WO2010113604A1 - 機能性フィルムおよび積層体 - Google Patents
機能性フィルムおよび積層体 Download PDFInfo
- Publication number
- WO2010113604A1 WO2010113604A1 PCT/JP2010/053891 JP2010053891W WO2010113604A1 WO 2010113604 A1 WO2010113604 A1 WO 2010113604A1 JP 2010053891 W JP2010053891 W JP 2010053891W WO 2010113604 A1 WO2010113604 A1 WO 2010113604A1
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- WIPO (PCT)
- Prior art keywords
- adhesive layer
- curing
- film
- martens hardness
- layer
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to a functional film and a laminate, and more particularly to a functional film and a laminate that do not reduce the surface hardness of the laminate when the functional film is attached to the surface of the adherend via an adhesive layer.
- a cured film is provided on the surface of the member.
- a cured film is obtained by applying a cured film coating solution or the like (Patent Document 1) or by bonding a film on which a cured film is formed via an adhesive layer (Patent Document 2). Provided.
- JP 2009-35703 A (prior art) JP 2008-50590 A (Claim 6)
- Patent Document 2 in which a cured film is formed on the surface of the member by bonding the film formed with the adhesive layer through the adhesive layer is simpler than that in which the coating film is directly provided on the member as described above.
- This method is excellent in that a cured film can be provided on the surface of the member without selecting the material or structure of the member.
- the surface hardness of a member bonded with a film having such a cured film is affected by the hardness of the adhesive layer.
- an adhesive layer with a soft hardness is used, there arises a problem that the surface hardness of a member bonded with a film on which a cured film is formed is lower than the surface hardness of the cured film itself.
- an object of the present invention is to provide a functional film and a laminate that do not reduce the surface hardness of the functional film even when an adhesive layer for adhering to other members is provided.
- the die-cutting process is performed when the bonded member is die-cut to a predetermined shape. Occasionally, it has also been found that floating and peeling can be prevented between the film and the adhesive layer, and the present invention has been completed.
- the functional film of the present invention is a functional film composed of a cured film on one surface of a plastic film, and a functional film having an adhesive layer on the other surface
- the adhesive layer includes a curable adhesive that is cured by ionizing radiation irradiation or heating,
- the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, and for the Martens hardness of the functional layer, Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- the laminate of the present invention is a laminate in which an adherend is attached to a plastic film having a functional layer composed of a cured film on one surface via an adhesive layer,
- the adhesive layer includes a curable adhesive that is cured by ionizing radiation irradiation or heating,
- the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, and for the Martens hardness of the functional layer, Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- the laminate of the present invention is a laminate in which an adherend is bonded to a plastic film having a functional layer composed of a cured film on one surface via an adhesive layer, and then the adhesive layer is cured.
- the adhesive layer includes a curable adhesive that is cured by ionizing radiation irradiation or heating,
- the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, and for the Martens hardness of the functional layer, Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- the “before curing” state includes “before curing” state, meaning that the curing reaction is started (for example, a state where the curing component of the curable adhesive is 100% in the adhesive layer), and curing.
- a state of “after curing has started” is meant to mean from the start of the reaction to before ending (for example, a state where the curing component of the curable adhesive is present in the adhesive layer with less than 100% and about 5% or more).
- “after the completion of curing” state which means after the curing reaction is completed (for example, a state where the curing component of the curable adhesive is present in the adhesive layer with less than about 5%), is excluded.
- after curing is used in the meaning of “after curing” and “after curing”, and is not limited to the above “after curing”. In this sense, it is not necessarily used for die cutting immediately after the start of curing, but in preparation for the case where it is used for the above processing after a certain time (after irradiation or heating, for example, about 1 to 3 days). It is a thing. “Before curing” is used to mean “before curing”.
- the functional film of the present invention can prevent the surface hardness of the functional film from being lower than the surface hardness of the functional layer when adhered to an adherend. Further, when the die-cutting process is performed, it is possible to prevent floating and peeling.
- the laminate of the present invention can prevent the surface hardness of the functional film from being lowered than the surface hardness of the functional layer. Further, when the die-cutting process is performed, it is possible to prevent floating and peeling.
- the functional film of the present invention is a functional layer composed of a cured film on one surface of a plastic film, a functional film having an adhesive layer on the other surface,
- the adhesive layer includes a curable adhesive that is cured by ionizing radiation irradiation or heating,
- the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, and for the Martens hardness of the functional layer, Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- Plastic films include films made of synthetic resins such as polyester, ABS (acrylonitrile-butadiene-styrene), polystyrene, polycarbonate, acrylic, polyolefin, cellulose resin, polysulfone, polyphenylene sulfide, polyethersulfone, polyetheretherketone, and polyimide. Can be used. Among them, a polyester film that has been particularly stretched or biaxially stretched is preferable because it is excellent in mechanical strength and dimensional stability, and has a high stiffness.
- synthetic resins such as polyester, ABS (acrylonitrile-butadiene-styrene), polystyrene, polycarbonate, acrylic, polyolefin, cellulose resin, polysulfone, polyphenylene sulfide, polyethersulfone, polyetheretherketone, and polyimide.
- a polyester film that has been particularly stretched or biaxially stretched is preferable because it is excellent in mechanical strength and dimensional stability, and has a high stiff
- the functional layer of the present invention is a layer composed of a cured film obtained by curing a resin composition containing a curable resin.
- a curable resin a thermosetting resin or an ionizing radiation curable resin can be used, and an ionizing radiation curable resin is preferable in order to increase the surface hardness.
- the functional layer can have functions such as a hard coat layer, an ultraviolet shielding layer, an infrared shielding layer, a conductive layer, and an antireflection layer.
- functions such as a hard coat layer, an ultraviolet shielding layer, an infrared shielding layer, a conductive layer, and an antireflection layer.
- the adhesive layer of the present invention includes a curable adhesive that is cured by irradiation with ionizing radiation or heating.
- the curable adhesive that is cured by irradiation with ionizing radiation it is preferable to use one that is formed from a paint that can be crosslinked and cured by irradiation with ionizing radiation.
- an ionizing radiation curable coating one or a mixture of two or more of a photocationic polymerizable resin capable of photocationic polymerization, a photopolymerizable prepolymer or a photopolymerizable monomer capable of radical photopolymerization, and the like. Can be used.
- various additives can be added to such an ionizing radiation curable coating. When ultraviolet rays are used for curing, a photopolymerization initiator, an ultraviolet sensitizer, or the like may be added. preferable.
- a coating solution containing a thermosetting resin is applied onto a plastic film and crosslinked and cured by heat, so that heat that can be crosslinked and cured by heat below the heat resistance temperature of the plastic film.
- a curable resin is preferred, and a melamine-based, epoxy-based, aminoalkyd-based, urethane-based, acrylic-based, polyester-based, phenol-based, or other crosslinkable resin is crosslinked and cured by heat, or a mixture of two or more.
- an acrylic thermosetting resin that can improve surface hardness and has good adhesion to a plastic film is preferable. These can be used alone, but it is desirable to add a curing agent in order to further improve the crosslinkability and the hardness of the crosslinked cured coating film.
- Such a curable adhesive is one whose curing reaction is initiated by irradiation with ionizing radiation or heating.
- a curable adhesive that is cured by irradiation with ionizing radiation it is preferable that the adhesive is adhered to an adherend before the curing reaction is started and then cured. By sticking before curing, the adhesive layer becomes hard, and bubbles can be prevented from being involved when sticking.
- a curable adhesive that cures by heating as with the case of using a curable adhesive that cures by irradiation with ionizing radiation, it can be applied to the adherend before the curing reaction is started, and then cured. However, after the curing reaction is started by heating, it can be attached to the adherend before the curing reaction is completed, and then the remaining curing reaction can be allowed to proceed.
- a compound such as polyisocyanate, amino resin, epoxy resin, carboxylic acid or the like can be appropriately used according to a suitable resin.
- the Martens hardness of the adhesive layer after curing is firstly compared to the Martens hardness of the functional layer.
- Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25 It can comprise by selecting the curable adhesive by which compounding, such as resin, a monomer, and an oligomer, was prepared so that it might satisfy
- the present invention applies not only to satisfying after the completion of curing but also to satisfying all states after the start of curing to the end of curing. Is included in “after curing”.
- the composition of the adhesive layer before curing is prepared so that the Martens hardness after curing of the adhesive layer is 25% or more, preferably 30% or more of the Martens hardness of the functional layer.
- Martens hardness represents the hardness (hardness of dent) of the adhesive layer obtained from the test load and the indentation surface area when the surface of the adhesive layer is pushed with a Vickers indenter, and is an index of the hardness of the adhesive layer.
- a curable adhesive prepared by blending resin, monomer, oligomer, etc. is selected so that the Martens hardness of the adhesive layer after curing is secondly 260 N / mm 2 or less. This can be configured.
- “after curing” does not necessarily require that the above numerical value is satisfied in all states from the start of curing to the end of curing, and at least from the start of curing to just before the end of curing.
- the Martens hardness of the adhesive layer after curing in the present invention was measured in an atmosphere of a temperature of 20 ° C. and a relative humidity of 60% using an ultra-micro hardness tester (trade name: Fisher Scope HM2000, Fisher Instruments). , Expressed by a value measured by a method based on ISO-144577-1.
- the curable adhesive is configured so that the Martens hardness of the adhesive layer after curing is 260 N / mm 2 or less, preferably 200 N / mm 2 or less.
- the Martens hardness is too large, curling may occur in the laminate due to curing shrinkage due to the curable adhesive, or partial unevenness may occur in the film or molded body on which the cured film is formed. In order to impair the properties, it is preferable that the Martens hardness is not too high.
- the Martens hardness of the adhesive layer after curing can be adjusted by preparing a blend of monomers and oligomers constituting a resin used for the adhesive layer before curing, and a blend of resin used for the adhesive layer before curing. Moreover, it can also adjust by including a thermoplastic resin other than a curable adhesive.
- the crosslink density after curing of the adhesive layer may be increased, and if the glass transition temperature of the homopolymer of the monomer component used for dilution is changed to a high one Good.
- a monomer having a high tetra- to hexa-functional cross-linking density for example, A-DPH (Shin Nakamura Chemical), A-TMMT (Shin Nakamura Chemical)
- A-DPH Shin Nakamura Chemical
- A-TMMT Shin Nakamura Chemical
- acrylic acid, acrylamide or the like may be added.
- the thickness of the adhesive layer is preferably 1 to 50 ⁇ m, the lower limit of the adhesive layer is more preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, particularly preferably 10 ⁇ m or more, and the upper limit is further preferably 40 ⁇ m or less, more preferably. 30 ⁇ m or less.
- the irradiation dose of ionizing radiation is preferably 500 to 1500 mJ / cm 2 .
- Such a functional film is stuck to an adherend through an adhesive layer, and can prevent a decrease in surface hardness of the functional layer of the laminate.
- the laminate of the present invention is a laminate in which an adherend is attached to a plastic film having a functional layer composed of a cured film on one surface via an adhesive layer, and the adhesive layer is irradiated with ionizing radiation.
- it contains a curable adhesive that cures by heating, and the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, and against the Martens hardness of the functional layer , Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- the laminate of the present invention is a laminate in which an adherend is bonded to a plastic film having a functional layer composed of a cured film on one surface via an adhesive layer, and then the adhesive layer is cured.
- the adhesive layer contains a curable adhesive that is cured by ionizing radiation irradiation or heating, and the Martens hardness of the adhesive layer after curing by ionizing radiation irradiation or heating is 260 N / mm 2 or less, And for the Martens hardness of the functional layer, Martens hardness of the adhesive layer after curing ⁇ Martens hardness of the functional layer ⁇ 0.25
- the adhesive layer is configured to satisfy the following relational expression.
- the adherend on which such a functional layer is laminated includes polyester, ABS (acrylonitrile-butadiene-styrene), polystyrene, polycarbonate, acrylic, polyolefin, cellulose resin, polysulfone, polyphenylene sulfide, polyethersulfone, polyetheretherketone.
- a molded product made of a synthetic resin such as polyimide can be used, and various shapes can be used. Among them, those excellent in film-like or sheet-like flatness are preferably used, and a polyester film that has been stretched or biaxially stretched is particularly preferable because it is excellent in mechanical strength and dimensional stability, and is firm.
- the plastic film having a functional layer can be the same as the functional film described above.
- the adhesive layer can be the same as the functional film.
- the adhesive layer may be provided on the other surface of the plastic film having the functional layer, or may be directly provided on the adherend on which the plastic film having the functional layer is provided. Further, it may be provided between a plastic film having a functional layer and an adherend.
- additives such as a leveling agent, an ultraviolet absorber, and an antioxidant may be added.
- the coating solution is prepared by dissolving or dispersing the components of each layer in an appropriate solvent, or by mixing the components of each layer without using a solvent.
- the coating solution is adjusted by applying the coating solution onto a plastic film by a known method such as roll coating method, bar coating method, spray coating method, air knife coating method, irradiation with ionizing radiation or heating. can give. It is also possible to form an adhesive layer by pouring the prepared solution without using the coating solution.
- Example 1 The following hard coat paint was applied to one side of a 75 ⁇ m thick plastic film (Cosmo Shine A4300: Toyobo Co., Ltd.) by the bar coater method, dried, and then irradiated with ultraviolet light with a high-pressure mercury lamp (irradiation amount 300 mJ / cm 2 ) A hard coat film of Example 1 having a thickness of 6 ⁇ m was formed, and a plastic film a having a hard coat layer was produced.
- a 75 ⁇ m thick plastic film Cosmo Shine A4300: Toyobo Co., Ltd.
- an adhesive layer coating material having the following formulation was applied to a thickness of 30 ⁇ m and dried to form an adhesive layer (before curing).
- a plastic film Cosmo Shine A4300: Toyobo Co., Ltd.
- a thickness of 188 ⁇ m as an adherend is attached to the adhesive layer so as to face each other, and then irradiated with ultraviolet rays with a high pressure mercury lamp (irradiation amount: 500 mJ / cm 2 ).
- the adhesive layer was completely cured (adhesive layer after “curing was completed”; the same applies hereinafter) to produce the laminate A of Example 1.
- Example 2 A laminate B of Example 2 was produced in the same manner as in Example 1 except that the adhesive layer coating material of Example 1 was changed to the following adhesive layer coating material.
- Example 3 Plastic film having a thickness of 75 [mu] m: on one side of (Cosmoshine A4300 manufactured by Toyobo Co.), the following hard coat coating applied by a bar coater method and dried, irradiated with ultraviolet rays at a high pressure mercury lamp (dose 300 mJ / cm 2) Then, a hard coat film of Example 3 having a thickness of 3 ⁇ m was formed to produce a plastic film b having a hard coat layer.
- an adhesive layer coating material having the following formulation was applied to a thickness of 30 ⁇ m and dried to form an adhesive layer (before curing).
- a plastic film Cosmo Shine A4300: Toyobo Co., Ltd.
- a thickness of 188 ⁇ m as an adherend is attached to the adhesive layer so as to face each other, and then irradiated with ultraviolet rays with a high pressure mercury lamp (irradiation amount: 500 mJ / cm 2 ).
- the adhesive layer was completely cured to produce a laminate C of Example 3.
- Example 4 A laminate D of Example 4 was produced in the same manner as in Example 3 except that the adhesive layer coating material of Example 3 was changed to the following adhesive layer coating material.
- Comparative Example 1 A laminate E of Comparative Example 1 was produced in the same manner as in Example 1 except that the adhesive layer coating material of Example 1 was changed to the following adhesive layer coating material.
- Comparative Example 2 A laminate F of Comparative Example 2 was produced in the same manner as in Example 1 except that the adhesive layer coating material of Example 1 was changed to the following adhesive layer coating material.
- an adhesive layer coating having the following formulation was applied to a thickness of 30 ⁇ m and dried to form an adhesive layer (before curing).
- a plastic film Cosmo Shine A4300: Toyobo Co., Ltd.
- a thickness of 188 ⁇ m as an adherend is attached to the adhesive layer so as to face each other, and then irradiated with ultraviolet rays with a high pressure mercury lamp (irradiation amount: 500 mJ / cm 2 ).
- the adhesive layer was completely cured to produce a laminate G of Comparative Example 3.
- Comparative Example 3 was the same as Comparative Example 3 except that the 50 ⁇ m thick plastic film (Cosmo Shine A4300: Toyobo Co., Ltd.) was changed to a 75 ⁇ m thick plastic film (Cosmo Shine A4300: Toyobo Co., Ltd.). A layered product H was produced.
- Comparative Example 3 is the same as Comparative Example 3 except that the 50 ⁇ m thick plastic film (Cosmo Shine A4300: Toyobo Co., Ltd.) is changed to a 250 ⁇ m thick plastic film (Cosmo Shine A4300: Toyobo Co., Ltd.). A laminate I was prepared.
- the Martens hardness of the surface of the adhesive layer after curing was measured by a method based on ISO-144577-1 (“Martens hardness of the adhesive layer” in Table 1).
- the measurement was performed using an ultra-micro hardness tester (trade name: Fisher Scope HM2000, Fisher Instruments) in an atmosphere at a temperature of 20 ° C. and a relative humidity of 60%.
- the maximum test load was 1 mN. The results are shown in Table 1.
- the laminates of Examples 1 and 3 to 4 were affected by the adhesive layer because the Martens hardness of the adhesive layer was 30% or more of the Martens hardness of the hard coat layer of the film having the hard coat layer. Not only the evaluation by pencil hardness but also the evaluation by Martens hardness was good.
- the Martens hardness of the adhesive layer was less than 25% of the Martens hardness of the hard coat layer of the film having the hard coat layer. The decrease in the surface hardness of the layer could not be prevented.
- the Martens hardness of the adhesive layer was 25% or more of the Martens hardness of the hard coat layer of the film having the hard coat layer, but the Martens hardness of the adhesive layer was 260 N / mm 2. Since it was larger, there was a problem in the proper punching process.
- Example 5 A laminated body A1 of Example 5 was produced in the same manner as in Example 1 except that the ultraviolet ray irradiation amount of the laminated body A of Example 1 was changed to 100 mJ / cm 2 and the adhesive layer was semi-cured.
- A1 in which the adhesive layer was in a semi-cured state was subjected to the same evaluation for punching as described above, the same result as in Example 1 was obtained.
- the laminate A1 in which the adhesive layer is in a semi-cured state is subjected to a die cutting process using a die cutter as described above, and then irradiated with ultraviolet rays with a high pressure mercury lamp (irradiation amount 400 mJ / cm 2 ). Completely cured.
- Example 1 The same evaluation as above (excluding the appropriateness of the punching process) was performed on the laminate A1 completely cured with the adhesive layer. As a result, an excellent evaluation was obtained as in Example 1. From the above, it can be confirmed that even when the adhesive layer is in a semi-cured state, if the Martens hardness of the adhesive layer is adjusted to a predetermined value, it is excellent in evaluation of pencil hardness and appropriateness for punching.
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- Organic Chemistry (AREA)
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- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して、
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されていることを特徴とする。
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して、
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されていることを特徴とする。
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して、
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されていることを特徴とする。
本発明の機能性フィルムは、プラスチックフィルムの一方の面に硬化膜で構成される機能層、他方の面に接着層を有する機能性フィルムであって、
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して、
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されていることを特徴とする。
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように、樹脂、モノマー、オリゴマーなどの配合が調製された硬化型接着剤を選択することにより構成することができる。なお、ここでの「硬化後」は、必ずしも硬化開始後から硬化終了後までの全ての状態で、上の関係を満たしていることを要求するものではなく、少なくとも硬化終了後に上の関係を満たしていればよいとする趣旨である。従って、硬化開始から硬化終了直前までは上の関係を満たしていないが、硬化終了後に満たすこととなる場合はもとより、硬化開始から硬化終了後の全ての状態で満たすこととなる場合も、本発明の「硬化後」に含まれる。
本発明では、接着層の硬化後のマルテンス硬さが、機能層のマルテンス硬さの25%以上、好ましくは30%以上となるように、硬化前の接着層の組成を調製する。接着層の硬化後のマルテンス硬さが機能層のマルテンス硬さの25%以上となるように硬化前の接着層の組成を調製することにより、機能層の表面硬度を低下させることがない。
本発明の接着層は、硬化後の接着層のマルテンス硬さが、第2に、260N/mm2 以下となるように、樹脂、モノマー、オリゴマーなどの配合が調製された硬化型接着剤を選択することにより構成することができる。なお、ここでの「硬化後」は、必ずしも硬化開始後から硬化終了後までの全ての状態で、上の数値以下を満たしていることを要求するものではなく、少なくとも硬化開始から硬化終了直前までの間に、上の数値以下を満たしていればよいとする趣旨である。従って、硬化終了後は上の数値以下を満たしていないが、硬化開始から硬化終了直前までの間は満たすこととなる場合はもとより、硬化開始から硬化終了後の全ての状態で満たすこととなる場合も本発明の「硬化後」に含まれる。
本発明では、硬化後の接着層のマルテンス硬さが、260N/mm2 以下、好ましくは、200N/mm2 以下となるように硬化型接着剤を構成する。260N/m2 以下となるように硬化前の接着層を構成することにより、型抜き処理を行った場合に、浮きや剥がれが生じないものとすることができる。
本発明の積層体は、一方の面に硬化膜で構成される機能層を有するプラスチックフィルムに接着層を介して被着体を貼着した積層体であって、前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して、
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されているものである。
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
の関係式を満たすこととなるように前記接着層が構成されているものである。
厚み75μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)の一方の面に、下記ハードコート塗料をバーコーター法により塗布、乾燥した後、高圧水銀灯で紫外線を照射し(照射量300mJ/cm2 )、厚み6μmの実施例1のハードコート膜を形成し、ハードコート層を有するプラスチックフィルムaを作製した。
・電離放射線硬化型樹脂組成物(固形分100%) 10部
(ビームセット575:荒川化学工業社)
・光重合開始剤 0.5部
(イルガキュア651:チバ・ジャパン社)
・プロピレングリコールモノメチルエーテル 23部
・電離放射線硬化型樹脂(固形分100%) 60部
(KAYARAD R-115:日本化薬社)
・2-ヒドロキシエチルメタクリレート 40部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
実施例1の接着層用塗料を下記接着層用塗料に変更した以外は、実施例1と同様にして実施例2の積層体Bを作製した。
・電離放射線硬化型樹脂(固形分100%) 20部
(KAYARAD R-115:日本化薬社)
・電離放射線硬化型樹脂(固形分100%) 40部
(NKオリゴ U-200PA:新中村化学工業社)
・2-ヒドロキシエチルメタクリレート 40部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
厚み75μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)の一方の面に、下記ハードコート塗料をバーコーター法により塗布、乾燥した後、高圧水銀灯で紫外線を照射し(照射量300mJ/cm2 )、厚み3μmの実施例3のハードコート膜を形成し、ハードコート層を有するプラスチックフィルムbを作製した。
ε-カプトラクトン変性トリス
-(2-ヒドロキシエチル)イソシアヌレート 5部
(SR368:サートマー社)(固形分100%)
・電離放射線硬化型樹脂組成物(固形分100%) 10部
(ビームセット575:荒川化学工業社)
・光重合開始剤 0.4部
(イルガキュア651:チバ・ジャパン社)
・プロピレングリコールモノメチルエーテル 30部
・電離放射線硬化型樹脂(固形分100%) 60部
(KAYARAD R-115:日本化薬社)
・2-ヒドロキシエチルメタクリレート 40部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
実施例3の接着層用塗料を下記接着層用塗料に変更した以外は、実施例3と同様にして実施例4の積層体Dを作製した。
・電離放射線硬化型樹脂(固形分100%) 30部
(KAYARAD R-115:日本化薬社)
・電離放射線硬化型樹脂(固形分100%) 30部
(NKオリゴ U-200PA:新中村化学工業社)
・2-ヒドロキシエチルメタクリレート 40部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
実施例1の接着層用塗料を下記接着層用塗料に変更した以外は、実施例1と同様にして比較例1の積層体Eを作製した。
・電離放射線硬化型樹脂(固形分100%) 52.5部
(NKオリゴ U-200PA:新中村化学工業社)
・2-ヒドロキシエチルメタクリレート 40部
・ブチルアクリレート 7.5部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
実施例1の接着層用塗料を下記接着層用塗料に変更した以外は、実施例1と同様にして比較例2の積層体Fを作製した。
・電離放射線硬化型樹脂(固形分100%) 100部
(NKエステル A-TMM-3N:新中村工業社)
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
厚み50μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)の一方の面に、下記ハードコート塗料をバーコーター法により塗布、乾燥した後、高圧水銀灯で紫外線を照射し(照射量300mJ/cm2 )、厚み6μmの比較例3のハードコート膜を形成し、ハードコート層を有するプラスチックフィルムcを作製した。
・電離放射線硬化型樹脂組成物(固形分80%) 20部
(UNIDIC17-806:DIC社)
・希釈溶媒 34部
・光重合開始剤 0.8部
(イルガキュア184:チバ・ジャパン社)
・電離放射線硬化型樹脂(固形分100%) 20部
(U-6HA:新中村化学社)
・希釈溶媒 20部
・光重合開始剤 5部
(イルガキュア184:チバ・ジャパン社)
比較例3の厚み50μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)を厚み75μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)に変更した以外は、比較例3と同様にして比較例4の積層体Hを作製した。
比較例3の厚み50μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)を厚み250μmのプラスチックフィルム(コスモシャインA4300:東洋紡績社)に変更した以外は、比較例3と同様にして比較例5の積層体Iを作製した。
実施例1~4および比較例1~5の接着層塗布液を厚み188μmの透明ポリエステルフィルム(コスモシャインA4300:東洋紡績社)に、厚みが30μmとなるように塗布、乾燥して接着層(硬化前)を形成した。次に、接着層上に離型フィルムを貼り合わせ、紫外線照射して、接着層を硬化させた。次に、紫外線照射から24時間が経過した後、離型フィルムを接着層から剥離した。離型フィルムを剥離した後の接着層は「硬化終了後」のものである。その後、硬化後の接着層の表面のマルテンス硬さをISO-14577-1に準拠した方法で測定した(表1の「接着層のマルテンス硬さ」)。測定は、温度20℃、相対湿度60%の雰囲気下で、超微小硬さ試験装置(商品名:フィッシャー・スコープ HM2000、フィッシャー・インストルメンツ社)を用いて行った。但し、最大試験荷重を1mNとして測定した。結果を表1に示す。
また、実施例1~4および比較例1~5の、積層体A~Iのハードコート層および、ハードコート層を有するプラスチックフィルムa~cのハードコート層面、の表面の各マルテンス硬さについても、上述した硬化後の接着層の表面のマルテンス硬さの測定と同じ方法で測定した(前者は表1の「積層体のハードコート層のマルテンス硬さ」、後者は表1の「ハードコート層を有するフィルムのマルテンス硬さ」)。結果を表1に示す。
積層体のハードコート層のマルテンス硬さが、ハードコート層を有するプラスチックフィルムのマルテンス硬さの92%未満であったものを「×」、92%以上96%未満であったものを「○」、96%以上であったものを「◎」とした。結果を表1に示す。
実施例1~4および比較例1~5の、積層体A~Iのハードコート層および、ハードコート層を有するプラスチックフィルムa~cのハードコート層、の表面の鉛筆硬度を、JIS K5600-5-4:1999に従い、測定した。積層体のハードコート層の鉛筆硬度が、ハードコート層を有するプラスチックフィルムの鉛筆硬度より低下したものを「×」、鉛筆硬度が低下しなかったものを「○」とした。結果を表1に示す。
実施例1~4および比較例1~5の、積層体A~Iに、型抜き機による型抜き処理を行い、各5枚のサンプル片を作製した。なお、型抜き処理は、硬化前接着層に紫外線を照射してから24時間が経過した後の積層体A~Iに対して行った。型抜き処理の際に、5枚のサンプル片全ての端部に浮きや剥がれが発生したものを「×」、5枚のサンプル片中1~4枚の端部に浮きや剥がれが発生したものを「△」、5枚のサンプル片全てに浮きや剥がれが発生しなかったものを「○」とした。結果を表1に示す。
実施例1~4の積層体は、接着層のマルテンス硬さが、ハードコート層を有するフィルムのハードコート層のマルテンス硬さの25%以上であったため、接着層の影響を受けずに、積層体のハードコート層の表面硬度の低下を防止することができるものであった。また、接着層のマルテンス硬さが、260N/mm2 以下であるため、抜き加工適正や平面性も良好なものであった。
実施例1の積層体Aの紫外線照射量を100mJ/cm2に変更し、接着層を半硬化させた以外は、実施例1と同様にして、実施例5の積層体A1を作製した。接着層が半硬化状態のA1に対し、上記同様の抜き加工適正評価を行ったところ、実施例1と同様の結果が得られた。
次に、接着層が半硬化状態の積層体A1に、上記同様、型抜き機による型抜き処理を行った後、さらに高圧水銀灯で紫外線を照射し(照射量400mJ/cm2)、接着層を完全に硬化させた。この接着層完全に硬化させた積層体A1を、上記同様の評価(抜き加工適正を除く)を行ったところ、実施例1と同様に、優れた評価が得られた。
以上のことから、接着層が半硬化状態でも、接着層のマルテンス硬さが所定値に調整されていれば、鉛筆硬度や抜き加工適正の評価に優れることが確認できた。
Claims (3)
- プラスチックフィルムの一方の面に硬化膜で構成される機能層、他方の面に硬化終了前の接着層を有する機能性フィルムであって、
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して下記関係式を満たすこととなるように前記接着層が構成されていることを特徴とする機能性フィルム。
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25 - 一方の面に硬化膜で構成される機能層を有するプラスチックフィルムに硬化終了前の接着層を介して被着体を貼着した積層体であって、
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して下記関係式を満たすこととなるように前記接着層が構成されていることを特徴とする積層体。
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25 - 一方の面に硬化膜で構成される機能層を有するプラスチックフィルムに、硬化終了後の接着層と被着体を順次積層させた積層体であって、
前記接着層は、電離放射線照射又は加熱により硬化する硬化型接着剤を含むものであり、
電離放射線照射又は加熱による硬化後の接着層のマルテンス硬さが、260N/mm2 以下となり、かつ前記機能層のマルテンス硬さに対して下記関係式を満たすこととなるように前記接着層が構成されていることを特徴とする積層体。
硬化後の接着層のマルテンス硬さ≧機能層のマルテンス硬さ×0.25
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-
2010
- 2010-03-09 KR KR1020117025187A patent/KR101625257B1/ko active IP Right Grant
- 2010-03-09 CN CN201080013832.7A patent/CN102365168B/zh active Active
- 2010-03-09 US US13/260,350 patent/US20120021214A1/en not_active Abandoned
- 2010-03-09 JP JP2011507073A patent/JP4932061B2/ja active Active
- 2010-03-09 WO PCT/JP2010/053891 patent/WO2010113604A1/ja active Application Filing
- 2010-03-09 EP EP10758380.9A patent/EP2415596A4/en not_active Withdrawn
- 2010-03-26 TW TW099109205A patent/TWI482834B/zh active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015186685A1 (ja) * | 2014-06-05 | 2015-12-10 | Dic株式会社 | 保護粘着フィルム、画像表示装置及び携帯電子端末 |
JP6002969B2 (ja) * | 2014-06-05 | 2016-10-05 | Dic株式会社 | 保護粘着フィルム、画像表示装置及び携帯電子端末 |
JPWO2015186685A1 (ja) * | 2014-06-05 | 2017-04-20 | Dic株式会社 | 保護粘着フィルム、画像表示装置及び携帯電子端末 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2010113604A1 (ja) | 2012-10-11 |
CN102365168B (zh) | 2016-01-20 |
CN102365168A (zh) | 2012-02-29 |
JP4932061B2 (ja) | 2012-05-16 |
TWI482834B (zh) | 2015-05-01 |
EP2415596A4 (en) | 2015-08-19 |
EP2415596A1 (en) | 2012-02-08 |
KR20110134924A (ko) | 2011-12-15 |
TW201043679A (en) | 2010-12-16 |
US20120021214A1 (en) | 2012-01-26 |
KR101625257B1 (ko) | 2016-05-27 |
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