The stress σ3 was measured and the peeling interface was observed, and Ft was determined according to the following criteria.
(6) When peeled at the interface between the first adherend and the pressure-sensitive adhesive layer, Ft=σ3.
(7) When peeled off at the interface between the instant adhesive and the glass or the instant adhesive and the pressure-sensitive adhesive layer, Ft>σ3.
手順1の測定で第2の被着材と粘着剤層の界面で剥離が生じて剥き出しになった粘着剤層面に瞬間接着剤を薄く塗布して、厚み4.0mm×幅30mm×長さ50mmの新しいガラスDの中央に固定した。その際、上記と同様に2つのガラスA、Dが互いに十字の位置関係になるよう貼合した。このようにして得られた測定用サンプルを23℃、相対湿度50%の環境下に30分間静置して瞬間接着剤を完全に硬化させた後、85℃、相対湿度20%未満の環境下に3時間置いた。その後、引張試験機を用いて、85℃、相対湿度20%未満の環境下で、速度5mm/minでそれぞれのガラスを厚み方向における反対方向にそれぞれのガラスが分離するまで引っ張り、その際の最大応力σ3の測定と剥離界面の観察を行い、以下の基準でFtを決定した。
(6)第1の被着材と粘着剤層の界面で剥離した場合、Ft=σ3とした。
(7)瞬間接着剤とガラス、又は、瞬間接着剤と粘着剤層の界面で剥離した場合、Ft>σ3とした。 (Procedure 3)
A thin adhesive is applied to the surface of the pressure-sensitive adhesive layer which has been peeled off at the interface between the second adherend and the pressure-sensitive adhesive layer in the measurement of
(6) When peeled at the interface between the first adherend and the pressure-sensitive adhesive layer, Ft=σ3.
(7) When peeled off at the interface between the instant adhesive and the glass or the instant adhesive and the pressure-sensitive adhesive layer, Ft>σ3.
<粘着剤層の凝集力(Fi)の測定>
実施例及び比較例で作製した積層体を、10mm×8mmの大きさに切り出し動的粘弾性装置Rheogel―E4000(株式会社ユービーエム製)の固体剪断試験用治具に瞬間接着剤(コニシ社製 アロンアルフア 速攻多用途EXTRA)を用いて固定して、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとした。 <Measurement of cohesive force (Fi) of adhesive layer>
The laminates produced in the examples and comparative examples were cut into a size of 10 mm×8 mm, and an instant adhesive (manufactured by Konishi Co., Ltd.) was applied to a solid shear test jig of a dynamic viscoelastic device Rheogel-E4000 (manufactured by UBM Co., Ltd.) AronAlpha is fixed by using haste multipurpose EXTRA), and the shear storage modulus G'of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C is measured under the conditions of solid shear mode,frequency 1 Hz, and strain 1.0%. The measurement was carried out, and the value of the shear storage elastic modulus G′ at 85° C. was defined as Fi.
実施例及び比較例で作製した積層体を、10mm×8mmの大きさに切り出し動的粘弾性装置Rheogel―E4000(株式会社ユービーエム製)の固体剪断試験用治具に瞬間接着剤(コニシ社製 アロンアルフア 速攻多用途EXTRA)を用いて固定して、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとした。 <Measurement of cohesive force (Fi) of adhesive layer>
The laminates produced in the examples and comparative examples were cut into a size of 10 mm×8 mm, and an instant adhesive (manufactured by Konishi Co., Ltd.) was applied to a solid shear test jig of a dynamic viscoelastic device Rheogel-E4000 (manufactured by UBM Co., Ltd.) AronAlpha is fixed by using haste multipurpose EXTRA), and the shear storage modulus G'of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C is measured under the conditions of solid shear mode,
<気泡・浮き剥がれ>
実施例及び比較例で作製した100mm×200mmの大きさの積層体サンプルを85℃、相対湿度20%未満の環境下に置き、100時間後に観察し、気泡や浮き剥がれの有無を評価した。
○:気泡や浮き剥がれがない
×:下記のいずれかのModeで気泡又は浮き剥がれが発生している
Mode1:第1の被着材と粘着剤層の界面で浮きが発生している
Mode2:粘着剤層中に0.1mmΦより大きい気泡が発生している
Mode3:第2の被着材と粘着剤層の界面で浮きが発生している <Bubbles/Peeling off>
The laminate samples of 100 mm×200 mm size produced in Examples and Comparative Examples were placed in an environment of 85° C. and a relative humidity of less than 20% and observed 100 hours later to evaluate the presence or absence of air bubbles and peeling.
○: No bubbles or floating peeling ×: Bubbles or floating peeling occurred in any of the following Mode Mode 1: Floating occurred at the interface between the first adherend and the pressure-sensitive adhesive layer Mode 2: Adhesion Bubbles larger than 0.1 mmΦ are generated in the agent layer Mode 3: Floating occurs at the interface between the second adherend and the adhesive layer
実施例及び比較例で作製した100mm×200mmの大きさの積層体サンプルを85℃、相対湿度20%未満の環境下に置き、100時間後に観察し、気泡や浮き剥がれの有無を評価した。
○:気泡や浮き剥がれがない
×:下記のいずれかのModeで気泡又は浮き剥がれが発生している
Mode1:第1の被着材と粘着剤層の界面で浮きが発生している
Mode2:粘着剤層中に0.1mmΦより大きい気泡が発生している
Mode3:第2の被着材と粘着剤層の界面で浮きが発生している <Bubbles/Peeling off>
The laminate samples of 100 mm×200 mm size produced in Examples and Comparative Examples were placed in an environment of 85° C. and a relative humidity of less than 20% and observed 100 hours later to evaluate the presence or absence of air bubbles and peeling.
○: No bubbles or floating peeling ×: Bubbles or floating peeling occurred in any of the following Mode Mode 1: Floating occurred at the interface between the first adherend and the pressure-sensitive adhesive layer Mode 2: Adhesion Bubbles larger than 0.1 mmΦ are generated in the agent layer Mode 3: Floating occurs at the interface between the second adherend and the adhesive layer
実施例で得られた積層体においては、粘着剤層における気泡の発生が抑制され、かつ各被着材から粘着剤層が浮いたり、剥がれたりすることが抑制されていた。
In the laminates obtained in the examples, generation of bubbles in the pressure-sensitive adhesive layer was suppressed, and the pressure-sensitive adhesive layer was suppressed from floating or peeling from each adherend.
1 積層体
2 第1の被着材
4 粘着剤層
6 第2の被着材
10 ガラスA
20 ガラスB
R 気泡(アウトガス) 1Laminated body 2 First adherend 4 Adhesive layer 6 Second adherend 10 Glass A
20 glass B
R air bubbles (outgas)
2 第1の被着材
4 粘着剤層
6 第2の被着材
10 ガラスA
20 ガラスB
R 気泡(アウトガス) 1
20 glass B
R air bubbles (outgas)
Claims (8)
- 第1の被着材、粘着剤層及び第2の被着材をこの順で積層した積層体であって、
85℃における飽和水蒸気圧をFvとし、
下記測定方法(a)で測定される85℃における前記第1の被着材と前記粘着剤層の界面密着力をFtとし、
下記測定方法(b)で測定される85℃における前記粘着剤層の剪断貯蔵弾性率(G’)をFiとし、
下記測定方法(c)で測定される85℃における前記第2の被着材と前記粘着剤層の界面密着力をFbとした場合、
Ft>Fv、Fi>Fv、及び、Fb>Fvの条件を満たす積層体;
測定方法(a):
10mm×10mmのサイズの積層体の第1の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第1の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Ft)として測定する;第1の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Ft)は引張最大応力よりも大きいものとする;
測定方法(b):
積層体を固体剪断試験用治具に接着剤を用いて固定し、固体剪断モード、周波数1Hz、歪み1.0%の条件で、20℃~120℃までの温度領域における粘着剤層の剪断貯蔵弾性率G’を測定し、85℃における剪断貯蔵弾性率G’の値をFiとする;
測定方法(c):
10mm×10mmのサイズの積層体の第2の被着材表面に接着剤を塗布し、厚み4.0mm×幅30mm×長さ50mmのガラス板の中央部に貼合する;粘着剤層側に厚み4.0mm×幅30mm×長さ50mmのガラス板を、2つのガラス板が互いに十字の位置関係になるよう接着剤を介して貼合し、測定用サンプルとする;測定用サンプルを、85℃、相対湿度20%未満の環境下に3時間置いた後に、85℃、相対湿度20%未満の環境下で、引張試験機を用いて、速度5mm/minでそれぞれのガラス板を厚み方向における反対方向に引っ張り、第2の被着材と粘着剤層の間で剥離した際の応力を界面密着力(Fb)として測定する;第2の被着材と粘着剤層の間で剥離しない場合には、界面密着力(Fb)は引張最大応力よりも大きいものとする。 A laminate in which a first adherend, an adhesive layer and a second adherend are laminated in this order,
Saturated water vapor pressure at 85°C is Fv,
Ft is the interfacial adhesion between the first adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measurement method (a),
The shear storage elastic modulus (G′) of the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (b) is Fi,
When the interface adhesion between the second adherend and the pressure-sensitive adhesive layer at 85° C. measured by the following measuring method (c) is Fb,
A laminate satisfying the conditions of Ft>Fv, Fi>Fv, and Fb>Fv;
Measuring method (a):
Adhesive is applied to the surface of the first adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the first adherend and the pressure-sensitive adhesive layer in the opposite direction is measured as the interfacial adhesion (Ft); when the first adherend and the pressure-sensitive adhesive layer do not peel. , The interfacial adhesion (Ft) shall be greater than the maximum tensile stress;
Measuring method (b):
The laminate is fixed to a jig for solid shear test with an adhesive, and the shear storage of the pressure-sensitive adhesive layer in the temperature range from 20°C to 120°C under the conditions of solid shear mode, frequency 1 Hz, and strain 1.0%. The elastic modulus G′ is measured and the value of the shear storage elastic modulus G′ at 85° C. is defined as Fi;
Measuring method (c):
Adhesive is applied to the surface of the second adherend of the laminate having a size of 10 mm×10 mm, and it is attached to the center of a glass plate having a thickness of 4.0 mm×a width of 30 mm×a length of 50 mm; on the adhesive layer side. A glass plate having a thickness of 4.0 mm, a width of 30 mm, and a length of 50 mm is attached to the two glass plates with an adhesive so that the two glass plates have a cross relationship with each other to obtain a measurement sample; After being placed in an environment of ℃, relative humidity less than 20% for 3 hours, each glass plate in the thickness direction at a speed of 5 mm/min using a tensile tester under an environment of 85° C., relative humidity less than 20%. The stress when peeling between the second adherend and the adhesive layer is measured in the opposite direction, and the stress is measured as the interfacial adhesion force (Fb); when the second adherend and the adhesive layer do not peel. In addition, the interfacial adhesion (Fb) is assumed to be larger than the maximum tensile stress. - 前記第1の被着材は、樹脂板である請求項1に記載の積層体。 The laminate according to claim 1, wherein the first adherend is a resin plate.
- 前記第1の被着材は、ポリカーボネート系樹脂を含む請求項1又は2に記載の積層体。 The laminated body according to claim 1 or 2, wherein the first adherend contains a polycarbonate resin.
- 前記第2の被着材は、ガラス板及び樹脂板から選択される少なくとも1種を含む請求項1~3のいずれか1項に記載の積層体。 The laminate according to any one of claims 1 to 3, wherein the second adherend includes at least one selected from a glass plate and a resin plate.
- 請求項1~4のいずれか1項に記載の積層体の製造方法であって、
後硬化性を有する粘着剤層に、第1の被着材と第2の被着材を貼合する工程と、
前記第1の被着材もしくは前記第2の被着材側から活性エネルギー線を照射する工程とを含む積層体の製造方法。 The method for producing a laminate according to any one of claims 1 to 4,
A step of laminating the first adherend and the second adherend to the pressure-sensitive adhesive layer having a post-curing property,
And a step of irradiating an active energy ray from the side of the first adherend or the second adherend. - 前記貼合する工程で用いられる前記粘着剤層は、粘着剤組成物を半硬化状態とした粘着剤層であり、
前記粘着剤組成物は、架橋性アクリル共重合体、架橋剤、光重合開始剤、単官能単量体及び多官能単量体を含む、請求項5に記載の積層体の製造方法。 The pressure-sensitive adhesive layer used in the step of laminating is a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state,
The method for producing a laminate according to claim 5, wherein the pressure-sensitive adhesive composition contains a crosslinkable acrylic copolymer, a crosslinking agent, a photopolymerization initiator, a monofunctional monomer and a polyfunctional monomer. - 前記単官能単量体は、ラウリルアクリレートである請求項6に記載の積層体の製造方法。 The method for producing a laminate according to claim 6, wherein the monofunctional monomer is lauryl acrylate.
- 前記多官能単量体は、1分子内にビスフェノール骨格を有する単量体である請求項6又は7に記載の積層体の製造方法。 The method for producing a laminate according to claim 6 or 7, wherein the polyfunctional monomer is a monomer having a bisphenol skeleton in one molecule.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201980079635.6A CN113165341B (en) | 2018-12-03 | 2019-12-02 | Laminate and method for producing laminate |
KR1020217018666A KR20210093308A (en) | 2018-12-03 | 2019-12-02 | Laminates and methods for manufacturing laminates |
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JP2018226580A JP6579254B1 (en) | 2018-12-03 | 2018-12-03 | Laminate and method for producing laminate |
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JP (1) | JP6579254B1 (en) |
KR (1) | KR20210093308A (en) |
CN (1) | CN113165341B (en) |
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Citations (3)
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WO2012032995A1 (en) * | 2010-09-06 | 2012-03-15 | 三菱樹脂株式会社 | Method for producing laminate for configuring image display device, and image display device using the laminate |
JP2014156552A (en) * | 2013-02-15 | 2014-08-28 | Nitto Denko Corp | Adhesive composition, optical adhesive sheet, optical film, and display |
JP2015199813A (en) * | 2014-04-07 | 2015-11-12 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
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JPH09226062A (en) * | 1996-02-27 | 1997-09-02 | Dainippon Printing Co Ltd | Reflection preventing film |
AU5813499A (en) * | 1998-09-04 | 2000-03-27 | Avery Dennison Corporation | Composite multilayer constructions |
JP6067405B2 (en) * | 2012-07-31 | 2017-01-25 | 日東電工株式会社 | Radiation curable adhesive, radiation curable adhesive layer, radiation curable adhesive sheet and laminate |
US20140226085A1 (en) * | 2013-02-14 | 2014-08-14 | Nitto Denko Corporation | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive sheet, optical component and touch panel |
US9758630B2 (en) * | 2014-03-27 | 2017-09-12 | Teijin Limited | Polymer substrate with hard coat layer and manufacturing method for such polymer substrate |
JP2017222085A (en) | 2016-06-15 | 2017-12-21 | 積水化学工業株式会社 | Method for manufacturing optical laminate and optical laminate |
JP6740753B2 (en) | 2016-07-01 | 2020-08-19 | 東亞合成株式会社 | Laminate comprising an adhesive composition and an adhesive layer |
JP6732614B2 (en) | 2016-09-16 | 2020-07-29 | ホシデン株式会社 | Optical laminate and touch input device including the same |
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- 2019-12-02 WO PCT/JP2019/047040 patent/WO2020116395A1/en active Application Filing
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WO2012032995A1 (en) * | 2010-09-06 | 2012-03-15 | 三菱樹脂株式会社 | Method for producing laminate for configuring image display device, and image display device using the laminate |
JP2014156552A (en) * | 2013-02-15 | 2014-08-28 | Nitto Denko Corp | Adhesive composition, optical adhesive sheet, optical film, and display |
JP2015199813A (en) * | 2014-04-07 | 2015-11-12 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive sheet |
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JP2020089983A (en) | 2020-06-11 |
KR20210093308A (en) | 2021-07-27 |
JP6579254B1 (en) | 2019-09-25 |
CN113165341B (en) | 2023-01-10 |
CN113165341A (en) | 2021-07-23 |
TW202108719A (en) | 2021-03-01 |
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