WO2022186180A1 - Method for inhibiting color-changeable pressure-sensitive adhesive sheet from discoloring and laminated sheet - Google Patents
Method for inhibiting color-changeable pressure-sensitive adhesive sheet from discoloring and laminated sheet Download PDFInfo
- Publication number
- WO2022186180A1 WO2022186180A1 PCT/JP2022/008527 JP2022008527W WO2022186180A1 WO 2022186180 A1 WO2022186180 A1 WO 2022186180A1 JP 2022008527 W JP2022008527 W JP 2022008527W WO 2022186180 A1 WO2022186180 A1 WO 2022186180A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- color
- adhesive sheet
- sensitive adhesive
- changeable
- sheet
- Prior art date
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 223
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000002401 inhibitory effect Effects 0.000 title description 2
- 239000000853 adhesive Substances 0.000 claims description 254
- 230000001070 adhesive effect Effects 0.000 claims description 254
- 238000002834 transmittance Methods 0.000 claims description 106
- 150000001875 compounds Chemical class 0.000 claims description 66
- 238000002845 discoloration Methods 0.000 claims description 50
- 238000004040 coloring Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 23
- 230000002829 reductive effect Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
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- 238000004132 cross linking Methods 0.000 description 33
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- 238000005259 measurement Methods 0.000 description 29
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- 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
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- C09J11/06—Non-macromolecular additives organic
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to a method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet and a laminated sheet.
- a transparent adhesive sheet that can color the irradiated area by irradiating light with a predetermined wavelength is known.
- a color-changeable adhesive sheet contains a post-colorant (component or components) that colors the adhesive sheet due to light irradiation.
- a display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover member.
- a color-changeable pressure-sensitive adhesive sheet is used for bonding the elements included in the laminated structure.
- the color-changeable adhesive sheet is attached to the adherend (lamination process).
- the presence or absence of foreign matter and air bubbles between the adherend and the color-changeable pressure-sensitive adhesive sheet is inspected. If it does not pass the inspection, the color changeable adhesive sheet is peeled off from the first adherend, and then the lamination process is redone using another color changeable adhesive sheet.
- predetermined portions of the color-changeable pressure-sensitive adhesive sheet on the first adherend are colored by irradiation with light of a predetermined wavelength in order to impart design properties, shielding properties, antireflection properties, and the like. That is, a colored region is formed on the color-changeable pressure-sensitive adhesive sheet.
- the second adherend is joined to the first adherend via the color-changeable pressure-sensitive adhesive sheet.
- a color-changeable pressure-sensitive adhesive sheet used in this way is described, for example, in Patent Document 1 below.
- the present invention is a color-changeable pressure-sensitive adhesive sheet that can be colored by applying an external stimulus. and a laminated sheet obtained by the method.
- the present invention [1] provides a color-changeable pressure-sensitive adhesive sheet having colorability due to an external stimulus, the color-changeable pressure-sensitive adhesive sheet including a colored region and a non-colored region; and a second step of contacting the color-changeable adhesive sheet with a color-lowering medium for reducing the colorability of the color-changeable adhesive sheet.
- a color-reducing medium for reducing the colorability of the pressure-sensitive adhesive sheet is brought into contact with the color-changeable pressure-sensitive adhesive sheet including the colored region and the non-colored region.
- Such a configuration is suitable for reducing the colorability of the non-colored regions in the color-changeable pressure-sensitive adhesive sheet including the colored regions and the non-colored regions, thereby suppressing the discoloration of the non-colored regions over time.
- a color-changeable pressure-sensitive adhesive sheet including colored regions and non-colored regions is prepared in the first step, with such a second step scheduled to be performed later.
- Such a configuration is suitable for preparing the color-changeable pressure-sensitive adhesive sheet as a pressure-sensitive adhesive sheet having a high colorability due to an external stimulus and having a well-colored colored region. Even if the color-changeable pressure-sensitive adhesive sheet has high colorability so that the colored region is well colored, the colorability is reduced by contact with the color-decreasing medium in the second step. Therefore, after the second step, Discoloration of the non-pigmented areas over time is suppressed. As described above, the method of the present invention achieves good coloring of the colored regions and suppression of discoloration over time of the non-colored regions after the formation of the colored regions in the variable color pressure-sensitive adhesive sheet that can be colored by applying an external stimulus. , suitable for compatibility.
- the color-changeable pressure-sensitive adhesive sheet contains a first compound that undergoes a first reaction upon receiving an external stimulus, and a second compound that develops color through a second reaction with the product of the first reaction. and the method for suppressing discoloration of the color-changeable pressure-sensitive adhesive sheet according to [1] above.
- a color-changeable pressure-sensitive adhesive sheet appropriately colored by cooperation of the first compound and the second compound can be prepared in the first step.
- the present invention [3] is the color-changeable pressure-sensitive adhesive sheet according to [2] above, wherein the first compound is a photoacid generator, and the second compound is a color-developing compound that develops color upon reaction with an acid. Including discoloration control method.
- the color-changeable adhesive sheet colored using light irradiation as the external stimulus can be prepared in the first step.
- an acid is generated from the photoacid generator at the irradiated site, and the color-developing compound reacts with the acid to develop a color, thereby coloring the site.
- the first compound is extracted from the color-changeable pressure-sensitive adhesive sheet into the reduced coloring medium, or the reduced coloring medium reduces the coloring.
- the color-reducing adhesive according to [2] or [3] above, wherein the coloring-reducing component is introduced from the coloring-reducing medium to the color-changeable adhesive sheet in the second step. Includes sheet discoloration suppression method.
- Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step.
- the present invention [5] is a first system in which the first compound, the second compound, and the coloring-reducing component coexist, wherein the reduction in transmittance ⁇ T1 due to the application of the external stimulus is determined by the presence of the coloring-reducing component.
- Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step.
- the present invention [6] is the color-changeable pressure-sensitive adhesive sheet according to [5] above, wherein the coloring-lowering component contains at least one selected from the group consisting of an ultraviolet absorber, a neutralizing agent, and a radical trapping agent. including a discoloration suppression method.
- Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step when a photoacid generator is used as the first component.
- the present invention is the above-described [1] to [6], wherein the reduced-colorability medium is a reduced-colorability sheet, and in the second step, the reduced-colorability sheet is attached to the color-changeable pressure-sensitive adhesive sheet.
- a method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of the above is included.
- Such a configuration is suitable for efficiently performing the second step in the manufacturing process of a device using a color-changeable adhesive sheet.
- a mask material is interposed between at least a part of the colored region of the color-changeable pressure-sensitive adhesive sheet and the reduced coloring sheet.
- Such a configuration is suitable for controlling portions of the color-changeable pressure-sensitive adhesive sheet in which the colorability is lowered in the second step.
- the present invention includes the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to [7] or [8] above, wherein the color-reducing sheet contains a polar group-containing polymer.
- Such a configuration is suitable for extracting the first compound from the color-changeable pressure-sensitive adhesive sheet to the color-reducing sheet in the second step.
- the present invention [10] includes the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of [7] to [9] above, wherein the reduced-colorability sheet is a pressure-sensitive adhesive sheet.
- Such a configuration is suitable for highly adhering the color-reducing sheet to the color-changeable pressure-sensitive adhesive sheet in the second step. Moreover, this configuration is suitable for making the laminated sheet (laminated body of the color-changeable adhesive sheet and the color-reducing sheet) obtained in the second step function as a double-sided adhesive sheet.
- the present invention [11] includes the method for suppressing discoloration according to any one of [1] to [6] above, wherein the reduced-coloring medium is a reduced-coloring solvent.
- Such a configuration is preferable for efficiently performing the second step.
- the present invention [12] is a laminated sheet obtained by the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of [7] to [10] above, comprising: the color-changeable pressure-sensitive adhesive sheet; A laminated sheet comprising the coloring-impaired sheet attached to an adhesive sheet.
- Such a laminated sheet is suitable for assembling a color-changeable pressure-sensitive adhesive sheet that satisfies both good coloring of colored regions and suppression of discoloration of non-colored regions as a structural member of a device such as a display panel.
- 1 shows the first step in one embodiment of the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet of the present invention.
- 2 shows the second step in one embodiment of the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet of the present invention.
- the case where the 1st member and the 2nd member were joined through the lamination sheet after the 2nd process shown in FIG. 2 is represented.
- the second step when a coloring-impaired solvent is used as the coloring-impaired medium, or when the coloring-impaired sheet is peeled off from the color-changeable pressure-sensitive adhesive sheet after the second step, after the second step, the first member and the second member are joined via the color-changeable pressure-sensitive adhesive sheet.
- the color-reducing sheet is attached to the color-changeable adhesive sheet with a mask material interposed between the colored region of the color-changeable adhesive sheet and the color-reducing sheet.
- the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet of the present invention includes a first step and a second step.
- a color-changeable adhesive sheet X is prepared.
- the variable color adhesive sheet X has a sheet shape with a predetermined thickness and extends in a direction (plane direction) perpendicular to the thickness direction.
- the color-changeable adhesive sheet X is formed from the first adhesive composition.
- the color-changeable adhesive sheet X is an adhesive sheet that is colored by an external stimulus. 12 (uncolored areas).
- the second region 12 preferably has transparency (visible light transmittance).
- the color-changeable pressure-sensitive adhesive sheet X comprises a base polymer, a first compound that undergoes a first reaction upon receiving an external stimulus, and a second compound that develops color through a second reaction with the product of the first reaction. contains. According to such a configuration, the color-changeable pressure-sensitive adhesive sheet X appropriately colored by cooperation of the first compound and the second compound can be prepared in the first step.
- Examples of external stimuli include light irradiation and heating, depending on the components contained in the color-changeable adhesive sheet X.
- Types of light for light irradiation include, for example, ultraviolet light, visible light, and infrared light, and ultraviolet light is preferable from the viewpoint of the diversity of equipment used.
- the first compound is a photoacid generator
- the second compound is a color-developing compound that develops color upon reaction with acid.
- the color-changeable pressure-sensitive adhesive sheet X By irradiating the color-changeable pressure-sensitive adhesive sheet X with light of a predetermined wavelength, an acid is generated from the photoacid generator at the irradiated portion, and the color-developing compound reacts with the acid to develop a color, thereby coloring the portion. More specifically, the components of the color-changeable pressure-sensitive adhesive sheet X are as described below.
- the color-changeable pressure-sensitive adhesive sheet X may be attached to a predetermined adherend.
- FIG. 1 exemplarily shows a state in which the color-changeable adhesive sheet X is attached to one surface of the first member 21 in the thickness direction T.
- the first member 21 is, for example, a display panel such as an organic EL panel.
- the first member 21 may be another electronic device or an optical device.
- an external stimulus is applied to a predetermined portion of the color-changeable pressure-sensitive adhesive sheet X to form the first region 11 .
- the presence or absence of foreign substances and air bubbles between the first member 21 and the color-changeable adhesive sheet X is inspected. .
- Discoloration media and extraction media are included as media with reduced coloration.
- the deactivating medium is a medium that contains a coloring property-reducing component for deteriorating the coloring property of the color-changeable adhesive sheet X, and is a medium for introducing the component into the color-changeable adhesive sheet X (the deactivating media is a variable It is a medium for inhibiting/deactivating coloring as a function of the colored adhesive sheet X).
- diffusion of the color-reducing component occurs so that the concentration distribution of the color-reducing component in the system becomes less biased.
- the extraction medium is a medium for extracting the first compound from the color-changeable adhesive sheet X to reduce the colorability of the color-changeable adhesive sheet X.
- FIG. In a system consisting of the color-changeable pressure-sensitive adhesive sheet X and an extraction medium in contact with the sheet, the first compound diffuses so that the concentration distribution of the first compound in the system is less biased. Thereby, the first compound can be extracted from the color-changeable adhesive sheet X to the extraction medium (extraction function).
- the disused media described above also serves as media for extraction when it has such an extraction function and the introduction function described above.
- the above deactivation media and extraction media are suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet X in the second step.
- the coloring-impaired media include a coloring-impairing sheet and a coloring-impairing solvent. That is, the color-reducing media includes deactivating sheets, extracting sheets, deactivating solvents, and extracting solvents.
- the color-reducing sheet is a pressure-sensitive adhesive sheet in this embodiment.
- FIG. 2 shows the case where the coloring-impaired sheet Y as the coloring-impaired medium is used in the second step.
- the color-reducing sheet Y is adhered to one side of the color-changeable pressure-sensitive adhesive sheet X in the thickness direction T.
- the coloring-reduced sheet Y has a sheet shape with a predetermined thickness and extends in a direction (surface direction) perpendicular to the thickness direction.
- the coloring-impaired sheet Y is a pressure-sensitive adhesive sheet formed from the second pressure-sensitive adhesive composition in this embodiment.
- the lamination sheet L is obtained by this process.
- the laminated sheet L includes a color-changeable pressure-sensitive adhesive sheet X and a color-lowering sheet Y attached to the color-changeable pressure-sensitive adhesive sheet X.
- the time for which the color-reducing adhesive sheet Y is brought into contact with the color-changeable pressure-sensitive adhesive sheet X is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 minutes or longer.
- the contact time is preferably 72 hours or less, more preferably 48 hours or less, even more preferably 24 hours or less, and particularly preferably 12 hours or less. is.
- the color-changeable pressure-sensitive adhesive sheet X is brought into contact with the coloring-lowering solvent in the second step.
- the specific components of the coloring-reducing solvent are as described below.
- the contact method includes, for example, immersing the color-changeable pressure-sensitive adhesive sheet X in the color-reducing solvent and spraying the color-changeable pressure-sensitive adhesive sheet X with the color-reducing solvent.
- the time for which the color-changing pressure-sensitive adhesive sheet X is brought into contact with the color-reducing solvent is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 minutes or longer.
- the contact time is preferably 72 hours or less, more preferably 48 hours or less, still more preferably 24 hours or less, and particularly preferably 12 hours or less.
- the second step it is preferable to heat the color-changeable pressure-sensitive adhesive sheet X and the reduced-colorability medium (the reduced-colorability sheet Y in FIG. 2).
- the heating promotes the movement of the color-reducing components in the disabling media to the color-changeable pressure-sensitive adhesive sheet X.
- FIG. When an extraction medium is used as the color-lowering medium, heating promotes the movement of the first component in the color-changeable pressure-sensitive adhesive sheet X to the extraction medium.
- the heating temperature in the second step is preferably 30° C. or higher, more preferably 50° C. or higher, and preferably 150° C. or lower, more preferably 100° C. or lower.
- the color-changeable adhesive sheet X including the first region 11 (colored region) and the second region 12 (non-colored region) is colored.
- a color reducing medium for reducing the properties is brought into contact.
- the configuration reduces the colorability of the first region 11 to suppress discoloration of the first region 11 over time, and the second compound (coloring component ), and therefore also suitable for ensuring the coloring stability of the first region 11 (specifically, for example, shown in Examples 7 and 8 and Comparative Example 3 below) as follows). That is, this method can also be implemented as a method for stabilizing coloring of the color-changeable pressure-sensitive adhesive sheet X having a colored region. Even when the colored region is formed on the entire surface of the color-changeable adhesive sheet X, the effect of stabilizing the coloring of the colored region can be obtained.
- Color stabilization of the colored regions of the color-changeable pressure-sensitive adhesive sheet X is preferable from the viewpoint of ensuring the functions (design, shielding, antireflection, etc.) of the colored regions according to the application of the color-changeable pressure-sensitive adhesive sheet X.
- the color-changeable adhesive sheet X including the first region 11 and the second region 12 is prepared in the first step, with such a second step scheduled to be performed later.
- Such a configuration is suitable for preparing the color-changeable pressure-sensitive adhesive sheet X as a pressure-sensitive adhesive sheet having a high colorability due to an external stimulus and a well-colored first region 11 (in the color-changeable pressure-sensitive adhesive sheet X, The higher the content of the first compound and/or the second compound, the higher the colorability of the color-changeable pressure-sensitive adhesive sheet X).
- the coloring property-reduced pressure-sensitive adhesive sheet X may be used in the second step. Since the colorability is lowered by the contact, the discoloration of the second region 12 over time is suppressed after such a second step.
- this method achieves both good coloring of the first region 11 and suppression of discoloration of the second region 12 over time in the color-changeable pressure-sensitive adhesive sheet X that can be colored by applying an external stimulus.
- the photoacid generator (first compound), the color-developing compound (second compound), and the coloring-reducing component are added before the coloring treatment. coexists, the color-changeable pressure-sensitive adhesive sheet has low coloring ability and is difficult to color.
- the predetermined region can sufficiently exhibit its coloring ability and can be satisfactorily obtained. While being colored (formation of the first region 11), the non-colored region (second region 12) is made difficult to discolor, thereby suppressing discoloration.
- the second member M2 is, for example, a transparent cover member.
- transparent cover members include transparent plastic films and transparent glass plates.
- the first member 21 and the second member 22 are joined via the color-changeable adhesive sheet X, as shown in FIG.
- the laminate Z2 having the first member 21, the color-changeable adhesive sheet X, and the second member 22 in order in the thickness direction T is obtained.
- the first adhesive composition forming the color-changeable adhesive sheet X is a second composition comprising a base polymer, a first compound that undergoes a first reaction upon receiving an external stimulus, and a product of the first reaction. and a second compound that develops color upon reaction.
- the base polymer is an adhesive component for developing adhesiveness in the color-changeable adhesive sheet X.
- the base polymer exhibits rubber elasticity in the room temperature range.
- Base polymers include, for example, acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and adhesiveness in the color-changeable pressure-sensitive adhesive sheet X, an acrylic polymer (first acrylic polymer) is preferably used as the base polymer.
- An acrylic polymer is, for example, a copolymer of a monomer component (first monomer component) containing a (meth)acrylic acid alkyl ester at a ratio of 50% by mass or more.
- (Meth)acrylic acid means acrylic acid and/or methacrylic acid.
- (Meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms.
- Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid.
- the (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination.
- an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferably used, and more preferably having methyl methacrylate and an alkyl group having 2 to 12 carbon atoms.
- a (meth)acrylic acid alkyl ester is used in combination, and more preferably, methyl methacrylate and 2-ethylhexyl acrylate are used in combination.
- the ratio of the (meth)acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the color-changeable pressure-sensitive adhesive sheet X. Preferably, it is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
- the first monomer component may contain a copolymerizable monomer copolymerizable with the (meth)acrylic acid alkyl ester.
- copolymerizable monomers include monomers having a polar group.
- Polar group-containing monomers include, for example, hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers.
- the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing cross-linking points into the acrylic polymer and securing the cohesive strength of the acrylic polymer.
- the copolymerizable monomer preferably contains at least one selected from the group consisting of hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers. More preferably, the copolymerizable monomer includes a hydroxyl group-containing monomer and/or a monomer having a nitrogen atom-containing ring.
- hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and ( 4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
- 2-hydroxyethyl (meth)acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
- the ratio of the hydroxyl group-containing monomer in the first monomer component is preferably 1% by mass or more, more preferably 3% by mass, from the viewpoints of introducing a crosslinked structure into the acrylic polymer and ensuring cohesive strength in the color-changeable pressure-sensitive adhesive sheet X. % or more, more preferably 5 mass % or more. From the viewpoint of adjusting the polarity of the acrylic polymer, the same ratio is preferably 30% by mass or less, more preferably 20% by mass or less.
- the polarity of the acrylic polymer is related to the compatibility between various additive components in the color-changeable pressure-sensitive adhesive sheet X and the acrylic polymer.
- Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole,
- the ratio of the monomer having a nitrogen atom-containing ring in the first monomer component is preferable from the viewpoint of ensuring the cohesive force of the color-changeable pressure-sensitive adhesive sheet X and the adhesion to the adherend of the color-changeable pressure-sensitive adhesive sheet X. is 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The same proportion is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer.
- Carboxy group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- the ratio of the carboxyl group-containing monomer in the first monomer component is used to introduce a crosslinked structure into the acrylic polymer, ensure the cohesive force of the color-changeable pressure-sensitive adhesive sheet X, and ensure the adhesion to the adherend of the color-changeable pressure-sensitive adhesive sheet X. From the viewpoint, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoints of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of acid corrosion of the adherend.
- the first monomer component may contain other copolymerizable monomers (the same applies to the second monomer component described later).
- Other copolymerizable monomers include, for example, acid anhydride monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, alkoxy group-containing monomers, and aromatic vinyl compounds. be done.
- the acrylic polymer can be formed by polymerizing the first monomer component described above.
- the polymerization method includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization.
- the polymerization initiator for example, a thermal polymerization initiator is used.
- the amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the first monomer component.
- Thermal polymerization initiators include, for example, azo polymerization initiators and peroxide polymerization initiators.
- azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2- imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, and 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride mentioned.
- Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxid
- the weight-average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force of the color-changeable pressure-sensitive adhesive sheet X.
- the weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
- the weight average molecular weight of the acrylic polymer is calculated by measuring by gel permeation chromatography (GPC) and converting to polystyrene.
- the glass transition temperature (Tg) of the acrylic polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower.
- the glass transition temperature is, for example, ⁇ 80° C. or higher.
- the glass transition temperature (Tg) of the polymer the glass transition temperature (theoretical value) obtained based on the following Fox formula can be used.
- the Fox equation is a relational expression between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of a homopolymer of monomers constituting the polymer.
- Tg represents the glass transition temperature (° C.) of the polymer
- Wi represents the weight fraction of the monomer i constituting the polymer
- Tgi represents the glass transition of the homopolymer formed from the monomer i.
- Literature values can be used for the glass transition temperature of homopolymers.
- the glass transition temperature of a homopolymer of a monomer can also be determined by the method specifically described in JP-A-2007-51271.
- the first adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer.
- Crosslinkers include, for example, isocyanate crosslinkers, epoxy crosslinkers, oxazoline crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, and metal chelate crosslinkers.
- the cross-linking agents may be used alone, or two or more of them may be used in combination.
- isocyanate cross-linking agents examples include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, isocyanates, and polymethylene polyphenyl isocyanates.
- the isocyanate cross-linking agent also includes derivatives of these isocyanates.
- isocyanate derivative examples include isocyanurate-modified products and polyol-modified products.
- Commercially available isocyanate cross-linking agents include, for example, Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh Corporation), Coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh Corporation), and Coronate HX. (isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) and Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.).
- epoxy cross-linking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether. , diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.
- the amount of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the base polymer. More preferably, it is 0.07 parts by mass or more.
- the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably It is 3 parts by mass or less.
- a cross-linking catalyst When a cross-linked structure is introduced into the base polymer, a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
- Cross-linking catalysts include, for example, dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, Nasem ferric iron, and butyltin oxide, preferably dibutyltin dilaurate.
- the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the base polymer.
- a cross-linking inhibitor that can be subsequently removed from the first adhesive composition may be blended into the first adhesive composition.
- dibutyltin dilaurate is used as the cross-linking catalyst
- acetylacetone is preferably used as the cross-linking inhibitor.
- acetylacetone is coordinated to dibutyltin dilaurate, and progress of the cross-linking reaction of the cross-linking agent with respect to the base polymer is suppressed.
- the acetylacetone is volatilized by heating at a desired timing to form a coating film. can be removed from This allows the cross-linking reaction of the cross-linking agent to proceed.
- the amount of the cross-linking inhibitor is preferably 100 parts by mass or more, more preferably 1000 parts by mass or more, relative to 100 parts by mass of the cross-linking catalyst. Moreover, the compounding amount is, for example, 5000 parts by mass or less.
- Examples of the first compound include acid generators.
- Acid generators include, for example, photoacid generators and thermal acid generators.
- the photoacid generator is excited by irradiation with light of a predetermined wavelength or wavelength range to cause an acid generation reaction and generate acid.
- the acid generation reaction is, for example, a decomposition reaction of the photoacid generator.
- the wavelength of light that efficiently causes the acid generating reaction varies depending on the type of photoacid generator.
- photoacid generators include onium compounds that generate acid when irradiated with ultraviolet rays.
- Onium compounds are provided, for example, in the form of onium salts of onium cations and anions.
- Onium cations include, for example, sulfonium and iodonium.
- Examples of anions include Cl ⁇ , Br ⁇ , I ⁇ , ZnCl 3 ⁇ , HSO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , C 4 F 9 HSO 3 ⁇ , (C 6 F 5 ) 4 B ⁇ , and (C 4 H 9 ) 4 B ⁇ .
- the photoacid generators may be used alone, or two or more of them may be used in combination.
- An onium salt of sulfonium and C 4 F 9 HSO 3 — and/or an onium salt of iodonium salt and C 4 F 9 HSO 3 — is preferably used as the photoacid generator.
- the amount of the photoacid generator to be blended with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more.
- the blending amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.
- the amount of the photoacid generator to be added to 100 parts by mass of the color forming compound described later is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more, and particularly preferably 330 parts by mass or more. is.
- the blending amount is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and even more preferably 500 parts by mass or less.
- Examples of the second compound include color-developing compounds that develop color upon reaction with an acid.
- Examples of such color-forming compounds include leuco dyes, triarylmethane dyes, diphenylmethane dyes, fluorane dyes, spiropyran dyes, and rhodamine dyes.
- the color-developing compounds may be used alone, or two or more of them may be used in combination.
- Leuco dyes include, for example, 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthene], 3-dibutylamino- 6-methyl-7-anilinofluorane, 3-dipropylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dimethylamino-6- Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xyridinofluorane, and 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole) -3-yl)-4-azaphthalide.
- triarylmethane dyes examples include p,p′,p′′-tris-dimethylaminotriphenylmethane.
- diphenylmethane dyes examples include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether.
- fluorane dyes examples include 3-diethylamino-6-methyl-7-chlorofluorane
- examples of spiropyran dyes include 3-methylspirodinaphthopyran
- examples of rhodamine dyes examples include: Examples include rhodamine-B-anilinolactam.
- the color-developing compound is preferably a leuco dye, more preferably 2'-anilino-6'-(N-ethyl-N-isopentylamino). -3'-methylspiro[phthalido-3,9'-[9H]xanthene] is used.
- the amount of the color-developing compound compounded with respect to 100 parts by mass of the base polymer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.
- the blending amount is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
- the first adhesive composition may contain other components as necessary.
- Other ingredients include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, sensitizers, and antistatic agents.
- the color-changeable pressure-sensitive adhesive sheet X can be produced, for example, by applying the varnish of the first pressure-sensitive adhesive composition described above to the base film to form a coating film, and then drying the coating film.
- base films include flexible plastic films.
- the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
- the thickness of the base film is, for example, 3 ⁇ m or more and, for example, 200 ⁇ m or less.
- the surface of the base film is preferably release-treated.
- the cross-linking reaction proceeds simultaneously with the above-described drying or by subsequent aging.
- Aging conditions are appropriately set according to the type of cross-linking agent.
- the aging temperature is, for example, 20°C to 160°C.
- Aging time is, for example, from 1 minute to 7 days.
- a release film may be further laminated on the color-changeable pressure-sensitive adhesive sheet X on the base film before or after aging.
- the release film is a flexible plastic film to which surface release treatment has been applied. Release films include, for example, the plastic films described above with respect to the base film.
- the color-changeable adhesive sheet X whose adhesive surface is covered and protected by the release film can be manufactured.
- Each release film is peeled off from the color-changeable pressure-sensitive adhesive sheet X when the color-changeable pressure-sensitive adhesive sheet X is used.
- the thickness of the color-changeable pressure-sensitive adhesive sheet X is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, from the viewpoint of ensuring sufficient adhesion to the adherend. From the viewpoint of handleability of the color-changeable pressure-sensitive adhesive sheet X, the thickness of the color-changeable pressure-sensitive adhesive sheet X is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the average transmittance of the color-changeable pressure-sensitive adhesive sheet X at a wavelength of 400 to 700 nm is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more.
- Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the color-changeable adhesive sheet X and the adherend after bonding the color-changeable adhesive sheet X to the adherend.
- the average transmittance at wavelengths from 400 to 700 nm can be measured by the method described below with respect to the examples below.
- the second adhesive composition forming the color-reducing sheet Y contains a base polymer.
- the base polymer includes the base polymer described above with respect to the first adhesive composition, preferably an acrylic polymer (second acrylic polymer).
- the monomer component (second monomer component) forming the second acrylic polymer contains a (meth)acrylic acid alkyl ester.
- the (meth)acrylic acid alkyl ester include the (meth)acrylic acid alkyl esters described above with respect to the first acrylic polymer, and preferably, an acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms is used. 2-ethylhexyl acrylate and/or isostearyl acrylate are more preferably used.
- the ratio of the (meth)acrylic acid alkyl ester in the second monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the color-reducing sheet Y. , more preferably 70% by mass or more.
- the same ratio is, for example, 99% by mass or less.
- the second monomer component may contain a copolymerizable monomer copolymerizable with the (meth)acrylic acid alkyl ester.
- the copolymerizable monomer include the copolymerizable monomers described above for the first acrylic polymer, preferably a polar group-containing monomer, more preferably a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and , a carboxy group-containing monomer is used.
- a polar group-containing monomer more preferably a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and , a carboxy group-containing monomer is used.
- 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate are preferably used as the hydroxyl group-containing monomer in the second monomer component.
- N-vinyl-2-pyrrolidone is preferably used as the monomer having a nitrogen atom-containing ring in the second monomer component.
- Acrylic acid is preferably used as the carboxy group-containing monomer in the second monomer component.
- the acrylic polymer as the copolymer of the second monomer component containing the polar group-containing monomer is a polar group-containing polymer. Such an acrylic polymer is preferable for extracting the first compound such as the above photoacid generator from the color-changeable pressure-sensitive adhesive sheet X to the color-reducing sheet Y.
- the ratio of the polar group-containing monomer in the second monomer component is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of ensuring cohesive strength of the acrylic polymer and adjusting the polarity of the acrylic polymer. It is more preferably 5% by mass or more, preferably 40% by mass or less, and more preferably 30% by mass or less.
- the coloring-impaired sheet Y is a sheet for extraction, from the viewpoint of ensuring ease of migration (extractability) of the photoacid generator from the color-changeable pressure-sensitive adhesive sheet X to the coloring-impaired sheet Y, the second monomer component
- the ratio of the polar group-containing monomer in is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 35% by mass or less. is.
- the second acrylic polymer can be formed by polymerizing the second monomer component described above.
- the polymerization method includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization.
- the polymerization initiator for example, the thermal polymerization initiator described above is used.
- the amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the second monomer component.
- the weight-average molecular weight of the second acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and still more preferably 500,000 or more, from the viewpoint of ensuring the cohesive strength of the reduced-colorability sheet Y.
- the weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
- the glass transition temperature (Tg) of the second acrylic polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower.
- the glass transition temperature is, for example, ⁇ 80° C. or higher.
- the second adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer.
- Cross-linking agents include, for example, the isocyanate cross-linking agents described above, the epoxy cross-linking agents described above, the oxazoline cross-linking agents, the aziridine cross-linking agents, the carbodiimide cross-linking agents, and the metal chelate cross-linking agents.
- the cross-linking agents may be used alone, or two or more of them may be used in combination.
- the amount of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the base polymer. More preferably, it is 0.07 parts by mass or more.
- the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably It is 3 parts by mass or less.
- a cross-linking catalyst When a cross-linked structure is introduced into the base polymer, a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
- the cross-linking catalyst include the cross-linking agents described above with respect to the first adhesive composition.
- the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the base polymer.
- a cross-linking inhibitor that can be subsequently removed from the second adhesive composition may be incorporated into the second adhesive composition.
- the cross-linking inhibitor include the cross-linking inhibitors described above with respect to the first adhesive composition.
- the amount of the cross-linking inhibitor to be blended is preferably 100 parts by mass or more, more preferably 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking catalyst. Moreover, the compounding amount is, for example, 5000 parts by mass or less.
- the second adhesive composition further contains a coloring-reducing component.
- the coloring-lowering component include an ultraviolet absorber, a neutralizer, and a radical trapping agent.
- the coloring-lowering component preferably contains at least one selected from the group consisting of ultraviolet absorbers, neutralizers, and radical trapping agents.
- the ultraviolet absorber After being introduced from the color-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above, the ultraviolet absorber absorbs part or all of the ultraviolet light received by the color-changeable pressure-sensitive adhesive sheet X.
- This UV absorption suppresses the acid generation reaction that occurs when the photoacid generator is exposed to UV irradiation, and thus suppresses the coloring of the color-developing compound. As a result, the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
- ultraviolet absorbers examples include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, oxybenzophenone ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, salicylic acid ester ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
- the neutralizing agent neutralizes part or all of the acid generated by the photoacid generator after being introduced from the color-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above.
- This neutralizing action suppresses the reaction between the acid and the color-developing compound that occurs when the photoacid generator is irradiated with ultraviolet rays. As a result, the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
- neutralizing agents include primary amines, secondary amines, and tertiary amines that exhibit alkalinity.
- Primary amines include, for example, monoethylamine and monoethanolamine.
- Secondary amines include, for example, diethylamine and diethanolamine.
- Tertiary amines include, for example, triethylamine, triethanolamine, N,N,N'-trimethylethylenediamine, N-methyldiethanolamine, and N,N-diethylhydroxylamine.
- the radical trapping agent traps radicals when radicals are generated at the start of the acid generation reaction of the photoacid generator after being introduced from the colorability-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above. , to suppress the progress of the acid generation reaction. As a result, the color development of the color-developing compound is suppressed, and the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
- radical trapping agents include hindered amine compounds, hindered phenol compounds, N-oxyl compounds, naphthalene derivatives, thioether compounds, and hydrazil compounds, preferably hindered amine compounds.
- the ratio of the coloring-lowering component in the second adhesive composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, relative to 100 parts by mass of the base polymer. .
- the same ratio is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less with respect to 100 parts by mass of the base polymer.
- the formation of the first regions 11 by applying an external stimulus to the color-changeable pressure-sensitive adhesive sheet X is inhibited.
- the color-reducing component when a deactivating medium is used as the color-reducing medium, the color-reducing component can be introduced into the color-changeable pressure-sensitive adhesive sheet X after the first region 11 is formed. can be avoided.
- the decrease in transmittance ⁇ T1 due to the application of an external stimulus in the first system in which the first compound, the second compound, and the coloring-reducing component coexist is preferably It is smaller than the decrease ⁇ T2 in transmittance due to the application of the same external stimulus to the second system that is the same as the first system.
- the difference between ⁇ T2 and ⁇ T1 ( ⁇ T2 ⁇ T1) is preferably 5% or more, more preferably 15% or more, even more preferably 30% or more, and particularly preferably 50% or more.
- the transmittance is, for example, the average transmittance at wavelengths from 400 to 700 nm, and can be measured by the method described below with respect to the examples below. Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet X in the second step.
- the second adhesive composition may contain other ingredients as necessary.
- Other ingredients include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
- the second adhesive composition that forms the color-reducing sheet Y does not contain the first compound such as the photoacid generator described above and the second compound such as the color-developing compound described above.
- the second adhesive composition that forms the coloring-reducing sheet Y as an extraction sheet does not contain coloring-reducing components such as UV absorbers, neutralizers, and radical trapping agents.
- the coloring-reduced sheet Y can be produced, for example, by applying the varnish of the above-described second adhesive composition onto the base film to form a coating film, and then drying the coating film. Specifically, it is the same as the method for manufacturing the color-changeable pressure-sensitive adhesive sheet X described above.
- the thickness of the colorability-reducing sheet Y is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, from the viewpoint of good expression of the colorability-reducing function. From the viewpoint of handleability of the coloring-impaired sheet Y, the thickness of the coloring-impaired sheet Y is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less.
- the average transmittance of the color-reducing sheet Y at a wavelength of 400 to 700 nm is higher than the average transmittance of the first region 11 of the color-changeable pressure-sensitive adhesive sheet X at a wavelength of 400 to 700 nm, for example, 40% or more. 99% or less.
- the average transmittance of the color-impaired sheet Y at a wavelength of 400 to 700 nm is preferably 45% or higher, more preferably 50% or higher, and even more preferably 60% or higher.
- the average transmittance is, for example, 100% or less.
- the wavelength of the reduced coloring sheet Y is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less.
- the average transmittance is, for example, 50% or more.
- a masking material M is interposed between the first region 11 of the color-changeable pressure-sensitive adhesive sheet X and the color-reducing sheet X, and the color-reducing sheet Y is subjected to a color-changeable process. It may be attached to the adhesive sheet X.
- the mask material M may be placed on the color-changeable adhesive sheet X before the first regions 11 are formed, or may be placed on the color-changeable adhesive sheet X after the first regions 11 are formed. good too.
- the mask material M is, for example, a transparent plastic film.
- Materials for plastic films include, for example, polyolefins, polyesters, polyamides, polyimides, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonates.
- Polyolefins include, for example, polyethylene and polypropylene.
- Polyesters include, for example, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.
- Polyamides include, for example, polyamide 6, polyamide 6,6, and partially aromatic polyamides.
- the masking material M In the region where the masking material M is arranged, component movement between the color-changeable pressure-sensitive adhesive sheet X and the color-reducing sheet Y is prevented.
- the use of such a masking material M can be achieved in the second step by introducing a colorability-reducing component from the color-reducing sheet Y into the color-reducing adhesive sheet X, or removing the color-reducing component from the color-reducing adhesive sheet X with the color-reducing sheet Y in the second step. It is suitable for selectively and efficiently extracting one compound from the second region 12 .
- the coloring-lowering solvent as the coloring-lowering medium may contain a polar solvent or a low-polar solvent (non-polar solvent) as the main agent.
- Polar solvents include, for example, water, alcohols, and carboxylic acids.
- Polar solvents also include moderately polar solvents such as ethyl acetate, acetone, and acetonitrile.
- Alcohols include, for example, methanol, ethanol, isopropyl alcohol, and butanol.
- Carboxylic acids include formic acid and acetic acid.
- Low polarity solvents include, for example, benzene, toluene, and methyl isobutyl ketone.
- a liquid monomer exhibiting sufficient component solubility as a deactivating solvent or an extracting solvent can also be appropriately selected and used.
- Such liquid monomers include, for example, various acrylate monomers.
- the coloration-reducing solvent when the coloration-reducing solvent is a deactivating coloration-reducing solvent, the coloration-reducing solvent further contains a coloration-reducing component.
- the coloring-lowering component preferably contains at least one selected from the group consisting of ultraviolet absorbers, neutralizers, and radical trapping agents. Examples of the ultraviolet absorber, neutralizing agent and radical trapping agent include the ultraviolet absorbing agent, neutralizing agent and radical trapping agent described above with respect to the color-reducing sheet Y, preferably the radical trapping agent.
- the proportion of the coloring-lowering component in the coloring-lowering solvent is preferably 1% by mass or more, more preferably 5% by mass or more, and is preferably 60% by mass or less, preferably 50% by mass or less.
- ⁇ Preparation of acrylic polymer P1 > 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2- Hydroxyethyl (HEA) 13 parts by mass, N-vinyl-2-pyrrolidone (NVP) 15 parts by mass, and 2,2'-azobisisobutyronitrile (AIBN) 0.2 parts by mass as a polymerization initiator , and 233 parts by mass of ethyl acetate as a solvent were stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). This gave a first polymer solution containing the acrylic polymer P1.
- the weight average molecular weight (Mw) of acrylic polymer P1 in the first polymer solution was 1.2 million.
- Adhesive composition C2 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of a radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was further added as a coloring-reducing component. did.
- a radical trapping agent trade name “Tinuvin 249”, manufactured by BASF
- Adhesive composition C3 was prepared in the same manner as adhesive composition C1 , except that 8 parts by mass of a radical trapping agent (trade name "Tinuvin 249", manufactured by BASF) was further added as a coloring - reducing component. did.
- ⁇ Preparation of adhesive composition C4 In the second polymer solution containing the acrylic polymer P2, an isocyanate cross-linking agent (trade name “Coronate HX”, isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) is added as a cross-linking agent per 100 parts by mass of the acrylic polymer P2.
- an isocyanate cross-linking agent (trade name “Coronate HX”, isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) is added as a cross-linking agent per 100 parts by mass of the acrylic polymer P2.
- Adhesive composition C5 was prepared in the same manner as adhesive composition C4 except that the amount of the radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was changed to 8 parts by mass instead of 4 parts by mass. was prepared.
- the radical trapping agent trade name “Tinuvin 249”, manufactured by BASF
- ⁇ Preparation of adhesive composition C6 > In the second polymer solution containing the acrylic polymer P2, 0.25 parts by mass of an isocyanate cross-linking agent (trade name "Coronate HX", manufactured by Tosoh Corporation) per 100 parts by mass of the acrylic polymer P2 (in terms of solid content) is added as a cross-linking agent. amount), 0.01 parts by mass (in terms of solid content) of dibutyltin dilaurate (trade name “OL-1”, manufactured by Tokyo Fine Chemical Co., Ltd.) as a cross-linking catalyst, and 3 parts by mass of acetylacetone as a cross-linking inhibitor. and mixed together to prepare adhesive composition C6 .
- an isocyanate cross-linking agent trade name "Coronate HX", manufactured by Tosoh Corporation
- dibutyltin dilaurate trade name “OL-1”, manufactured by Tokyo Fine Chemical Co., Ltd.
- Adhesive Composition C7 was prepared in the same manner as Adhesive Composition C6, except that a third polymer solution was used in place of the second polymer solution.
- Adhesive composition C8 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
- Adhesive composition C9 was prepared in the same manner as adhesive composition C1, except that 8 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
- an ultraviolet absorber trade name "Tinuvin 571", manufactured by BASF
- composition C11 ⁇ Preparation of adhesive composition C11 > Radical trap agent (Tinuvin 249) In place of 4 parts by mass, an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) 8 parts by mass was used. Composition C11 was prepared.
- Adhesive composition C1 was applied onto the release - treated surface of a 38 ⁇ m-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. The coating was then dried by heating at 132°C for 3 minutes. Thus, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m was formed on the base film. Next, the release-treated surface of a 38 ⁇ m-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together.
- MRF#38 polyester film, manufactured by Mitsubishi Plastics Co., Ltd.
- a color-changeable pressure-sensitive adhesive sheet R1 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C2 was used instead of the pressure - sensitive adhesive composition C1.
- a color-changeable pressure-sensitive adhesive sheet R2 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure - sensitive adhesive composition C3 was used instead of the pressure - sensitive adhesive composition C1.
- a color-changeable pressure - sensitive adhesive sheet R3 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C8 was used instead of the pressure - sensitive adhesive composition C1.
- a color-changeable pressure-sensitive adhesive sheet R4 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C9 was used instead of the pressure - sensitive adhesive composition C1.
- Adhesive composition C4 was applied onto the release-treated surface of a 38 ⁇ m-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. Next, the coating film was allowed to stand at room temperature for 10 minutes, then dried by heating at 80° C. for 5 minutes and then heating at 130° C. for 1 minute. Thus, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m was formed on the base film.
- the release-treated surface of a 38 ⁇ m-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together. After that, aging treatment was performed at 60° C. for 24 hours to advance the cross-linking reaction in the pressure-sensitive adhesive layer. As described above, a deactivating pressure-sensitive adhesive sheet D 1 (thickness: 25 ⁇ m) with a protective film was produced.
- Deactivated adhesive sheet D2 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C5 was used instead of adhesive composition C4 .
- Deactivated adhesive sheet D3 with a protective film was prepared in the same manner as deactivated adhesive sheet D1 , except that adhesive composition C10 was used instead of adhesive composition C4 .
- Deactivated adhesive sheet D4 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C11 was used instead of adhesive composition C4 .
- Example 1 A laminate L 1 was obtained from the color-changeable adhesive sheet X 1 and the deactivating adhesive sheet D 1 in the following manner.
- the color-changeable pressure-sensitive adhesive sheet X1 was prepared (first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on eagle glass and peeling off the release film from the deactivating adhesive sheet D1, the deactivating adhesive sheet D1 is applied to the color - changeable adhesive sheet X1. were pasted together (second step).
- the laminate L1 of Example 1 was obtained.
- the laminate L 1 includes, in order, eagle glass, a color-changeable adhesive sheet X 1 (25 ⁇ m thick), a disabling adhesive sheet D 1 (25 ⁇ m thick), and a base film.
- Laminate L1 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D1.
- Example 2 A laminate L2 of Example 2 was obtained by carrying out the same steps as in Example 1 , except that the deactivated adhesive sheet D2 was used instead of the deactivated adhesive sheet D1 in the second step.
- Laminate L2 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D2, and a base film.
- Laminate L2 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
- Laminate L3 of Example 3 was obtained by performing the same steps as in Example 1 , except that in the second step, the deactivated adhesive sheet D3 was used instead of the deactivated adhesive sheet D1. .
- Laminate L3 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film.
- Laminate L3 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D3 .
- Laminate L4 of Example 4 was obtained by carrying out the same steps as in Example 1 , except that in the second step, deactivated adhesive sheet D4 was used instead of deactivated adhesive sheet D1. .
- Laminate L4 comprises, in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film.
- Laminate L 4 includes a laminate of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 4 .
- Laminate L 5 comprises, in order, eagle glass, color-changeable adhesive sheet X 1 and substrate film (without disabling adhesive sheet).
- Example 5 A laminate L6 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D1 in the following manner. First, the laminate L 1 (Eagle glass/color-changeable pressure-sensitive adhesive sheet X 1 /disabling pressure-sensitive adhesive sheet D 1 /base film) of Example 1 was prepared. Next, the base film was peeled off from the deactivated pressure-sensitive adhesive sheet D- 1 in this laminate L- 1 .
- a triacetyl cellulose (TAC) film (trade name “KC2UA”, thickness 28 ⁇ m, manufactured by Konica Minolta) and an adhesive tape having an ultraviolet absorption function (trade name “CS9934U”) , manufactured by Nitto Denko) and a polyethylene terephthalate (PET) film (trade name “G981 E75”, thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Corporation) were laminated in this order.
- TAC triacetyl cellulose
- CS9934U an adhesive tape having an ultraviolet absorption function
- PET polyethylene terephthalate
- Laminate L 6 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 ⁇ m), deactivating adhesive sheet D 1 (thickness 25 ⁇ m), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order. Laminate L 6 includes a laminated sheet of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 1 .
- Laminate L 7 is composed of Eagle glass, color-changeable adhesive sheet X 1 (thickness 25 ⁇ m), deactivating adhesive sheet D 2 (thickness 25 ⁇ m), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order.
- Laminate L7 includes a laminate of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
- Laminate L 8 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 ⁇ m), TAC film, UV-absorbing adhesive tape, and PET film (base film) in this order (disabling adhesive without a seat).
- Example 7 A laminate L9 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D3 in the following manner.
- the color-changeable pressure-sensitive adhesive sheet X1 was prepared (first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.).
- the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass was irradiated with ultraviolet rays (UV) (second step). Specifically, under an environment of 23° C. and a relative humidity of 50%, the color-changeable pressure - sensitive adhesive sheet X1 on eagle glass was irradiated with UV from the base film side (the side opposite to the eagle glass). As a result, in the color-changeable pressure-sensitive adhesive sheet X1, an acid was generated from the photoacid generator, and the leuco dye was colored by the acid.
- UV ultraviolet rays
- a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm.
- the integrated irradiation light amount was set to 8000 mJ/cm 2 .
- the disabling adhesive sheet D3 is applied to the color - changeable adhesive sheet X1. were pasted together (third step).
- a TAC film (trade name “KC2UA”, thickness 28 ⁇ m, manufactured by Konica Minolta Co., Ltd.) and an ultraviolet An adhesive tape (trade name: “CS9934U”, manufactured by Nitto Denko Corporation) having an absorption function and a PET film (trade name: "G981 E75", thickness: 75 ⁇ m, manufactured by Mitsubishi Chemical Corporation) were laminated in this order.
- Laminate L 9 includes eagle glass, colored variable color adhesive sheet X 1 (25 ⁇ m thick), deactivated adhesive sheet D 3 (25 ⁇ m thick), TAC film, and UV-absorbing adhesive tape.
- a PET film (base film) is provided in order.
- Laminate L 9 comprises a laminated sheet of colored variable color adhesive sheet X 1 and deactivating adhesive sheet D 3 .
- Laminate L10 of Example 8 was obtained by carrying out the same steps as in Example 7, except that the deactivated adhesive sheet D4 was used instead of the deactivated adhesive sheet D3 in the third step.
- Laminate L 10 includes eagle glass, colored variable color adhesive sheet X 1 (thickness 25 ⁇ m), deactivation adhesive sheet D 4 (thickness 25 ⁇ m), TAC film, UV-absorbing adhesive tape, A PET film (base film) is provided in order.
- Laminate L 10 comprises a laminated sheet of colored variable color adhesive sheet X 1 and deactivating adhesive sheet D 4 .
- Comparative Example 3 A laminate L- 11 of Comparative Example 3 was obtained by carrying out the same steps as in Example 7, except that the third step (bonding of the deactivating pressure-sensitive adhesive sheet D3) was not carried out.
- the laminate L 11 includes eagle glass, a colored variable-color adhesive sheet X 1 (thickness 25 ⁇ m), a TAC film, an ultraviolet-absorbing adhesive tape, and a PET film (base film) in this order. not equipped with a utilization adhesive sheet).
- a laminate L 12 was obtained from the color-changeable adhesive sheet X 1 , the deactivating adhesive sheet D 1 , and the mask film in the following manner.
- a color-changeable pressure-sensitive adhesive sheet X 1 (50 mm ⁇ 100 mm) was prepared (first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.).
- Laminate L12 comprises, in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D1, and base film.
- Laminate L12 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D1.
- Example 10 The same steps as in Example 9 were carried out except that the deactivated adhesive sheet D 2 (50 mm ⁇ 100 mm) was used instead of the deactivated adhesive sheet D 1 in the second step, and the laminate of Example 10 was obtained.
- L13 was obtained.
- Laminate L13 comprises , in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D2, and base film.
- Laminate L13 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D2.
- Laminate L14 of Comparative Example 4 was obtained by performing the same steps as in Example 9.
- Laminate L 14 comprises eagle glass, color-changeable adhesive sheet X 1 , mask film for partially masking color-changeable adhesive sheet X 1 , and base film in order (without deactivating adhesive sheet). .
- Laminate L15 of Example 11 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E1 was used instead of the deactivating adhesive sheet D1 in the second step.
- the laminate L 15 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 1 , and a base film.
- the laminate L 15 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 1 .
- Example 12 A laminate L16 of Example 12 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E2 was used instead of the deactivating adhesive sheet D1 in the second step. .
- the laminate L 16 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 2 , and a base film.
- the laminate L 16 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 2 .
- Example 13 A laminate L17 of Example 13 was obtained as follows. First , a variable color pressure-sensitive adhesive sheet X1 was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass, the color-changeable pressure - sensitive adhesive sheet X1 was immersed in ethanol together with the eagle glass (immersion treatment as a treatment for reducing coloring property). The immersion time was 2 minutes.
- the color-changeable pressure - sensitive adhesive sheet X1 with eagle glass was removed from ethanol and dried by heating at 132° C. for 3 minutes.
- a 38 ⁇ m-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was attached to the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass.
- a laminate L17 of Example 13 was obtained.
- the laminate L 17 comprises, in order, eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a base film.
- Example 14 A laminate L18 of Example 14 was obtained in the same manner as in Example 13, except that ethyl acetate was used in place of ethanol in the color reduction treatment.
- Laminate L 18 comprises, in order, eagle glass, a color-changing adhesive sheet X 1 that has undergone immersion in ethyl acetate, and a base film.
- Example 15 A laminate L19 of Example 15 was obtained as follows. First, a variable color adhesive sheet X 1 (50 mm ⁇ 100 mm) was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on the eagle glass, a 25 ⁇ m-thick mask film (trade name “Lumirror S10”, 50 mm ⁇ 50 mm, transparent polyester film, Toray) was placed on the same sheet. company) was laminated.
- Eagle Glass thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.
- the color-changeable pressure - sensitive adhesive sheet X1 whose surface (the surface opposite to the eagle glass side surface) was partially masked by the mask film was immersed in ethanol together with the eagle glass (as a coloration reduction treatment, immersion treatment). The immersion time was 2 minutes.
- the color-changeable pressure-sensitive adhesive sheet X 1 with eagle glass (the surface was partially masked with a mask film) was taken out of the ethanol and dried by heating at 132° C. for 3 minutes.
- a base film with a thickness of 38 ⁇ m (trade name “MRF # 38”, polyester film, Mitsubishi Resin Co., Ltd.) was pasted together. As described above, the laminate L19 of Example 15 was obtained.
- Laminate L 19 comprises, in order, Eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a mask film and a base film on the same sheet.
- Laminate L 19 includes a laminated sheet of color-changeable adhesive sheet X 1 that has undergone ethanol immersion and a mask film.
- Reference Example 1 A laminate L21 of Reference Example 1 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R1 was used instead of the color - changeable adhesive sheet X1.
- Laminate L21 includes Eagle glass, color-changeable pressure-sensitive adhesive sheet R1 , and base film in this order.
- Laminate L22 of Reference Example 2 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R2 was used instead of the color - changeable adhesive sheet X1.
- Laminate L22 comprises, in order, Eagle glass, color-changeable adhesive sheet R2 , and base film.
- Reference Example 3 A laminate L23 of Reference Example 3 was obtained by performing the same step as the first step of Example 1, except that the color-changeable adhesive sheet R3 was used instead of the color - changeable adhesive sheet X1.
- Laminate L 23 includes Eagle glass, color-changeable adhesive sheet R 3 and base film in this order.
- Reference Example 4 A laminate L24 of Reference Example 4 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R4 was used instead of the color - changeable adhesive sheet X1.
- Laminate L 24 comprises, in order, eagle glass, color-changeable adhesive sheet R 4 and base film.
- the laminate was irradiated with ultraviolet rays (UV) (first UV irradiation).
- UV ultraviolet rays
- the color-changeable pressure-sensitive adhesive sheet in the laminate was irradiated with UV from the base film side.
- an acid was generated from the photoacid generator, and the leuco dye was colored by the acid.
- a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm.
- the integrated irradiation light amount was set to 8000 mJ/cm 2 .
- the laminate was measured for average transmittance at a wavelength of 400 to 700 nm (second transmittance measurement).
- the apparatus and conditions used in this measurement are the same as the apparatus and conditions used in the first transmittance measurement.
- Table 1 shows the measured average transmittance as transmittance T 1 (%).
- the laminates L 1 to L 4 of Examples 1 to 4 had significantly smaller ⁇ T than the laminate L 5 of Comparative Example 1, and exhibited good discoloration suppression properties.
- the laminate L 5 of Comparative Example 1 (the color-reducing component is not blended in the color-changeable pressure-sensitive adhesive sheet) and the laminates L 21 to L 24 of Reference Examples 1-4 (the color-changeable pressure-sensitive adhesive sheet contains
- the difference in transmittance T1 from the sample containing the color-lowering component indicates the color-lowering performance of the color-lowering component.
- variable color adhesive sheets R 1 to R 4 since the coloring-reducing component exerts coloring-reducing performance, the transmittance decrease ⁇ T due to ultraviolet irradiation (external stimulus application) in the first system is UV irradiation (applying external stimulus) to the color-changeable adhesive sheets R 1 and R 2 (first system) of the laminates L 21 to L 24 and the color-changeable adhesive sheet X 1 (second system) of the same laminate L 5 is less than the decrease in transmittance ⁇ T' due to .
- the color-changeable pressure-sensitive adhesive sheet when the photoacid generator (first compound) and the color-developing compound (second compound) coexist with the color-reducing component before the coloring treatment, the color-changeable pressure-sensitive adhesive sheet is It can be seen that the coloring ability is low and coloring is difficult (Reference Examples 1 to 4).
- the predetermined region by impregnating the color-changing pressure-sensitive adhesive sheet after the predetermined region has been colored with the color-reducing component, the predetermined region can be sufficiently colored by exhibiting its coloring ability.
- the non-colored area transparent area
- can be prevented from being discolored present invention.
- the laminate was placed in the chamber of a weather resistance test device (trade name "Super Xenon Weather Meter SX75", manufactured by Suga Test Instruments Co., Ltd.). Specifically, the laminate was placed in the chamber such that the base film of the laminate was positioned on the light source (super xenon lamp) side. Next, in an environment of 55° C. and 55% relative humidity, the color-changeable pressure-sensitive adhesive sheet in the laminate was irradiated with light from a super xenon lamp (wavelength 300-400 nm) for 24 hours.
- a super xenon lamp wavelength 300-400 nm
- the laminates L 6 and L 7 of Examples 5 and 6 had a significantly smaller ⁇ T than the laminate L 8 of Comparative Example 2 and exhibited good discoloration suppressing properties.
- the laminates L 9 and L 10 of Examples 7 and 8 had a significantly smaller absolute value of ⁇ T than the laminate L 11 of Comparative Example 3, and exhibited good discoloration suppression properties. .
- the laminate was irradiated with ultraviolet rays (UV).
- UV irradiation method and conditions are the same as described above for the first UV irradiation.
- the average transmittance at a wavelength of 400 to 700 nm for each of the regions where the mask film is arranged (mask region) and the region where the mask film is not arranged (non-mask region) in the laminate is It was measured.
- the apparatus and conditions used in this measurement are the same as those used in the first and second transmittance measurements.
- Table 4 shows the measured average transmittance as transmittance T 1 (%).
- Table 4 also shows the difference in transmittance T1 between masked and unmasked areas (inter - regional transmittance difference).
- the laminate immediately after production was irradiated with ultraviolet rays (second UV irradiation), and then the average transmittance of the laminate was measured at a wavelength of 400 to 700 nm (fourth transmittance measurement).
- Another laminate after 48 hours from the production at 25 ° C. was irradiated with ultraviolet rays (third UV irradiation), and then the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (fifth transmittance measurement).
- Another laminate after 48 hours at 85 ° C. from the bonding in the second step is irradiated with ultraviolet rays (fourth UV irradiation), and then the laminate has an average transmittance at a wavelength of 400 to 700 nm.
- the equipment and conditions used for the second to fourth UV irradiations are the same as those used for the first UV irradiation.
- the equipment and conditions used in the fourth to sixth transmittance measurements are the same as those used in the first transmittance measurement. Let the average transmittance measured in the fourth transmittance measurement be the transmittance T 3 (%), let the average transmittance measured in the fifth transmittance measurement be the transmittance T 4 (%), and let the sixth transmittance Table 5 shows the average transmittance measured by transmittance measurement as transmittance T 5 (%).
- both the transmittance difference T 4 ⁇ T 3 and the transmittance difference T 5 ⁇ T 3 are significantly larger than the laminate L 5 of Comparative Example 1.
- a decrease in colorability (discoloration suppression property) was exhibited.
- the laminate L 16 of Example 11 had a high degree of deterioration in the colorability of the color-changeable pressure-sensitive adhesive sheet at higher temperatures (that is, the transmittance difference T 5 -T 3 was large), and exhibited excellent discoloration suppression properties. .
- the average transmittance at a wavelength of 400 to 700 nm was measured for the intermediate laminate obtained by laminating the color-changeable adhesive sheet X 1 (with a base film on one side) to Eagle Glass. (7th transmittance measurement).
- the laminate prepared through the coloring property reduction treatment is irradiated with ultraviolet rays (fifth UV irradiation), and then the average transmittance of the laminate at a wavelength of 400 to 700 nm is measured. (eighth transmittance measurement).
- an eighth transmittance measurement was performed for each of the region where the mask film was arranged (mask region) and the region where the mask film was not arranged (non-mask region).
- the equipment and conditions used in the fifth UV irradiation are the same as those used in the first UV irradiation.
- the apparatus and conditions used in the seventh and eighth transmittance measurements are the same as the apparatus and conditions used in the first transmittance measurement.
- Let the average transmittance measured in the seventh transmittance measurement be the transmittance T 6 (%), and let the average transmittance measured in the eighth transmittance measurement be the transmittance T 7 (%), Tables 6 and 7 shown in Table 6 also shows the difference ⁇ T ( T 7 -T 6 ) between the transmittances T 6 and T 7 .
- Table 6 also shows the transmittance measurement results (T 0 , T 1 , T 0 ⁇ T 1 ) shown in Table 1 for the laminate L 5 of Comparative Example 1 for comparison.
- Table 6 the laminates L 17 and L 18 of Examples 13 and 14 had significantly smaller ⁇ T than the laminate L 5 of Comparative Example 1, and exhibited good discoloration suppressing properties.
- Table 7 also shows the difference in transmittance T7 between the masked area and the non-masked area (transmittance difference between areas).
- Table 7 also shows the transmittance measurement results (T 0 , T 1 , transmittance difference between the masked area and the non-masked area) shown in Table 4 for the laminate L14 of Comparative Example 4 for comparison.
- T 0 , T 1 transmittance difference between the masked area and the non-masked area
- the method for suppressing discoloration of the color-changeable pressure-sensitive adhesive sheet and the laminated sheet of the present invention can be used, for example, in the manufacturing process of display panels.
- Color-changeable adhesive sheet Y Color-lowering sheet 11 First region (colored region) 12 Second area (non-colored area) 21 First member 22 Second member L Laminated sheet
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Abstract
This method includes a first step and a second step. In the first step is prepared a color-changeable pressure-sensitive adhesive sheet (X) which has the property of being colored by an external stimulus. The color-changeable pressure-sensitive adhesive sheet (X) includes a colored region (11) and an uncolored region (12). In the second step, a colorability-reducing medium for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet (X) is brought into contact with the color-changeable pressure-sensitive adhesive sheet (X).
Description
本発明は、可変色粘着シートの変色抑制方法および積層シートに関する。
The present invention relates to a method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet and a laminated sheet.
所定波長の光照射によって照射箇所を着色可能な透明な粘着シート（可変色粘着シート）が知られている。可変色粘着シートは、光照射に起因して当該粘着シートを着色させる事後的着色剤（成分または成分群）を含有する。
A transparent adhesive sheet (color-changeable adhesive sheet) that can color the irradiated area by irradiating light with a predetermined wavelength is known. A color-changeable adhesive sheet contains a post-colorant (component or components) that colors the adhesive sheet due to light irradiation.
一方、有機ＥＬパネルなどのディスプレイパネルは、画素パネルおよびカバー部材などを含む積層構造を有する。そのようなディスプレイパネルの製造過程では、積層構造に含まれる要素どうしの貼り合わせのために、例えば可変色粘着シートが用いられる。例えば、次のとおりである。
On the other hand, a display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover member. In the manufacturing process of such a display panel, for example, a color-changeable pressure-sensitive adhesive sheet is used for bonding the elements included in the laminated structure. For example:
まず、可変色粘着シートが被着体に貼り合わされる（貼合せ工程）。次に、被着体と可変色粘着シートとの間における異物および気泡の有無が、検査される。検査を通過しない場合、第１被着体から可変色粘着シートが剥がされ、その後、別の可変色粘着シートを用いて貼合せ工程がやり直される。検査を通過する場合、第１被着体上の可変色粘着シートの所定箇所に意匠性、遮蔽性、反射防止性などを付与するために、当該箇所が所定波長の光照射によって着色される。すなわち、可変色粘着シートに着色済領域が形成される。その後、第１被着体に対し、当該可変色粘着シートを介して第２被着体が接合される。例えばこのように用いられる可変色粘着シートは、例えば下記の特許文献１に記載されている。
First, the color-changeable adhesive sheet is attached to the adherend (lamination process). Next, the presence or absence of foreign matter and air bubbles between the adherend and the color-changeable pressure-sensitive adhesive sheet is inspected. If it does not pass the inspection, the color changeable adhesive sheet is peeled off from the first adherend, and then the lamination process is redone using another color changeable adhesive sheet. When passing the inspection, predetermined portions of the color-changeable pressure-sensitive adhesive sheet on the first adherend are colored by irradiation with light of a predetermined wavelength in order to impart design properties, shielding properties, antireflection properties, and the like. That is, a colored region is formed on the color-changeable pressure-sensitive adhesive sheet. After that, the second adherend is joined to the first adherend via the color-changeable pressure-sensitive adhesive sheet. For example, a color-changeable pressure-sensitive adhesive sheet used in this way is described, for example, in Patent Document 1 below.
可変色粘着シートにおいて、良好な着色性を実現するためには、事後的着色剤の配合量は多い方がよい。しかし、着色済領域の形成後の可変色粘着シートにおいては、事後的着色剤の配合量が多いほど、着色済領域が形成されていない領域（非着色済領域）が経時的に変色しやすい。非着色済領域の変色は、着色済領域および非着色済領域の機能の劣化を招き、好ましくない。
In order to achieve good colorability in the color-changeable pressure-sensitive adhesive sheet, it is better to add a large amount of post-coloring agent. However, in the color-changeable pressure-sensitive adhesive sheet after the formation of the colored regions, the larger the amount of the post-colorant compounded, the more likely the regions where the colored regions are not formed (non-colored regions) will discolor over time. Discoloration of the non-colored areas is undesirable because it leads to deterioration of the functionality of the colored and non-colored areas.
本発明は、外部刺激の付与によって着色可能な可変色粘着シートにおいて、着色済領域の良好な着色と、着色済領域形成後の非着色済領域の経時的な変色の抑制とを、両立するのに適した方法、および、これによって得られる積層シートを提供する。
INDUSTRIAL APPLICABILITY The present invention is a color-changeable pressure-sensitive adhesive sheet that can be colored by applying an external stimulus. and a laminated sheet obtained by the method.
本発明［１］は、外部刺激に因る着色性を有する可変色粘着シートであって、着色済領域と非着色済領域とを含む可変色粘着シートを、用意する第１工程と、前記可変色粘着シートの前記着色性を低下させるための着色性低下メディアを、前記可変色粘着シートに接触させる、第２工程とを含む、可変色粘着シートの変色抑制方法を含む。
The present invention [1] provides a color-changeable pressure-sensitive adhesive sheet having colorability due to an external stimulus, the color-changeable pressure-sensitive adhesive sheet including a colored region and a non-colored region; and a second step of contacting the color-changeable adhesive sheet with a color-lowering medium for reducing the colorability of the color-changeable adhesive sheet.
本方法では、第２工程において、着色済領域と非着色済領域とを含む可変色粘着シートに対し、当該粘着シートの着色性を低下させるための着色性低下メディアを接触させる。このような構成は、着色済領域と非着色済領域とを含む可変色粘着シートにおいて、非着色済領域の着色性を低下させて、非着色済領域の経時的な変色を抑制するのに適する。また、本方法では、そのような第２工程が後に実施される予定の下、第１工程において、着色済領域と非着色済領域とを含む可変色粘着シートが用意される。このような構成は、可変色粘着シートを、外部刺激に因る着色性が高くて着色済領域が良好に着色している粘着シートとして、用意するのに適する。着色済領域が良好に着色するほどに着色性が高い可変色粘着シートであっても、第２工程において着色性低下メディアとの接触によって着色性が低下されるため、当該第２工程後には、非着色済領域の経時的な変色が抑制される。このように、本方法は、外部刺激の付与によって着色可能な可変色粘着シートにおいて、着色済領域の良好な着色と、着色済領域形成後の非着色済領域の経時的な変色の抑制とを、両立するのに適する。
In this method, in the second step, a color-reducing medium for reducing the colorability of the pressure-sensitive adhesive sheet is brought into contact with the color-changeable pressure-sensitive adhesive sheet including the colored region and the non-colored region. Such a configuration is suitable for reducing the colorability of the non-colored regions in the color-changeable pressure-sensitive adhesive sheet including the colored regions and the non-colored regions, thereby suppressing the discoloration of the non-colored regions over time. . Also, in this method, a color-changeable pressure-sensitive adhesive sheet including colored regions and non-colored regions is prepared in the first step, with such a second step scheduled to be performed later. Such a configuration is suitable for preparing the color-changeable pressure-sensitive adhesive sheet as a pressure-sensitive adhesive sheet having a high colorability due to an external stimulus and having a well-colored colored region. Even if the color-changeable pressure-sensitive adhesive sheet has high colorability so that the colored region is well colored, the colorability is reduced by contact with the color-decreasing medium in the second step. Therefore, after the second step, Discoloration of the non-pigmented areas over time is suppressed. As described above, the method of the present invention achieves good coloring of the colored regions and suppression of discoloration over time of the non-colored regions after the formation of the colored regions in the variable color pressure-sensitive adhesive sheet that can be colored by applying an external stimulus. , suitable for compatibility.
本発明［２］は、前記可変色粘着シートが、外部刺激を受けて第１反応を生ずる第１化合物と、前記第１反応の生成物との第２反応によって発色する第２化合物とを含有する、上記［１］に記載の可変色粘着シートの変色抑制方法を含む。
In the present invention [2], the color-changeable pressure-sensitive adhesive sheet contains a first compound that undergoes a first reaction upon receiving an external stimulus, and a second compound that develops color through a second reaction with the product of the first reaction. and the method for suppressing discoloration of the color-changeable pressure-sensitive adhesive sheet according to [1] above.
このような構成によると、第１化合物と第２化合物との協働によって適切に着色させた可変色粘着シートを、第１工程において用意できる。
According to such a configuration, a color-changeable pressure-sensitive adhesive sheet appropriately colored by cooperation of the first compound and the second compound can be prepared in the first step.
本発明［３］は、前記第１化合物が光酸発生剤であり、前記第２化合物が、酸との反応により発色する発色性化合物である、上記［２］に記載の可変色粘着シートの変色抑制方法を含む。
The present invention [3] is the color-changeable pressure-sensitive adhesive sheet according to [2] above, wherein the first compound is a photoacid generator, and the second compound is a color-developing compound that develops color upon reaction with an acid. Including discoloration control method.
このような構成によると、上記外部刺激として光照射を利用して着色させた可変色粘着シートを、第１工程において用意できる。可変色粘着シートに対する所定波長の光照射により、当該照射箇所において、光酸発生剤から酸を発生させ、当該酸との反応によって発色性化合物を発色させて、当該箇所を着色できる。
According to such a configuration, the color-changeable adhesive sheet colored using light irradiation as the external stimulus can be prepared in the first step. By irradiating the color-changeable pressure-sensitive adhesive sheet with light of a predetermined wavelength, an acid is generated from the photoacid generator at the irradiated site, and the color-developing compound reacts with the acid to develop a color, thereby coloring the site.
本発明［４］は、前記第２工程では、前記可変色粘着シートから前記第１化合物を前記着色性低下メディアに抽出するか、または、前記着色性低下メディアが、前記着色性を低下させるための着色性低下成分を含有し、前記第２工程では、前記着色性低下成分を前記着色性低下メディアから前記可変色粘着シートに導入する、上記［２］または［３］に記載の可変色粘着シートの変色抑制方法を含む。
In the present invention [4], in the second step, the first compound is extracted from the color-changeable pressure-sensitive adhesive sheet into the reduced coloring medium, or the reduced coloring medium reduces the coloring. The color-reducing adhesive according to [2] or [3] above, wherein the coloring-reducing component is introduced from the coloring-reducing medium to the color-changeable adhesive sheet in the second step. Includes sheet discoloration suppression method.
このような構成は、第２工程において可変色粘着シートの着色性を低下させるのに適する。
Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step.
本発明［５］は、前記第１化合物、前記第２化合物、および前記着色性低下成分が共存する第１の系における前記外部刺激付与による透過率の低下ΔＴ１が、前記着色性低下成分が存在しないこと以外は前記第１の系と同じ第２の系における前記外部刺激付与と同じ外部刺激付与による透過率の低下ΔＴ２より小さい、上記［４］に記載の可変色粘着シートの変色抑制方法を含む。
The present invention [5] is a first system in which the first compound, the second compound, and the coloring-reducing component coexist, wherein the reduction in transmittance ΔT1 due to the application of the external stimulus is determined by the presence of the coloring-reducing component. The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to [4] above, which is smaller than the decrease ΔT2 in transmittance due to the application of the same external stimulus as the application of the external stimulus in the second system, which is the same as the first system except that the include.
このような構成は、第２工程において可変色粘着シートの着色性を低下させるのに適する。
Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step.
本発明［６］は、前記着色性低下成分が、紫外線吸収剤、中和剤、およびラジカルトラップ剤からなる群より選択される少なくとも一つを含む、上記［５］に記載の可変色粘着シートの変色抑制方法を含む。
The present invention [6] is the color-changeable pressure-sensitive adhesive sheet according to [5] above, wherein the coloring-lowering component contains at least one selected from the group consisting of an ultraviolet absorber, a neutralizing agent, and a radical trapping agent. including a discoloration suppression method.
このような構成は、上記第１成分として光酸発生剤を用いる場合において、第２工程で可変色粘着シートの着色性を低下させるのに適する。
Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet in the second step when a photoacid generator is used as the first component.
本発明［７］は、前記着色性低下メディアが着色性低下シートであり、前記第２工程では、前記着色性低下シートを前記可変色粘着シートに貼り合わせる、上記［１］から［６］のいずれか一つに記載の可変色粘着シートの変色抑制方法を含む。
The present invention [7] is the above-described [1] to [6], wherein the reduced-colorability medium is a reduced-colorability sheet, and in the second step, the reduced-colorability sheet is attached to the color-changeable pressure-sensitive adhesive sheet. A method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of the above is included.
このような構成は、可変色粘着シートが用いられるデバイスの製造過程で、効率よく第２工程を実施するのに適する。
Such a configuration is suitable for efficiently performing the second step in the manufacturing process of a device using a color-changeable adhesive sheet.
本発明［８］は、前記第２工程では、前記可変色粘着シートの前記着色済領域の少なくとも一部と前記着色性低下シートとの間にマスク材を介在させた状態で、前記着色性低下シートを前記可変色粘着シートに貼り合わせる、上記［７］に記載の可変色粘着シートの変色抑制方法を含む。
In the present invention [8], in the second step, a mask material is interposed between at least a part of the colored region of the color-changeable pressure-sensitive adhesive sheet and the reduced coloring sheet. The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to [7] above, wherein a sheet is attached to the color-changeable pressure-sensitive adhesive sheet.
このような構成は、第２工程において、可変色粘着シートの着色性低下箇所を制御するのに適する。
Such a configuration is suitable for controlling portions of the color-changeable pressure-sensitive adhesive sheet in which the colorability is lowered in the second step.
本発明［９］は、前記着色性低下シートが、極性基含有ポリマーを含有する、上記［７］または［８］に記載の可変色粘着シートの変色抑制方法を含む。
The present invention [9] includes the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to [7] or [8] above, wherein the color-reducing sheet contains a polar group-containing polymer.
このような構成は、第２工程において、可変色粘着シートから第１化合物を着色性低下シートに抽出するのに適する。
Such a configuration is suitable for extracting the first compound from the color-changeable pressure-sensitive adhesive sheet to the color-reducing sheet in the second step.
本発明［１０］は、前記着色性低下シートが粘着シートである、上記［７］から［９］のいずれか一つに記載の可変色粘着シートの変色抑制方法を含む。
The present invention [10] includes the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of [7] to [9] above, wherein the reduced-colorability sheet is a pressure-sensitive adhesive sheet.
このような構成は、第２工程において、可変色粘着シートに対して着色性低下シートを高密着させるのに適する。また、当該構成は、第２工程で得られる積層シート（可変色粘着シートと着色性低下シートとの積層体）を両面粘着シートとして機能させるのに適する。
Such a configuration is suitable for highly adhering the color-reducing sheet to the color-changeable pressure-sensitive adhesive sheet in the second step. Moreover, this configuration is suitable for making the laminated sheet (laminated body of the color-changeable adhesive sheet and the color-reducing sheet) obtained in the second step function as a double-sided adhesive sheet.
本発明［１１］は、前記着色性低下メディアが着色性低下溶媒である、上記［１］から［６］のいずれか一つに記載の変色抑制方法を含む。
The present invention [11] includes the method for suppressing discoloration according to any one of [1] to [6] above, wherein the reduced-coloring medium is a reduced-coloring solvent.
このような構成は、第２工程を効率よく実施するのに好ましい。
Such a configuration is preferable for efficiently performing the second step.
本発明［１２］は、上記［７］から［１０］のいずれか一つに記載の可変色粘着シートの変色抑制方法によって得られる積層シートであって、前記可変色粘着シートと、前記可変色粘着シートに貼り合わされた前記着色性低下シートとを備える、積層シートを含む。
The present invention [12] is a laminated sheet obtained by the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to any one of [7] to [10] above, comprising: the color-changeable pressure-sensitive adhesive sheet; A laminated sheet comprising the coloring-impaired sheet attached to an adhesive sheet.
このような積層シートは、着色済領域の良好な着色と非着色済領域の変色抑制とが両立された可変色粘着シートを、ディスプレイパネルなどのデバイスの構造部材として組み付けるのに適する。
Such a laminated sheet is suitable for assembling a color-changeable pressure-sensitive adhesive sheet that satisfies both good coloring of colored regions and suppression of discoloration of non-colored regions as a structural member of a device such as a display panel.
本発明の可変色粘着シートの変色抑制方法は、第１工程と第２工程とを含む。
The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet of the present invention includes a first step and a second step.
まず、第１工程では、図１に示すように、可変色粘着シートＸを用意する。
First, in the first step, as shown in FIG. 1, a color-changeable adhesive sheet X is prepared.
可変色粘着シートＸは、所定の厚さのシート形状を有し、厚さ方向と直交する方向（面方向）に延びる。可変色粘着シートＸは、第１粘着性組成物から形成されている。また、可変色粘着シートＸは、外部刺激に因る着色性を有する粘着シートであり、既に着色された第１領域１１（着色済領域）と、第１領域１１が形成されていない第２領域１２（非着色済領域）とを含む。第２領域１２は、好ましくは透明性（可視光透過性）を有する。可変色粘着シートＸは、本実施形態では、ベースポリマーと、外部刺激を受けて第１反応を生ずる第１化合物と、第１反応の生成物との第２反応によって発色する第２化合物とを含有する。このような構成によると、第１化合物と第２化合物との協働によって適切に着色させた可変色粘着シートＸを、第１工程において用意できる。
The variable color adhesive sheet X has a sheet shape with a predetermined thickness and extends in a direction (plane direction) perpendicular to the thickness direction. The color-changeable adhesive sheet X is formed from the first adhesive composition. Also, the color-changeable adhesive sheet X is an adhesive sheet that is colored by an external stimulus. 12 (uncolored areas). The second region 12 preferably has transparency (visible light transmittance). In this embodiment, the color-changeable pressure-sensitive adhesive sheet X comprises a base polymer, a first compound that undergoes a first reaction upon receiving an external stimulus, and a second compound that develops color through a second reaction with the product of the first reaction. contains. According to such a configuration, the color-changeable pressure-sensitive adhesive sheet X appropriately colored by cooperation of the first compound and the second compound can be prepared in the first step.
外部刺激としては、可変色粘着シートＸが含有する成分に応じて、例えば、光照射および加熱が挙げられる。光照射における光の種類としては、例えば、紫外線、可視光、および赤外線が挙げられ、使用設備の多様性の観点から紫外線が好ましい。可変色粘着シートＸにおいて、好ましくは、第１化合物が光酸発生剤であり、且つ、第２化合物が、酸との反応により発色する発色性化合物である。このような構成によると、上記外部刺激として光照射を利用して着色させた可変色粘着シートＸを、第１工程において用意できる。可変色粘着シートＸに対する所定波長の光照射により、当該照射箇所において、光酸発生剤から酸を発生させ、当該酸との反応によって発色性化合物を発色させて、当該箇所を着色できる。可変色粘着シートＸの成分は、より具体的には、後述のとおりである。
Examples of external stimuli include light irradiation and heating, depending on the components contained in the color-changeable adhesive sheet X. Types of light for light irradiation include, for example, ultraviolet light, visible light, and infrared light, and ultraviolet light is preferable from the viewpoint of the diversity of equipment used. In the color-changeable pressure-sensitive adhesive sheet X, preferably, the first compound is a photoacid generator, and the second compound is a color-developing compound that develops color upon reaction with acid. With such a configuration, the color-changeable adhesive sheet X colored by using light irradiation as the external stimulus can be prepared in the first step. By irradiating the color-changeable pressure-sensitive adhesive sheet X with light of a predetermined wavelength, an acid is generated from the photoacid generator at the irradiated portion, and the color-developing compound reacts with the acid to develop a color, thereby coloring the portion. More specifically, the components of the color-changeable pressure-sensitive adhesive sheet X are as described below.
第１工程において、可変色粘着シートＸは、所定の被着体に貼り合わされていてもよい。図１は、可変色粘着シートＸが、第１部材２１の厚さ方向Ｔの一方面に貼り合わされている状態を、例示的に示す。第１部材２１は、例えば、有機ＥＬパネルなどのディスプレイパネルである。第１部材２１は、他の電子デバイスであってもよいし、光学デバイスであってもよい。好ましくは、可変色粘着シートＸが被着体に貼り合わされた後に、可変色粘着シートＸの所定箇所に外部刺激が付与されて、第１領域１１が形成される。第１部材２１に対する可変色粘着シートＸの貼り合わせの後、好ましくは第１領域１１の形成前に、第１部材２１と可変色粘着シートＸとの間における異物および気泡の有無が検査される。
In the first step, the color-changeable pressure-sensitive adhesive sheet X may be attached to a predetermined adherend. FIG. 1 exemplarily shows a state in which the color-changeable adhesive sheet X is attached to one surface of the first member 21 in the thickness direction T. As shown in FIG. The first member 21 is, for example, a display panel such as an organic EL panel. The first member 21 may be another electronic device or an optical device. Preferably, after the color-changeable pressure-sensitive adhesive sheet X is attached to the adherend, an external stimulus is applied to a predetermined portion of the color-changeable pressure-sensitive adhesive sheet X to form the first region 11 . After bonding the color-changeable adhesive sheet X to the first member 21, preferably before forming the first region 11, the presence or absence of foreign substances and air bubbles between the first member 21 and the color-changeable adhesive sheet X is inspected. .
次に、第２工程では、そのような可変色粘着シートＸに対して、可変色粘着シートＸの着色性を低下させるための着色性低下メディアを接触させる。
Next, in the second step, such a color-changeable pressure-sensitive adhesive sheet X is brought into contact with a color-lowering medium for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet X.
着色性低下メディアとしては、失活用メディアおよび抽出用メディアが挙げられる。失活用メディアとは、可変色粘着シートＸの着色性を低下させるための着色性低下成分を含有し、当該成分を可変色粘着シートＸに導入するためのメディアである（失活用メディアは、可変色粘着シートＸの機能としての着色性の阻害・失活のためのメディアである）。可変色粘着シートＸと、当該シートに接触する失活用メディアとからなる系では、系内における着色性低下成分の濃度分布の偏りが小さくなるように、着色性低下成分の拡散が生じる。これにより、失活用メディアから可変色粘着シートＸに着色性低下成分を導入できる（導入機能）。一方、抽出用メディアは、可変色粘着シートＸから上述の第１化合物を抽出して可変色粘着シートＸの着色性を低下させるためのメディアである。可変色粘着シートＸと、当該シートに接触する抽出用メディアとからなる系では、系内における第１化合物の濃度分布の偏りが小さくなるように、第１化合物の拡散が生じる。これにより、可変色粘着シートＸから抽出用メディアに第１化合物を抽出できる（抽出機能）。上述の失活用メディアは、このような抽出機能と上述の導入機能とを併有する場合、抽出用メディアを兼ねる。以上のような失活用メディアおよび抽出用メディアは、第２工程において、可変色粘着シートＸの着色性を低下させるのに適する。また、着色性低下メディアとしては、着色性低下シートおよび着色性低下溶媒が挙げられる。すなわち、着色性低下メディアには、失活用シート、抽出用シート、失活用溶媒、および抽出用溶媒が含まれる。着色性低下シートは、本実施形態では、粘着シートである。
Discoloration media and extraction media are included as media with reduced coloration. The deactivating medium is a medium that contains a coloring property-reducing component for deteriorating the coloring property of the color-changeable adhesive sheet X, and is a medium for introducing the component into the color-changeable adhesive sheet X (the deactivating media is a variable It is a medium for inhibiting/deactivating coloring as a function of the colored adhesive sheet X). In a system composed of the color-changeable pressure-sensitive adhesive sheet X and the deactivating medium in contact with the sheet, diffusion of the color-reducing component occurs so that the concentration distribution of the color-reducing component in the system becomes less biased. As a result, it is possible to introduce the color-lowering component from the deactivating medium to the color-changeable pressure-sensitive adhesive sheet X (introduction function). On the other hand, the extraction medium is a medium for extracting the first compound from the color-changeable adhesive sheet X to reduce the colorability of the color-changeable adhesive sheet X. FIG. In a system consisting of the color-changeable pressure-sensitive adhesive sheet X and an extraction medium in contact with the sheet, the first compound diffuses so that the concentration distribution of the first compound in the system is less biased. Thereby, the first compound can be extracted from the color-changeable adhesive sheet X to the extraction medium (extraction function). The disused media described above also serves as media for extraction when it has such an extraction function and the introduction function described above. The above deactivation media and extraction media are suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet X in the second step. Moreover, the coloring-impaired media include a coloring-impairing sheet and a coloring-impairing solvent. That is, the color-reducing media includes deactivating sheets, extracting sheets, deactivating solvents, and extracting solvents. The color-reducing sheet is a pressure-sensitive adhesive sheet in this embodiment.
図２は、着色性低下メディアとしての着色性低下シートＹを、第２工程で用いる場合を表す。この場合、第２工程では、可変色粘着シートＸの厚さ方向Ｔの一方面に着色性低下シートＹを貼り合わせる。着色性低下シートＹは、所定の厚さのシート形状を有し、厚さ方向と直交する方向（面方向）に延びる。着色性低下シートＹは、本実施形態では、第２粘着性組成物から形成された粘着シートである。また、本工程により、積層シートＬが得られる。積層シートＬは、可変色粘着シートＸと、可変色粘着シートＸに貼り合わされた着色性低下シートＹとを備える。
FIG. 2 shows the case where the coloring-impaired sheet Y as the coloring-impaired medium is used in the second step. In this case, in the second step, the color-reducing sheet Y is adhered to one side of the color-changeable pressure-sensitive adhesive sheet X in the thickness direction T. As shown in FIG. The coloring-reduced sheet Y has a sheet shape with a predetermined thickness and extends in a direction (surface direction) perpendicular to the thickness direction. The coloring-impaired sheet Y is a pressure-sensitive adhesive sheet formed from the second pressure-sensitive adhesive composition in this embodiment. Moreover, the lamination sheet L is obtained by this process. The laminated sheet L includes a color-changeable pressure-sensitive adhesive sheet X and a color-lowering sheet Y attached to the color-changeable pressure-sensitive adhesive sheet X.
可変色粘着シートＸに対して着色性低下シートＹを接触させる時間は、好ましくは１分以上、より好ましくは３分以上、更に好ましくは５分以上である。可変色粘着シートＸから着色性低下シートＹが事後的に剥離される場合、接触時間は、好ましくは７２時間以下、より好ましくは４８時間以下、更に好ましくは２４時間以下、特に好ましくは１２時間以下である。
The time for which the color-reducing adhesive sheet Y is brought into contact with the color-changeable pressure-sensitive adhesive sheet X is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 minutes or longer. When the color-reducing sheet Y is subsequently removed from the color-changeable pressure-sensitive adhesive sheet X, the contact time is preferably 72 hours or less, more preferably 48 hours or less, even more preferably 24 hours or less, and particularly preferably 12 hours or less. is.
着色性低下メディアとして着色性低下溶媒を第２工程で用いる場合、第２工程では、可変色粘着シートＸに対して着色性低下溶媒を接触させる。着色性低下溶媒の成分は、具体的には後述のとおりである。接触方法としては、例えば、着色性低下溶媒に対す可変色粘着シートＸの浸漬、および、可変色粘着シートＸに対する着色性低下溶媒の噴霧が挙げられる。
When using the coloring-lowering solvent as the coloring-lowering medium in the second step, the color-changeable pressure-sensitive adhesive sheet X is brought into contact with the coloring-lowering solvent in the second step. The specific components of the coloring-reducing solvent are as described below. The contact method includes, for example, immersing the color-changeable pressure-sensitive adhesive sheet X in the color-reducing solvent and spraying the color-changeable pressure-sensitive adhesive sheet X with the color-reducing solvent.
可変色粘着シートＸに対して着色性低下溶媒を接触させる時間は、好ましくは１分以上、より好ましくは３分以上、更に好ましくは５分以上である。当該接触時間は、好ましくは７２時間以下、より好ましくは４８時間以下、更に好ましくは２４時間以下、特に好ましくは１２時間以下である。
The time for which the color-changing pressure-sensitive adhesive sheet X is brought into contact with the color-reducing solvent is preferably 1 minute or longer, more preferably 3 minutes or longer, and even more preferably 5 minutes or longer. The contact time is preferably 72 hours or less, more preferably 48 hours or less, still more preferably 24 hours or less, and particularly preferably 12 hours or less.
第２工程では、可変色粘着シートＸおよび着色性低下メディア（図２では着色性低下シートＹ）を加熱するのが好ましい。着色性低下メディアとして失活用メディアを用いる場合、加熱により、失活用メディア中の着色性低下成分の、可変色粘着シートＸへの移動が促進される。着色性低下メディアとして抽出用メディアを用いる場合、加熱により、可変色粘着シートＸ中の第１成分の、抽出用メディアへの移動が促進される。第２工程での加熱温度は、好ましくは３０℃以上、より好ましくは５０℃以上であり、また、好ましくは１５０℃以下、より好ましくは１００℃以下である。
In the second step, it is preferable to heat the color-changeable pressure-sensitive adhesive sheet X and the reduced-colorability medium (the reduced-colorability sheet Y in FIG. 2). When disabling media is used as the color-reducing media, the heating promotes the movement of the color-reducing components in the disabling media to the color-changeable pressure-sensitive adhesive sheet X. FIG. When an extraction medium is used as the color-lowering medium, heating promotes the movement of the first component in the color-changeable pressure-sensitive adhesive sheet X to the extraction medium. The heating temperature in the second step is preferably 30° C. or higher, more preferably 50° C. or higher, and preferably 150° C. or lower, more preferably 100° C. or lower.
本方法では、上述のように、第２工程において、第１領域１１（着色済領域）と第２領域１２（非着色済領域）とを含む可変色粘着シートＸに対し、当該粘着シートの着色性を低下させるための着色性低下メディアを接触させる。このような構成は、第１領域１１と第２領域１２とを含む可変色粘着シートＸにおいて、第２領域１２の着色性を低下させて、第２領域１２の経時的な変色を抑制するのに適する。加えて、当該構成は、第１領域１１の着色性を低下させて当該第１領域１１の経時的な変色を抑制することや、第１領域１１内で発色している第２化合物（着色成分）の劣化を抑制することに適し、従って、第１領域１１の着色安定性を確保するのにも適する（具体的には、例えば後記の実施例７,８および比較例３を以って示すとおりである）。すなわち、本方法は、着色済領域を有する可変色粘着シートＸの着色安定化方法としても、実施できる。着色済領域が可変色粘着シートＸにおいて全面的に形成されている場合であっても、当該着色済領域の着色安定化効果を享受できる。可変色粘着シートＸの着色済領域の着色安定化は、可変色粘着シートＸの用途に応じた着色済領域の機能（意匠性、遮蔽性、反射防止性など）の確保の観点から好ましい。
In this method, as described above, in the second step, the color-changeable adhesive sheet X including the first region 11 (colored region) and the second region 12 (non-colored region) is colored. A color reducing medium for reducing the properties is brought into contact. Such a configuration reduces the colorability of the second region 12 in the color-changeable pressure-sensitive adhesive sheet X including the first region 11 and the second region 12, thereby suppressing the discoloration of the second region 12 over time. Suitable for In addition, the configuration reduces the colorability of the first region 11 to suppress discoloration of the first region 11 over time, and the second compound (coloring component ), and therefore also suitable for ensuring the coloring stability of the first region 11 (specifically, for example, shown in Examples 7 and 8 and Comparative Example 3 below) as follows). That is, this method can also be implemented as a method for stabilizing coloring of the color-changeable pressure-sensitive adhesive sheet X having a colored region. Even when the colored region is formed on the entire surface of the color-changeable adhesive sheet X, the effect of stabilizing the coloring of the colored region can be obtained. Color stabilization of the colored regions of the color-changeable pressure-sensitive adhesive sheet X is preferable from the viewpoint of ensuring the functions (design, shielding, antireflection, etc.) of the colored regions according to the application of the color-changeable pressure-sensitive adhesive sheet X.
また、本方法では、そのような第２工程が後に実施される予定の下、第１工程において、第１領域１１と第２領域１２とを含む可変色粘着シートＸが用意される。このような構成は、可変色粘着シートＸを、外部刺激に因る着色性が高くて第１領域１１が良好に着色している粘着シートとして、用意するのに適する（可変色粘着シートＸにおける第１化合物および／または第２化合物の含有量が多いほど、可変色粘着シートＸの着色性は高い）。第１領域１１が良好に着色するほどに第１化合物および／または第２化合物の含有量が多くて着色性が高い可変色粘着シートＸであっても、第２工程において着色性低下メディアとの接触によって着色性が低下されるため、そのような第２工程後には、第２領域１２の経時的な変色が抑制される。
In addition, in this method, the color-changeable adhesive sheet X including the first region 11 and the second region 12 is prepared in the first step, with such a second step scheduled to be performed later. Such a configuration is suitable for preparing the color-changeable pressure-sensitive adhesive sheet X as a pressure-sensitive adhesive sheet having a high colorability due to an external stimulus and a well-colored first region 11 (in the color-changeable pressure-sensitive adhesive sheet X, The higher the content of the first compound and/or the second compound, the higher the colorability of the color-changeable pressure-sensitive adhesive sheet X). Even if the color-changeable pressure-sensitive adhesive sheet X contains a large amount of the first compound and/or the second compound and has a high colorability so that the first region 11 is well colored, the coloring property-reduced pressure-sensitive adhesive sheet X may be used in the second step. Since the colorability is lowered by the contact, the discoloration of the second region 12 over time is suppressed after such a second step.
以上のように、本方法は、外部刺激の付与によって着色可能な可変色粘着シートＸにおいて、第１領域１１の良好な着色と、第２領域１２の経時的な変色の抑制とを、両立するのに適する。後記の参考例１～４を以って示すように、可変色粘着シートにおいては、着色処理前から光酸発生剤（第１化合物）および発色性化合物（第２化合物）と着色性低下成分とが共存する場合、当該可変色粘着シートは着色能力が低くて着色しにくい。これに対し、所定領域を着色させた後の可変色粘着シートＸに対して事後的に着色性低下成分を浸透させることにより、前記所定領域については、その着色能力を十分に発揮させて良好に着色させられるとともに（第１領域１１の形成）、非着色領域（第２領域１２）については、変色しにくくさせて変色を抑制できる。
As described above, this method achieves both good coloring of the first region 11 and suppression of discoloration of the second region 12 over time in the color-changeable pressure-sensitive adhesive sheet X that can be colored by applying an external stimulus. suitable for As shown in Reference Examples 1 to 4 below, in the color-changeable pressure-sensitive adhesive sheet, the photoacid generator (first compound), the color-developing compound (second compound), and the coloring-reducing component are added before the coloring treatment. coexists, the color-changeable pressure-sensitive adhesive sheet has low coloring ability and is difficult to color. On the other hand, by impregnating the color-changing pressure-sensitive adhesive sheet X after the predetermined region has been colored with the color-lowering component afterward, the predetermined region can sufficiently exhibit its coloring ability and can be satisfactorily obtained. While being colored (formation of the first region 11), the non-colored region (second region 12) is made difficult to discolor, thereby suppressing discoloration.
図２に示す第２工程の後には、例えば、図３に示すように、第１部材２１と第２部材２２とが積層シートＬを介して接合される。第２部材Ｍ２は、例えば透明カバー部材である。透明カバー部材としては、例えば、透明プラスチックフィルムおよび透明ガラス板が挙げられる。本工程により、第１部材２１と、積層シートＬ（可変色粘着シートＸと着色性低下シートＹ）と、第２部材２２とを厚さ方向Ｔに順に備える積層体Ｚ１が得られる。
After the second step shown in FIG. 2, for example, the first member 21 and the second member 22 are joined via the laminated sheet L, as shown in FIG. The second member M2 is, for example, a transparent cover member. Examples of transparent cover members include transparent plastic films and transparent glass plates. Through this step, a laminate Z1 having the first member 21, the laminate sheet L (the color-changeable adhesive sheet X and the coloring-reducing sheet Y), and the second member 22 in order in the thickness direction T is obtained.
第２工程において着色性低下メディアとして着色性低下溶媒を用いた場合、または、図２に示す第２工程の後に可変色粘着シートＸから着色性低下シートＹが剥離された場合、そのような第２工程の後には、例えば、図４に示すように、第１部材２１と第２部材２２とが可変色粘着シートＸを介して接合される。これにより、第１部材２１と、可変色粘着シートＸと、第２部材２２とを厚さ方向Ｔに順に備える積層体Ｚ２が得られる。
In the second step, when a coloring-impaired solvent is used as the coloring-impaired medium, or when the coloring-impaired sheet Y is peeled off from the color-changeable pressure-sensitive adhesive sheet X after the second step shown in FIG. After the second step, for example, the first member 21 and the second member 22 are joined via the color-changeable adhesive sheet X, as shown in FIG. As a result, the laminate Z2 having the first member 21, the color-changeable adhesive sheet X, and the second member 22 in order in the thickness direction T is obtained.
可変色粘着シートＸを形成する第１粘着性組成物は、本実施形態では、ベースポリマーと、外部刺激を受けて第１反応を生ずる第１化合物と、第１反応の生成物との第２反応によって発色する第２化合物とを含有する。
In the present embodiment, the first adhesive composition forming the color-changeable adhesive sheet X is a second composition comprising a base polymer, a first compound that undergoes a first reaction upon receiving an external stimulus, and a product of the first reaction. and a second compound that develops color upon reaction.
ベースポリマーは、可変色粘着シートＸにおいて粘着性を発現させるための粘着成分である。ベースポリマーは、室温域でゴム弾性を示す。ベースポリマーとしては、例えば、アクリルポリマー、ゴムポリマー、ポリエステルポリマー、ウレタンポリマー、ポリエーテルポリマー、シリコーンポリマー、ポリアミドポリマー、およびフッ素ポリマーが挙げられる。可変色粘着シートＸにおける良好な透明性および粘着性を確保する観点から、ベースポリマーとしては、好ましくはアクリルポリマー（第１アクリルポリマー）が用いられる。
The base polymer is an adhesive component for developing adhesiveness in the color-changeable adhesive sheet X. The base polymer exhibits rubber elasticity in the room temperature range. Base polymers include, for example, acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and adhesiveness in the color-changeable pressure-sensitive adhesive sheet X, an acrylic polymer (first acrylic polymer) is preferably used as the base polymer.
アクリルポリマーは、例えば、（メタ）アクリル酸アルキルエステルを５０質量％以上の割合で含むモノマー成分（第１モノマー成分）の共重合体である。「（メタ）アクリル酸」は、アクリル酸および／またはメタクリル酸を意味する。
An acrylic polymer is, for example, a copolymer of a monomer component (first monomer component) containing a (meth)acrylic acid alkyl ester at a ratio of 50% by mass or more. "(Meth)acrylic acid" means acrylic acid and/or methacrylic acid.
（メタ）アクリル酸アルキルエステルとしては、例えば、直鎖状または分岐状の炭素数１～２０のアルキル基を有する（メタ）アクリル酸アルキルエステルが挙げられる。そのような（メタ）アクリル酸アルキルエステルとしては、例えば、（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ｎ－ブチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸イソトリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸イソテトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸イソオクタデシル（アクリル酸イソステアリル）、（メタ）アクリル酸ノナデシル、および（メタ）アクリル酸エイコシルが挙げられる。（メタ）アクリル酸アルキルエステルは、単独で用いられてもよいし、二種類以上が併用されてもよい。（メタ）アクリル酸アルキルエステルとしては、好ましくは、炭素数１～１２のアルキル基を有するアクリル酸アルキルエステルが用いられ、より好ましくは、メタクリル酸メチルと、炭素数２～１２のアルキル基を有する（メタ）アクリル酸アルキルエステルとが併用され、更に好ましくは、メタクリル酸メチルと、アクリル酸２－エチルヘキシルとが併用される。
(Meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms. Examples of such (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. Isopropyl, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) ) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( meth)decyl acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, isotridecyl (meth)acrylate, tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate (isostearyl acrylate), nonadecyl (meth)acrylate, and Eicosyl (meth)acrylate can be mentioned. The (meth)acrylic acid alkyl esters may be used alone, or two or more of them may be used in combination. As the (meth)acrylic acid alkyl ester, an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferably used, and more preferably having methyl methacrylate and an alkyl group having 2 to 12 carbon atoms. A (meth)acrylic acid alkyl ester is used in combination, and more preferably, methyl methacrylate and 2-ethylhexyl acrylate are used in combination.
モノマー成分における（メタ）アクリル酸アルキルエステルの割合は、可変色粘着シートＸにおいて粘着性等の基本特性を適切に発現させる観点から、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上である。同割合は、例えば９９質量％以下である。
The ratio of the (meth)acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the color-changeable pressure-sensitive adhesive sheet X. Preferably, it is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
第１モノマー成分は、（メタ）アクリル酸アルキルエステルと共重合可能な共重合性モノマーを含んでもよい。共重合性モノマーとしては、例えば、極性基を有するモノマーが挙げられる。極性基含有モノマーとしては、例えば、水酸基含有モノマー、窒素原子含有環を有するモノマー、および、カルボキシ基含有モノマーが挙げられる。極性基含有モノマーは、アクリルポリマーへの架橋点の導入、アクリルポリマーの凝集力の確保など、アクリルポリマーの改質に役立つ。
The first monomer component may contain a copolymerizable monomer copolymerizable with the (meth)acrylic acid alkyl ester. Examples of copolymerizable monomers include monomers having a polar group. Polar group-containing monomers include, for example, hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers. The polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing cross-linking points into the acrylic polymer and securing the cohesive strength of the acrylic polymer.
共重合性モノマーは、好ましくは、水酸基含有モノマー、窒素原子含有環を有するモノマー、および、カルボキシ基含有モノマーからなる群から選択される少なくとも一種を含む。より好ましくは、共重合性モノマーは、水酸基含有モノマーおよび／または窒素原子含有環を有するモノマーを含む。
The copolymerizable monomer preferably contains at least one selected from the group consisting of hydroxyl group-containing monomers, nitrogen atom-containing ring-containing monomers, and carboxy group-containing monomers. More preferably, the copolymerizable monomer includes a hydroxyl group-containing monomer and/or a monomer having a nitrogen atom-containing ring.
水酸基含有モノマーとしては、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２－ヒドロキシプロピル、(メタ)アクリル酸２－ヒドロキシブチル、(メタ)アクリル酸３－ヒドロキシプロピル、(メタ)アクリル酸４－ヒドロキシブチル、(メタ)アクリル酸６－ヒドロキシヘキシル、(メタ)アクリル酸８－ヒドロキシオクチル、(メタ)アクリル酸１０－ヒドロキシデシル、(メタ)アクリル酸１２－ヒドロキシラウリル、および(４－ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレートが挙げられる。水酸基含有モノマーとしては、好ましくは(メタ)アクリル酸２－ヒドロキシエチルが用いられ、より好ましくはアクリル酸２－ヒドロキシエチルが用いられる。
Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and ( 4-hydroxymethylcyclohexyl)methyl (meth)acrylate. As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
第１モノマー成分における水酸基含有モノマーの割合は、アクリルポリマーへの架橋構造の導入、および、可変色粘着シートＸにおける凝集力の確保の観点からは、好ましくは１質量％以上、より好ましくは３質量％以上、更に好ましくは５質量％以上である。同割合は、アクリルポリマーの極性の調整の観点からは、好ましくは３０質量％以下、より好ましくは２０質量％以下である。アクリルポリマーの極性は、可変色粘着シートＸにおける各種添加剤成分とアクリルポリマーとの相溶性に関わる。
The ratio of the hydroxyl group-containing monomer in the first monomer component is preferably 1% by mass or more, more preferably 3% by mass, from the viewpoints of introducing a crosslinked structure into the acrylic polymer and ensuring cohesive strength in the color-changeable pressure-sensitive adhesive sheet X. % or more, more preferably 5 mass % or more. From the viewpoint of adjusting the polarity of the acrylic polymer, the same ratio is preferably 30% by mass or less, more preferably 20% by mass or less. The polarity of the acrylic polymer is related to the compatibility between various additive components in the color-changeable pressure-sensitive adhesive sheet X and the acrylic polymer.
窒素原子含有環を有するモノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピリジン、Ｎ－ビニルピペリドン、Ｎ－ビニルピリミジン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルオキサゾール、Ｎ－(メタ)アクリロイル－２－ピロリドン、Ｎ－(メタ)アクリロイルピペリジン、Ｎ－(メタ)アクリロイルピロリジン、Ｎ－ビニルモルホリン、Ｎ－ビニル－３－モルホリノン、Ｎ－ビニル－２－カプロラクタム、Ｎ－ビニル－１,３－オキサジン－２－オン、Ｎ－ビニル－３,５－モルホリンジオン、Ｎ－ビニルピラゾール、Ｎ－ビニルイソオキサゾール、Ｎ－ビニルチアゾール、およびＮ－ビニルイソチアゾールが挙げられる。窒素原子含有環を有するモノマーとしては、好ましくはＮ－ビニル－２－ピロリドンが用いられる。
Examples of monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -vinylthiazole, and N-vinylisothiazole. N-vinyl-2-pyrrolidone is preferably used as the monomer having a nitrogen atom-containing ring.
第１モノマー成分における、窒素原子含有環を有するモノマーの割合は、可変色粘着シートＸにおける凝集力の確保、および、可変色粘着シートＸにおける対被着体密着力の確保の観点からは、好ましくは１質量％以上、より好ましくは３質量％以上、更に好ましくは５質量％以上である。同割合は、アクリルポリマーのガラス転移温度の調整、および、アクリルポリマーの極性の調整の観点からは、好ましくは３０質量％以下、より好ましくは２０質量％以下である。
The ratio of the monomer having a nitrogen atom-containing ring in the first monomer component is preferable from the viewpoint of ensuring the cohesive force of the color-changeable pressure-sensitive adhesive sheet X and the adhesion to the adherend of the color-changeable pressure-sensitive adhesive sheet X. is 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The same proportion is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer.
カルボキシ基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、およびイソクロトン酸が挙げられる。
Carboxy group-containing monomers include, for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
第１モノマー成分におけるカルボキシ基含有モノマーの割合は、アクリルポリマーへの架橋構造の導入、可変色粘着シートＸにおける凝集力の確保、および、可変色粘着シートＸにおける対被着体密着力の確保の観点からは、好ましくは１質量％以上、より好ましくは３質量％以上、更に好ましくは５質量％以上である。同割合は、アクリルポリマーのガラス転移温度の調整、および、酸による被着体の腐食リスクの回避の観点からは、好ましくは３０質量％以下、より好ましくは２０質量％以下である。
The ratio of the carboxyl group-containing monomer in the first monomer component is used to introduce a crosslinked structure into the acrylic polymer, ensure the cohesive force of the color-changeable pressure-sensitive adhesive sheet X, and ensure the adhesion to the adherend of the color-changeable pressure-sensitive adhesive sheet X. From the viewpoint, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. The ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoints of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of acid corrosion of the adherend.
第１モノマー成分は、他の共重合性モノマーを含んでいてもよい（後記の第２モノマー成分についても同様である）。他の共重合性モノマーとしては、例えば、酸無水物モノマー、スルホン酸基含有モノマー、リン酸基含有モノマー、エポキシ基含有モノマー、シアノ基含有モノマー、アルコキシ基含有モノマー、および芳香族ビニル化合物が挙げられる。
The first monomer component may contain other copolymerizable monomers (the same applies to the second monomer component described later). Other copolymerizable monomers include, for example, acid anhydride monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, alkoxy group-containing monomers, and aromatic vinyl compounds. be done.
アクリルポリマーは、上述の第１モノマー成分を重合させることによって形成できる。重合方法としては、例えば溶液重合、塊状重合、および乳化重合が挙げられ、好ましくは溶液重合が挙げられる。重合の開始剤としては、例えば熱重合開始剤が用いられる。重合開始剤の使用量は、第１モノマー成分１００質量部に対して、例えば０.０５質量部以上であり、また、例えば１質量部以下である。
The acrylic polymer can be formed by polymerizing the first monomer component described above. The polymerization method includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization. As the polymerization initiator, for example, a thermal polymerization initiator is used. The amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the first monomer component.
熱重合開始剤としては、例えば、アゾ重合開始剤および過酸化物重合開始剤が挙げられる。アゾ重合開始剤としては、例えば、２,２'－アゾビスイソブチロニトリル、２,２'－アゾビス－２－メチルブチロニトリル、２,２'－アゾビス(２－メチルプロピオン酸)ジメチル、４,４'－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、２,２'－アゾビス(２－アミジノプロパン)ジヒドロクロライド、２,２'－アゾビス[２－(５－メチル－２－イミダゾリン－２－イル)プロパン]ジヒドロクロライド、２,２'－アゾビス(２－メチルプロピオンアミジン)二硫酸塩、および、２,２'－アゾビス(Ｎ,Ｎ'－ジメチレンイソブチルアミジン)ジヒドロクロライドが挙げられる。過酸化物重合開始剤としては、例えば、ジベンゾイルペルオキシド、ｔ－ブチルペルマレエ－ト、および過酸化ラウロイルが挙げられる。
Thermal polymerization initiators include, for example, azo polymerization initiators and peroxide polymerization initiators. Examples of azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2-methylpropionate)dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2- imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, and 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride mentioned. Peroxide polymerization initiators include, for example, dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
アクリルポリマーの重量平均分子量は、可変色粘着シートＸにおける凝集力の確保の観点からは、好ましくは１０万以上、より好ましくは３０万以上、更に好ましくは５０万以上である。同重量平均分子量は、好ましくは５００万以下、より好ましくは３００万以下、更に好ましくは２００万以下である。アクリルポリマー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（ＧＰＣ）によって測定してポリスチレン換算により算出される。
The weight-average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force of the color-changeable pressure-sensitive adhesive sheet X. The weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less. The weight average molecular weight of the acrylic polymer is calculated by measuring by gel permeation chromatography (GPC) and converting to polystyrene.
アクリルポリマーのガラス転移温度（Ｔｇ）は、好ましくは０℃以下、より好ましくは－１０℃以下、更に好ましくは－２０℃以下である。同ガラス転移温度は、例えば－８０℃以上である。
The glass transition temperature (Tg) of the acrylic polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower. The glass transition temperature is, for example, −80° C. or higher.
ポリマーのガラス転移温度（Ｔｇ）については、下記のＦｏｘの式に基づき求められるガラス転移温度（理論値）を用いることができる。Ｆｏｘの式は、ポリマーのガラス転移温度Ｔｇと、当該ポリマーを構成するモノマーのホモポリマーのガラス転移温度Ｔｇｉとの関係式である。下記のＦｏｘの式において、Ｔｇはポリマーのガラス転移温度（℃）を表し、Ｗｉは当該ポリマーを構成するモノマーｉの重量分率を表し、Ｔｇｉは、モノマーｉから形成されるホモポリマーのガラス転移温度（℃）を示す。ホモポリマーのガラス転移温度については文献値を用いることができ、例えば、「Polymer Handbook」（第４版，John Wiley & Sons, Inc., 1999年）および「新高分子文庫７ 塗料用合成樹脂入門」（北岡協三著，高分子刊行会，1995年）には、各種のホモポリマーのガラス転移温度が挙げられている。一方、モノマーのホモポリマーのガラス転移温度については、特開２００７－５１２７１号公報に具体的に記載されている方法によって求めることも可能である。
For the glass transition temperature (Tg) of the polymer, the glass transition temperature (theoretical value) obtained based on the following Fox formula can be used. The Fox equation is a relational expression between the glass transition temperature Tg of a polymer and the glass transition temperature Tgi of a homopolymer of monomers constituting the polymer. In the Fox formula below, Tg represents the glass transition temperature (° C.) of the polymer, Wi represents the weight fraction of the monomer i constituting the polymer, and Tgi represents the glass transition of the homopolymer formed from the monomer i. Indicates temperature (°C). Literature values can be used for the glass transition temperature of homopolymers. (Kyozo Kitaoka, Kobunshi Kankokai, 1995) lists the glass transition temperatures of various homopolymers. On the other hand, the glass transition temperature of a homopolymer of a monomer can also be determined by the method specifically described in JP-A-2007-51271.
Ｆｏｘの式 １／（２７３＋Ｔｇ）＝Σ［Ｗｉ／（２７３＋Ｔｇｉ）］
Fox's formula 1/(273+Tg)=Σ[Wi/(273+Tgi)]
第１粘着性組成物は、ベースポリマーへの架橋構造の導入の観点から、架橋剤を含有してもよい。架橋剤としては、例えば、イソシアネート架橋剤、エポキシ架橋剤、オキサゾリン架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、および金属キレート架橋剤が挙げられる。架橋剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。
The first adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer. Crosslinkers include, for example, isocyanate crosslinkers, epoxy crosslinkers, oxazoline crosslinkers, aziridine crosslinkers, carbodiimide crosslinkers, and metal chelate crosslinkers. The cross-linking agents may be used alone, or two or more of them may be used in combination.
イソシアネート架橋剤としては、例えば、ト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、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート、およびポリメチレンポリフェニルイソシアネートが挙げられる。また、イソシアネート架橋剤としては、これらイソシアネートの誘導体も挙げられる。当該イソシアネート誘導体としては、例えば、イソシアヌレート変性体およびポリオール変性体が挙げられる。イソシアネート架橋剤の市販品としては、例えば、コロネートＬ（トリレンジイソシアネートのトリメチロールプロパンアダクト体，東ソー社製）、コロネートＨＬ（へキサメチレンジイソシアネートのトリメチロールプロパンアダクト体，東ソー社製）、コロネートＨＸ（ヘキサメチレンジイソシアネートのイソシアヌレート体，東ソー社製）、およびタケネートＤ１１０Ｎ（キシリレンジイソシアネートのトリメチロールプロパンアダクト体，三井化学社製）が挙げられる。
Examples of isocyanate cross-linking agents include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, isocyanates, and polymethylene polyphenyl isocyanates. The isocyanate cross-linking agent also includes derivatives of these isocyanates. Examples of the isocyanate derivative include isocyanurate-modified products and polyol-modified products. Commercially available isocyanate cross-linking agents include, for example, Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh Corporation), Coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh Corporation), and Coronate HX. (isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) and Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.).
エポキシ架橋剤としては、ビスフェノールＡ、エピクロルヒドリン型のエポキシ樹脂、エチレン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、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１,６-ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ,Ｎ,Ｎ',Ｎ'-テトラグリシジル-ｍ-キシリレンジアミン、および１,３-ビス(Ｎ,Ｎ-ジグリシジルアミノメチル)シクロヘキサンが挙げられる。
Examples of epoxy cross-linking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether. , diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.
架橋剤の配合量は、可変色粘着シートＸの凝集力を確保する観点からは、ベースポリマー１００質量部に対して、好ましくは０.０１質量部以上、より好ましくは０.０５質量部以上、更に好ましくは０.０７質量部以上である。可変色粘着シートＸにおいて良好なタック性を確保する観点からは、ベースポリマー１００質量部に対する架橋剤の配合量は、好ましくは１０質量部以下であり、より好ましくは５質量部以下、更に好ましくは３質量部以下である。
From the viewpoint of ensuring the cohesive strength of the color-changeable pressure-sensitive adhesive sheet X, the amount of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the base polymer. More preferably, it is 0.07 parts by mass or more. From the viewpoint of ensuring good tackiness in the color-changeable pressure-sensitive adhesive sheet X, the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably It is 3 parts by mass or less.
ベースポリマーに架橋構造が導入される場合、架橋反応を効果的に進行させるために架橋触媒が用いられてもよい。架橋触媒としては、例えば、ジラウリン酸ジブチルスズ、テトラ－ｎ－ブチルチタネート、テトライソプロピルチタネート、ナーセム第二鉄、およびブチルスズオキシドが挙げられ、好ましくはジラウリン酸ジブチルスズが用いられる。架橋触媒の使用量は、ベースポリマー１００質量部に対して例えば０.０００１質量部以上であり、また、例えば１質量部以下である。
When a cross-linked structure is introduced into the base polymer, a cross-linking catalyst may be used to effectively promote the cross-linking reaction. Cross-linking catalysts include, for example, dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, Nasem ferric iron, and butyltin oxide, preferably dibutyltin dilaurate. The amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the base polymer.
架橋触媒が用いられる場合、第１粘着性組成物から事後的に除去可能な架橋抑制剤が第１粘着性組成物に配合されてもよい。架橋触媒としてジラウリン酸ジブチルスズが用いられる場合、架橋抑制剤としては、好ましくはアセチルアセトンが用いられる。この場合、第１粘着性組成物においては、アセチルアセトンがジラウリン酸ジブチルスズに配位し、ベースポリマーに対する架橋剤の架橋反応の進行は抑制される。可変色粘着シートＸの後述の製造過程において、基材フィルム上に第１粘着性組成物が塗布されて塗膜が形成された後、所望のタイミングでの加熱により、アセチルアセトンを揮発させて塗膜から除去できる。これにより、架橋剤の架橋反応を進行させることができる。
When a cross-linking catalyst is used, a cross-linking inhibitor that can be subsequently removed from the first adhesive composition may be blended into the first adhesive composition. When dibutyltin dilaurate is used as the cross-linking catalyst, acetylacetone is preferably used as the cross-linking inhibitor. In this case, in the first adhesive composition, acetylacetone is coordinated to dibutyltin dilaurate, and progress of the cross-linking reaction of the cross-linking agent with respect to the base polymer is suppressed. In the manufacturing process of the color-changeable pressure-sensitive adhesive sheet X described later, after the first adhesive composition is applied onto the base film to form a coating film, the acetylacetone is volatilized by heating at a desired timing to form a coating film. can be removed from This allows the cross-linking reaction of the cross-linking agent to proceed.
架橋抑制剤の配合量は、架橋触媒１００質量部に対して、好ましくは１００質量部以上、より好ましくは１０００質量部以上である。また、同配合量は、例えば５０００質量部以下である。
The amount of the cross-linking inhibitor is preferably 100 parts by mass or more, more preferably 1000 parts by mass or more, relative to 100 parts by mass of the cross-linking catalyst. Moreover, the compounding amount is, for example, 5000 parts by mass or less.
第１化合物としては、例えば、酸発生剤が挙げられる。酸発生剤としては、例えば、光酸発生剤および熱酸発生剤が挙げられる。
Examples of the first compound include acid generators. Acid generators include, for example, photoacid generators and thermal acid generators.
光酸発生剤は、所定の波長または波長範囲の光が照射されることによって励起されて、酸発生反応を引き起こし、酸を発生する。酸発生反応は、例えば、光酸発生剤の分解反応である。酸発生反応を効率よく生じさせる光の波長は、光酸発生剤の種類によって異なる。
The photoacid generator is excited by irradiation with light of a predetermined wavelength or wavelength range to cause an acid generation reaction and generate acid. The acid generation reaction is, for example, a decomposition reaction of the photoacid generator. The wavelength of light that efficiently causes the acid generating reaction varies depending on the type of photoacid generator.
光酸発生剤としては、例えば、紫外線照射によって酸を発生するオニウム化合物が挙げられる。オニウム化合物は、例えば、オニウムカチオンとアニオンとのオニウム塩の形態で提供される。オニウムカチオンとしては、例えば、スルホニウムおよびヨードニウムが挙げられる。アニオンとしては、例えば、Ｃｌ－，Ｂｒ－，Ｉ－，ＺｎＣｌ３
－，ＨＳＯ３
－，ＢＦ４
－，ＰＦ６
－，ＡｓＦ６
－，ＳｂＦ６
－，ＣＨ３ＳＯ３
－，ＣＦ３ＳＯ３
－，Ｃ４Ｆ９ＨＳＯ３
－，(Ｃ６Ｆ５)４Ｂ－，および(Ｃ４Ｈ９)４Ｂ－が挙げられる。光酸発生剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。光酸発生剤としては、好ましくは、スルホニウムとＣ４Ｆ９ＨＳＯ３
－とのオニウム塩、および／またはヨードニウム塩とＣ４Ｆ９ＨＳＯ３
－とのオニウム塩が用いられる。
Examples of photoacid generators include onium compounds that generate acid when irradiated with ultraviolet rays. Onium compounds are provided, for example, in the form of onium salts of onium cations and anions. Onium cations include, for example, sulfonium and iodonium. Examples of anions include Cl − , Br − , I − , ZnCl 3 − , HSO 3 − , BF 4 − , PF 6 − , AsF 6 − , SbF 6 − , CH 3 SO 3 − , CF 3 SO 3 − , C 4 F 9 HSO 3 − , (C 6 F 5 ) 4 B − , and (C 4 H 9 ) 4 B − . The photoacid generators may be used alone, or two or more of them may be used in combination. An onium salt of sulfonium and C 4 F 9 HSO 3 — and/or an onium salt of iodonium salt and C 4 F 9 HSO 3 — is preferably used as the photoacid generator.
ベースポリマー１００質量部に対する光酸発生剤の配合量は、好ましくは１質量部以上、より好ましくは２質量部以上、更に好ましくは５質量部以上、特に好ましくは７質量部以上である。同配合量は、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１２質量部以下である。
The amount of the photoacid generator to be blended with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more. The blending amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.
また、後記の発色性化合物１００質量部に対する光酸発生剤の配合量は、好ましくは１００質量部以上、より好ましくは２００質量部以上、更に好ましくは３００質量部以上、特に好ましくは３３０質量部以上である。同配合量は、好ましくは１０００質量部以下、より好ましくは７００質量部以下、更に好ましくは５００質量部以下である。
The amount of the photoacid generator to be added to 100 parts by mass of the color forming compound described later is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more, and particularly preferably 330 parts by mass or more. is. The blending amount is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and even more preferably 500 parts by mass or less.
第２化合物としては、例えば、酸との反応により発色する発色性化合物が挙げられる。当該発色性化合物としては、例えば、ロイコ色素、トリアリールメタン色素、ジフェニルメタン色素、フルオラン色素、スピロピラン色素、およびローダミン色素が挙げられる。発色性化合物は、単独で用いられてもよいし、二種類以上が併用されてもよい。
Examples of the second compound include color-developing compounds that develop color upon reaction with an acid. Examples of such color-forming compounds include leuco dyes, triarylmethane dyes, diphenylmethane dyes, fluorane dyes, spiropyran dyes, and rhodamine dyes. The color-developing compounds may be used alone, or two or more of them may be used in combination.
ロイコ色素としては、例えば、２'－アニリノ－６'－(Ｎ－エチル－Ｎ－イソペンチルアミノ)－３'－メチルスピロ[フタリド－３,９'－[９Ｈ]キサンテン]、３－ジブチルアミノ－６－メチル－７－アニリノフルオラン、３－ジプロピルアミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－メチル－７－アニリノフルオラン、３－ジメチルアミノ－６－メチル－７－アニリノフルオラン、３－ジエチルアミノ－６－メチル－７－キシリジノフルオラン、および、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリドが挙げられる。
Leuco dyes include, for example, 2'-anilino-6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalide-3,9'-[9H]xanthene], 3-dibutylamino- 6-methyl-7-anilinofluorane, 3-dipropylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dimethylamino-6- Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xyridinofluorane, and 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole) -3-yl)-4-azaphthalide.
トリアリールメタン色素としては、例えば、ｐ,ｐ',ｐ”－トリス－ジメチルアミノトリフェニルメタンが挙げられる。ジフェニルメタン色素としては、例えば、４,４－ビス－ジメチルアミノフェニルベンズヒドリルベンジルエーテルが挙げられる。フルオラン色素としては、例えば、３－ジエチルアミノ－６－メチル－７－クロロフルオランが挙げられる。スピロピラン色素としては、例えば、３-メチルスピロジナフトピランが挙げられる。ローダミン色素としては、例えば、ローダミン－Ｂ－アニリノラクタムが挙げられる。
Examples of triarylmethane dyes include p,p′,p″-tris-dimethylaminotriphenylmethane. Examples of diphenylmethane dyes include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether. Examples of fluorane dyes include 3-diethylamino-6-methyl-7-chlorofluorane, examples of spiropyran dyes include 3-methylspirodinaphthopyran, and examples of rhodamine dyes include: Examples include rhodamine-B-anilinolactam.
可変色粘着シートＸにおいて良好な着色性を確保する観点からは、発色性化合物としては、好ましくはロイコ色素、より好ましくは２'－アニリノ－６'－(Ｎ－エチル－Ｎ－イソペンチルアミノ)－３'－メチルスピロ[フタリド－３,９'－[９Ｈ]キサンテン]が用いられる。
From the viewpoint of ensuring good coloring properties in the color-changeable pressure-sensitive adhesive sheet X, the color-developing compound is preferably a leuco dye, more preferably 2'-anilino-6'-(N-ethyl-N-isopentylamino). -3'-methylspiro[phthalido-3,9'-[9H]xanthene] is used.
ベースポリマー１００質量部に対する発色性化合物の配合量は、好ましくは０.５質量部以上、より好ましくは１質量部以上である。同配合量は、好ましくは１０質量部以下、より好ましくは７質量部以下である。
The amount of the color-developing compound compounded with respect to 100 parts by mass of the base polymer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. The blending amount is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
第１粘着性組成物は、必要に応じて他の成分を含有してもよい。他の成分としては、例えば、シランカップリング剤、粘着性付与剤、可塑剤、軟化剤、酸化防止剤、界面活性剤、増感剤、および帯電防止剤が挙げられる。
The first adhesive composition may contain other components as necessary. Other ingredients include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, sensitizers, and antistatic agents.
可変色粘着シートＸは、例えば、上述の第１粘着性組成物のワニスを基材フィルム上に塗布して塗膜を形成した後、当該塗膜を乾燥させることによって、製造できる。基材フィルムとしては、例えば、可撓性を有するプラスチックフィルムが挙げられる。当該プラスチックフィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、およびポリエステルフィルムが挙げられる。基材フィルムの厚さは、例えば３μｍ以上であり、また、例えば２００μｍ以下である。基材フィルムの表面は、好ましくは離型処理されている。
The color-changeable pressure-sensitive adhesive sheet X can be produced, for example, by applying the varnish of the first pressure-sensitive adhesive composition described above to the base film to form a coating film, and then drying the coating film. Examples of base films include flexible plastic films. Examples of the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film. The thickness of the base film is, for example, 3 μm or more and, for example, 200 μm or less. The surface of the base film is preferably release-treated.
第１粘着性組成物が架橋剤を含む場合、上述の乾燥と同時に又はその後のエージングによって、架橋反応が進行する。エージング条件は、架橋剤の種類によって適宜設定される。エージング温度は、例えば２０℃～１６０℃である。エージング時間は、例えば、１分から７日である。
When the first adhesive composition contains a cross-linking agent, the cross-linking reaction proceeds simultaneously with the above-described drying or by subsequent aging. Aging conditions are appropriately set according to the type of cross-linking agent. The aging temperature is, for example, 20°C to 160°C. Aging time is, for example, from 1 minute to 7 days.
エージングの前または後に、基材フィルム上の可変色粘着シートＸの上に更に剥離フィルム（はく離ライナー）を積層してもよい。剥離フィルムは、表面離型処理が施された可撓性のプラスチックフィルムである。剥離フィルムとしては、例えば、基材フィルムに関して上述したプラスチックフィルムが挙げられる。
A release film (release liner) may be further laminated on the color-changeable pressure-sensitive adhesive sheet X on the base film before or after aging. The release film is a flexible plastic film to which surface release treatment has been applied. Release films include, for example, the plastic films described above with respect to the base film.
以上のようにして、剥離フィルムによって粘着面が被覆保護された可変色粘着シートＸを製造できる。各剥離フィルムは、可変色粘着シートＸを使用する際に必要に応じて可変色粘着シートＸから剥がされる。
As described above, the color-changeable adhesive sheet X whose adhesive surface is covered and protected by the release film can be manufactured. Each release film is peeled off from the color-changeable pressure-sensitive adhesive sheet X when the color-changeable pressure-sensitive adhesive sheet X is used.
可変色粘着シートＸの厚さは、被着体に対する充分な粘着性を確保する観点から、好ましくは１０μｍ以上、より好ましくは１５μｍ以上である。可変色粘着シートＸのハンドリング性の観点からは、可変色粘着シートＸの厚さは、好ましくは３００μｍ以下、より好ましくは２００μｍ以下、更に好ましくは１００μｍ以下、特に好ましくは５０μｍ以下である。
The thickness of the color-changeable pressure-sensitive adhesive sheet X is preferably 10 μm or more, more preferably 15 μm or more, from the viewpoint of ensuring sufficient adhesion to the adherend. From the viewpoint of handleability of the color-changeable pressure-sensitive adhesive sheet X, the thickness of the color-changeable pressure-sensitive adhesive sheet X is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less.
可変色粘着シートＸの波長４００～７００ｎｍでの平均透過率（外部刺激付与前の平均透過率）は、好ましくは８０％以上、より好ましくは８５％以上、更に好ましくは９０％以上、特に好ましくは９５％以上である。このような構成は、可変色粘着シートＸを被着体に貼り合わせた後に可変色粘着シートＸと被着体との間における異物および気泡の有無を検査するのに適する。波長４００～７００ｎｍでの平均透過率は、後記の実施例に関して後述する方法によって測定できる。
The average transmittance of the color-changeable pressure-sensitive adhesive sheet X at a wavelength of 400 to 700 nm (average transmittance before application of an external stimulus) is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more. Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the color-changeable adhesive sheet X and the adherend after bonding the color-changeable adhesive sheet X to the adherend. The average transmittance at wavelengths from 400 to 700 nm can be measured by the method described below with respect to the examples below.
着色性低下シートＹを形成する第２粘着性組成物は、ベースポリマーを含有する。ベースポリマーとしては、第１粘着性組成物に関して上述したベースポリマーが挙げられ、好ましくはアクリルポリマー（第２アクリルポリマー）が用いられる。
The second adhesive composition forming the color-reducing sheet Y contains a base polymer. The base polymer includes the base polymer described above with respect to the first adhesive composition, preferably an acrylic polymer (second acrylic polymer).
第２アクリルポリマーを形成するモノマー成分（第２モノマー成分）は、（メタ）アクリル酸アルキルエステルを含む。当該（メタ）アクリル酸アルキルエステルとしては、例えば、第１アクリルポリマーに関して上記した（メタ）アクリル酸アルキルエステルが挙げられ、好ましくは、炭素数６～１８のアルキル基を有するアクリル酸アルキルエステルが用いられ、より好ましくはアクリル酸２－エチルヘキシルおよび／またはアクリル酸イソステアリルが用いられる。
The monomer component (second monomer component) forming the second acrylic polymer contains a (meth)acrylic acid alkyl ester. Examples of the (meth)acrylic acid alkyl ester include the (meth)acrylic acid alkyl esters described above with respect to the first acrylic polymer, and preferably, an acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms is used. 2-ethylhexyl acrylate and/or isostearyl acrylate are more preferably used.
第２モノマー成分における（メタ）アクリル酸アルキルエステルの割合は、着色性低下シートＹにおいて粘着性等の基本特性を適切に発現させる観点から、好ましくは５０質量％以上、より好ましくは６０質量％以上、更に好ましくは７０質量％以上である。同割合は、例えば９９質量％以下である。
The ratio of the (meth)acrylic acid alkyl ester in the second monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the color-reducing sheet Y. , more preferably 70% by mass or more. The same ratio is, for example, 99% by mass or less.
第２モノマー成分は、（メタ）アクリル酸アルキルエステルと共重合可能な共重合性モノマーを含んでもよい。当該共重合性モノマーとしては、第１アクリルポリマーに関して上記した共重合性モノマーが挙げられ、好ましくは極性基含有モノマーが用いられ、より好ましくは、水酸基含有モノマー、窒素原子含有環を有するモノマー、および、カルボキシ基含有モノマーからなる群より選択される少なくとも一つが用いられる。第２モノマー成分における水酸基含有モノマーとしては、好ましくは、アクリル酸２－ヒドロキシエチルおよび／またはアクリル酸４－ヒドロキシブチルが用いられる。第２モノマー成分における窒素原子含有環を有するモノマーとしては、好ましくはＮ－ビニル－２－ピロリドンが用いられる。第２モノマー成分におけるカルボキシ基含有モノマーとしては、好ましくはアクリル酸が用いられる。極性基含有モノマーを含む第２モノマー成分の共重合体としてのアクリルポリマーは、極性基含有ポリマーである。このようなアクリルポリマーは、可変色粘着シートＸから上述の光酸発生剤など第１化合物を着色性低下シートＹに抽出するのに好ましい。
The second monomer component may contain a copolymerizable monomer copolymerizable with the (meth)acrylic acid alkyl ester. Examples of the copolymerizable monomer include the copolymerizable monomers described above for the first acrylic polymer, preferably a polar group-containing monomer, more preferably a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and , a carboxy group-containing monomer is used. As the hydroxyl group-containing monomer in the second monomer component, 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate are preferably used. N-vinyl-2-pyrrolidone is preferably used as the monomer having a nitrogen atom-containing ring in the second monomer component. Acrylic acid is preferably used as the carboxy group-containing monomer in the second monomer component. The acrylic polymer as the copolymer of the second monomer component containing the polar group-containing monomer is a polar group-containing polymer. Such an acrylic polymer is preferable for extracting the first compound such as the above photoacid generator from the color-changeable pressure-sensitive adhesive sheet X to the color-reducing sheet Y.
第２モノマー成分における極性基含有モノマーの割合は、アクリルポリマーの凝集力の確保の観点、および、アクリルポリマーの極性の調整の観点から、好ましくは１質量％以上、より好ましくは３質量％以上、更に好ましくは５質量％以上であり、また、好ましくは４０質量％以下、より好ましくは３０質量％以下である。着色性低下シートＹが抽出用シートである場合、可変色粘着シートＸから着色性低下シートＹへの光酸発生剤の移行のしやすさ（抽出性）を確保する観点から、第２モノマー成分における極性基含有モノマーの割合は、好ましくは５質量％以上、より好ましくは１０質量％以上、更に好ましくは１５質量％以上であり、また、好ましくは５０質量％以下、より好ましくは３５質量％以下である。
The ratio of the polar group-containing monomer in the second monomer component is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of ensuring cohesive strength of the acrylic polymer and adjusting the polarity of the acrylic polymer. It is more preferably 5% by mass or more, preferably 40% by mass or less, and more preferably 30% by mass or less. When the coloring-impaired sheet Y is a sheet for extraction, from the viewpoint of ensuring ease of migration (extractability) of the photoacid generator from the color-changeable pressure-sensitive adhesive sheet X to the coloring-impaired sheet Y, the second monomer component The ratio of the polar group-containing monomer in is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 35% by mass or less. is.
第２アクリルポリマーは、上述の第２モノマー成分を重合させることによって形成できる。重合方法としては、例えば溶液重合、塊状重合、および乳化重合が挙げられ、好ましくは溶液重合が挙げられる。重合の開始剤としては、例えば、上記の熱重合開始剤が用いられる。重合開始剤の使用量は、第２モノマー成分１００質量部に対して、例えば０.０５質量部以上であり、また、例えば１質量部以下である。
The second acrylic polymer can be formed by polymerizing the second monomer component described above. The polymerization method includes, for example, solution polymerization, bulk polymerization, and emulsion polymerization, preferably solution polymerization. As the polymerization initiator, for example, the thermal polymerization initiator described above is used. The amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the second monomer component.
第２アクリルポリマーの重量平均分子量は、着色性低下シートＹにおける凝集力の確保の観点からは、好ましくは１０万以上、より好ましくは３０万以上、更に好ましくは５０万以上である。同重量平均分子量は、好ましくは５００万以下、より好ましくは３００万以下、更に好ましくは２００万以下である。
The weight-average molecular weight of the second acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, and still more preferably 500,000 or more, from the viewpoint of ensuring the cohesive strength of the reduced-colorability sheet Y. The weight-average molecular weight is preferably 5 million or less, more preferably 3 million or less, still more preferably 2 million or less.
第２アクリルポリマーのガラス転移温度（Ｔｇ）は、好ましくは０℃以下、より好ましくは－１０℃以下、更に好ましくは－２０℃以下である。同ガラス転移温度は、例えば－８０℃以上である。
The glass transition temperature (Tg) of the second acrylic polymer is preferably 0°C or lower, more preferably -10°C or lower, and even more preferably -20°C or lower. The glass transition temperature is, for example, −80° C. or higher.
第２粘着性組成物は、ベースポリマーへの架橋構造の導入の観点から、架橋剤を含有してもよい。架橋剤としては、例えば、上記のイソシアネート架橋剤、上記のエポキシ架橋剤、オキサゾリン架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、および金属キレート架橋剤が挙げられる。架橋剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。架橋剤の配合量は、着色性低下シートＹの凝集力を確保する観点からは、ベースポリマー１００質量部に対して、好ましくは０.０１質量部以上、より好ましくは０.０５質量部以上、更に好ましくは０.０７質量部以上である。着色性低下シートＹにおいて良好なタック性を確保する観点からは、ベースポリマー１００質量部に対する架橋剤の配合量は、好ましくは１０質量部以下であり、より好ましくは５質量部以下、更に好ましくは３質量部以下である。
The second adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer. Cross-linking agents include, for example, the isocyanate cross-linking agents described above, the epoxy cross-linking agents described above, the oxazoline cross-linking agents, the aziridine cross-linking agents, the carbodiimide cross-linking agents, and the metal chelate cross-linking agents. The cross-linking agents may be used alone, or two or more of them may be used in combination. From the viewpoint of securing the cohesive strength of the coloring-reduced sheet Y, the amount of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the base polymer. More preferably, it is 0.07 parts by mass or more. From the viewpoint of ensuring good tackiness in the coloring-reduced sheet Y, the amount of the cross-linking agent blended with respect to 100 parts by mass of the base polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably It is 3 parts by mass or less.
ベースポリマーに架橋構造が導入される場合、架橋反応を効果的に進行させるために架橋触媒が用いられてもよい。当該架橋触媒としては、例えば、第１粘着性組成物に関して上記した架橋剤が挙げられる。架橋触媒の使用量は、ベースポリマー１００質量部に対して例えば０.０００１質量部以上であり、また、例えば１質量部以下である。架橋触媒が用いられる場合、第２粘着性組成物から事後的に除去可能な架橋抑制剤が第２粘着性組成物に配合されてもよい。当該架橋抑制剤としては、第１粘着性組成物に関して上記した架橋抑制剤が挙げられる。架橋抑制剤の配合量は、架橋触媒１００質量部に対して、好ましくは１００質量部以上、より好ましくは１０００質量部以上である。また、同配合量は、例えば５０００質量部以下である。
When a cross-linked structure is introduced into the base polymer, a cross-linking catalyst may be used to effectively promote the cross-linking reaction. Examples of the cross-linking catalyst include the cross-linking agents described above with respect to the first adhesive composition. The amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the base polymer. When a cross-linking catalyst is used, a cross-linking inhibitor that can be subsequently removed from the second adhesive composition may be incorporated into the second adhesive composition. Examples of the cross-linking inhibitor include the cross-linking inhibitors described above with respect to the first adhesive composition. The amount of the cross-linking inhibitor to be blended is preferably 100 parts by mass or more, more preferably 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking catalyst. Moreover, the compounding amount is, for example, 5000 parts by mass or less.
着色性低下シートＹが失活用シートである場合、第２粘着性組成物は、更に、着色性低下成分を含有する。可変色粘着シートＸが上述の第１成分として光酸発生剤を含有する場合、着色性低下成分としては、例えば、紫外線吸収剤、中和剤、およびラジカルトラップ剤が挙げられる。着色性低下成分は、好ましくは、紫外線吸収剤、中和剤、およびラジカルトラップ剤からなる群より選択される少なくとも一つを含む。
When the coloring-reducing sheet Y is a deactivation sheet, the second adhesive composition further contains a coloring-reducing component. When the color-changeable pressure-sensitive adhesive sheet X contains a photoacid generator as the above-described first component, examples of the coloring-lowering component include an ultraviolet absorber, a neutralizer, and a radical trapping agent. The coloring-lowering component preferably contains at least one selected from the group consisting of ultraviolet absorbers, neutralizers, and radical trapping agents.
紫外線吸収剤は、上述の第２工程において着色性低下シートＹから可変色粘着シートＸに導入された後、可変色粘着シートＸが受ける紫外線の一部または全部を吸収する。この紫外線吸収により、光酸発生剤が紫外線照射を受けた場合に生ずる酸発生反応が抑制され、従って、発色性化合物の発色が抑制される。これにより、第２工程後の可変色粘着シートＸの着色性が低下する。
After being introduced from the color-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above, the ultraviolet absorber absorbs part or all of the ultraviolet light received by the color-changeable pressure-sensitive adhesive sheet X. This UV absorption suppresses the acid generation reaction that occurs when the photoacid generator is exposed to UV irradiation, and thus suppresses the coloring of the color-developing compound. As a result, the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
紫外線吸収剤としては、例えば、ベンゾトリアゾール紫外線吸収剤、ベンゾフェノン紫外線吸収剤、オキシベンゾフェノン紫外線吸収剤、ヒドロキシフェニルトリアジン紫外線吸収剤、サリチル酸エステル紫外線吸収剤、およびシアノアクリレート紫外線吸収剤が挙げられる。
Examples of ultraviolet absorbers include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, oxybenzophenone ultraviolet absorbers, hydroxyphenyltriazine ultraviolet absorbers, salicylic acid ester ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
中和剤は、上述の第２工程において着色性低下シートＹから可変色粘着シートＸに導入された後、光酸発生剤が生ずる酸の一部または全部を中和する。この中和作用により、光酸発生剤が紫外線照射を受けた場合に生ずる酸と発色性化合物との反応が抑制される。これにより、第２工程後の可変色粘着シートＸの着色性が低下する。
The neutralizing agent neutralizes part or all of the acid generated by the photoacid generator after being introduced from the color-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above. This neutralizing action suppresses the reaction between the acid and the color-developing compound that occurs when the photoacid generator is irradiated with ultraviolet rays. As a result, the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
中和剤としては、例えば、アルカリ性を示す第一級アミン、第二級アミン、および第三級アミンが挙げられる。第一級アミンとしては、例えば、モノエチルアミンおよびモノエタノールアミンが挙げられる。第二級アミンとしては、例えば、ジエチルアミンおよびジエタノールアミンが挙げられる。第三級アミンとしては、例えば、トリエチルアミン、トリエタノールアミン、Ｎ，Ｎ,Ｎ'－トリメチルエチレンジアミン、Ｎ－メチルジエタノールアミン、およびＮ,Ｎ－ジエチルヒドロキシルアミンが挙げられる。
Examples of neutralizing agents include primary amines, secondary amines, and tertiary amines that exhibit alkalinity. Primary amines include, for example, monoethylamine and monoethanolamine. Secondary amines include, for example, diethylamine and diethanolamine. Tertiary amines include, for example, triethylamine, triethanolamine, N,N,N'-trimethylethylenediamine, N-methyldiethanolamine, and N,N-diethylhydroxylamine.
ラジカルトラップ剤は、上述の第２工程において着色性低下シートＹから可変色粘着シートＸに導入された後、光酸発生剤の酸発生反応の開始時にラジカルが生じる場合に当該ラジカルを捕捉して、酸発生反応の進行を抑制する。これにより、発色性化合物の発色が抑制されて、第２工程後の可変色粘着シートＸの着色性が低下する。
The radical trapping agent traps radicals when radicals are generated at the start of the acid generation reaction of the photoacid generator after being introduced from the colorability-reducing sheet Y into the color-changeable pressure-sensitive adhesive sheet X in the second step described above. , to suppress the progress of the acid generation reaction. As a result, the color development of the color-developing compound is suppressed, and the colorability of the color-changeable pressure-sensitive adhesive sheet X after the second step is lowered.
ラジカルトラップ剤としては、例えば、ヒンダードアミン化合物、ヒンダードフェノール化合物、Ｎ－オキシル化合物、ナフタレン誘導体、チオエーテル化合物、およびヒドラジル化合物が挙げられ、好ましくはヒンダードアミン化合物が用いられる。
Examples of radical trapping agents include hindered amine compounds, hindered phenol compounds, N-oxyl compounds, naphthalene derivatives, thioether compounds, and hydrazil compounds, preferably hindered amine compounds.
第２粘着性組成物における着色性低下成分の割合は、ベースポリマー１００質量部に対して、好ましくは０.１質量部以上、より好ましくは１質量部以上、更に好ましくは２質量部以上である。同割合は、ベースポリマー１００質量部に対して、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１０質量部以下である。
The ratio of the coloring-lowering component in the second adhesive composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, relative to 100 parts by mass of the base polymer. . The same ratio is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less with respect to 100 parts by mass of the base polymer.
第１領域１１（着色済領域）形成前の可変色粘着シートＸに着色性低下成分が配合されている場合、可変色粘着シートＸに対する外部刺激付与による第１領域１１の形成は、阻害される。本発明の可変色粘着シートの変色抑制方法において、着色性低下メディアとして失活用メディアを用いる場合、第１領域１１形成後に可変色粘着シートＸに着色性低下成分を導入できるので、そのような不具合を回避できる。
When the color-lowering component is blended in the color-changeable pressure-sensitive adhesive sheet X before forming the first regions 11 (colored regions), the formation of the first regions 11 by applying an external stimulus to the color-changeable pressure-sensitive adhesive sheet X is inhibited. . In the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet of the present invention, when a deactivating medium is used as the color-reducing medium, the color-reducing component can be introduced into the color-changeable pressure-sensitive adhesive sheet X after the first region 11 is formed. can be avoided.
失活用メディアにおいて、第１化合物、第２化合物、および着色性低下成分が共存する第１の系における外部刺激付与による透過率の低下ΔＴ１は、好ましくは、着色性低下成分が存在しないこと以外は第１の系と同じ第２の系における外部刺激付与と同じ外部刺激付与による透過率の低下ΔＴ２より小さい。ΔＴ２とΔＴ１との差（ΔＴ２－ΔＴ１）は、好ましくは５％以上、より好ましくは１５％以上、更に好ましくは３０％以上、特に好ましくは５０％以上である。透過率は、例えば、波長４００～７００ｎｍでの平均透過率であり、後記の実施例に関して後述する方法によって測定できる。このような構成は、第２工程において可変色粘着シートＸの着色性を低下させるのに適する。
In the devitalized media, the decrease in transmittance ΔT1 due to the application of an external stimulus in the first system in which the first compound, the second compound, and the coloring-reducing component coexist is preferably It is smaller than the decrease ΔT2 in transmittance due to the application of the same external stimulus to the second system that is the same as the first system. The difference between ΔT2 and ΔT1 (ΔT2−ΔT1) is preferably 5% or more, more preferably 15% or more, even more preferably 30% or more, and particularly preferably 50% or more. The transmittance is, for example, the average transmittance at wavelengths from 400 to 700 nm, and can be measured by the method described below with respect to the examples below. Such a configuration is suitable for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet X in the second step.
第２粘着性組成物は、必要に応じて他の成分を含有してもよい。他の成分としては、例えば、シランカップリング剤、粘着性付与剤、可塑剤、軟化剤、酸化防止剤、界面活性剤、および帯電防止剤が挙げられる。
The second adhesive composition may contain other ingredients as necessary. Other ingredients include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
着色性低下シートＹを形成する第２粘着性組成物は、上述の光酸発生剤など第１化合物、および、上述の発色性化合物など第２化合物を、含有しない。また、抽出用シートとしての着色性低下シートＹを形成する第２粘着性組成物は、紫外線吸収剤、中和剤、およびラジカルトラップ剤など着色性低下成分を、含有しない。
The second adhesive composition that forms the color-reducing sheet Y does not contain the first compound such as the photoacid generator described above and the second compound such as the color-developing compound described above. In addition, the second adhesive composition that forms the coloring-reducing sheet Y as an extraction sheet does not contain coloring-reducing components such as UV absorbers, neutralizers, and radical trapping agents.
着色性低下シートＹは、例えば、上述の第２粘着性組成物のワニスを基材フィルム上に塗布して塗膜を形成した後、当該塗膜を乾燥させることによって、製造できる。具体的には、可変色粘着シートＸの上述の製造方法と同様である。
The coloring-reduced sheet Y can be produced, for example, by applying the varnish of the above-described second adhesive composition onto the base film to form a coating film, and then drying the coating film. Specifically, it is the same as the method for manufacturing the color-changeable pressure-sensitive adhesive sheet X described above.
着色性低下シートＹの厚さは、着色性低下機能の良好な発現の観点から、好ましくは１０μｍ以上、より好ましくは２０μｍ以上である。着色性低下シートＹのハンドリング性の観点からは、着色性低下シートＹの厚さは、好ましくは３００μｍ以下、より好ましくは２００μｍ以下である。
The thickness of the colorability-reducing sheet Y is preferably 10 μm or more, more preferably 20 μm or more, from the viewpoint of good expression of the colorability-reducing function. From the viewpoint of handleability of the coloring-impaired sheet Y, the thickness of the coloring-impaired sheet Y is preferably 300 μm or less, more preferably 200 μm or less.
着色性低下シートＹの波長４００～７００ｎｍでの平均透過率は、可変色粘着シートＸの第１領域１１の波長４００～７００ｎｍでの平均透過率より高く、例えば４０％以上であり、また、例えば９９％以下である。例えば、積層シートＬの面方向における、第２領域１２（非着色済領域）部分の透過率調整の観点、および、第２領域１２部分と第１領域１１（着色済領域）部分とのコントラスト差向上の観点からは、着色性低下シートＹの波長４００～７００ｎｍでの平均透過率は、好ましくは４５％以上、より好ましくは５０％以上、更に好ましくは６０％以上である。当該平均透過率は例えば１００％以下である。例えば、積層シートＬの面方向における、第２領域１２（非着色済領域）部分での反射防止の観点、および、第２領域１２部分の見栄え調整の観点からは、着色性低下シートＹの波長４００～７００ｎｍでの平均透過率は、好ましくは９０％以下、より好ましくは８０％以下、更に好ましくは７０％以下である。当該平均透過率は例えば５０％以上である。
The average transmittance of the color-reducing sheet Y at a wavelength of 400 to 700 nm is higher than the average transmittance of the first region 11 of the color-changeable pressure-sensitive adhesive sheet X at a wavelength of 400 to 700 nm, for example, 40% or more. 99% or less. For example, from the viewpoint of adjusting the transmittance of the second region 12 (non-colored region) in the plane direction of the laminated sheet L, and the contrast difference between the second region 12 and the first region 11 (colored region) From the viewpoint of improvement, the average transmittance of the color-impaired sheet Y at a wavelength of 400 to 700 nm is preferably 45% or higher, more preferably 50% or higher, and even more preferably 60% or higher. The average transmittance is, for example, 100% or less. For example, from the viewpoint of antireflection in the second region 12 (non-colored region) portion in the plane direction of the laminated sheet L, and from the viewpoint of adjusting the appearance of the second region 12 portion, the wavelength of the reduced coloring sheet Y The average transmittance at 400-700 nm is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. The average transmittance is, for example, 50% or more.
第２工程では、図５に示すように、可変色粘着シートＸの第１領域１１と着色性低下シートＸとの間にマスク材Ｍを介在させた状態で、着色性低下シートＹを可変色粘着シートＸに貼り合わせてもよい。マスク材Ｍは、例えば、第１領域１１が形成される前に可変色粘着シートＸ上に配置されてもよいし、第１領域１１が形成された後に可変色粘着シートＸ上に配置されてもよい。
In the second step, as shown in FIG. 5, a masking material M is interposed between the first region 11 of the color-changeable pressure-sensitive adhesive sheet X and the color-reducing sheet X, and the color-reducing sheet Y is subjected to a color-changeable process. It may be attached to the adhesive sheet X. For example, the mask material M may be placed on the color-changeable adhesive sheet X before the first regions 11 are formed, or may be placed on the color-changeable adhesive sheet X after the first regions 11 are formed. good too.
マスク材Ｍは、例えば、透明なプラスチックフィルムである。プラスチックフィルムの材料としては、例えば、ポリオレフィン、ポリエステル、ポリアミド、ポリイミド、ポリ塩化ビニル、ポリ塩化ビニリデン、セルロース、ポリスチレン、およびポリカーボネートが挙げられる。ポリオレフィンとしては、例えば、ポリエチレンおよびポリプロピレンが挙げられる。ポリエステルとしては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、およびポリブチレンテレフタレートが挙げられる。ポリアミドとしては、例えば、ポリアミド６、ポリアミド６,６、および部分芳香族ポリアミドが挙げられる。
The mask material M is, for example, a transparent plastic film. Materials for plastic films include, for example, polyolefins, polyesters, polyamides, polyimides, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonates. Polyolefins include, for example, polyethylene and polypropylene. Polyesters include, for example, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Polyamides include, for example, polyamide 6, polyamide 6,6, and partially aromatic polyamides.
マスク材Ｍが配置されている領域では、可変色粘着シートＸと着色性低下シートＹとの間の成分移動は阻止される。このようなマスク材Ｍの使用は、第２工程において、可変色粘着シートＸに対する着色性低下シートＹによる着色性低下成分の導入、または、着色性低下シートＹによる可変色粘着シートＸからの第１化合物の抽出を、第２領域１２に対して選択的に効率よく実施するのに適する。
In the region where the masking material M is arranged, component movement between the color-changeable pressure-sensitive adhesive sheet X and the color-reducing sheet Y is prevented. The use of such a masking material M can be achieved in the second step by introducing a colorability-reducing component from the color-reducing sheet Y into the color-reducing adhesive sheet X, or removing the color-reducing component from the color-reducing adhesive sheet X with the color-reducing sheet Y in the second step. It is suitable for selectively and efficiently extracting one compound from the second region 12 .
着色性低下メディアとしての着色性低下溶媒は、主剤として、極性溶媒を含んでもよいし、低極性溶媒（非極性溶媒）を含んでもよい。極性溶媒としては、例えば、水、アルコール、およびカルボン酸が挙げられる。極性溶媒としては、酢酸エチル、アセトン、アセトニトリルなどの中極性溶媒も挙げられる。アルコールとしては、例えば、メタノール、エタノール、イソプロピルアルコール、およびブタノールが挙げられる。カルボン酸としては、ギ酸および酢酸が挙げられる。低極性溶媒としては、例えば、ベンゼン、トルエン、およびメチルイソブチルケトンが挙げられる。また、機能性液体である着色性低下溶媒としては、失活用溶媒または抽出用溶媒として充分な成分溶解性を示す液状モノマーも、適宜選択して使用できる。そのような液状モノマーとしては、例えば、各種のアクリレートモノマーが挙げられる。
The coloring-lowering solvent as the coloring-lowering medium may contain a polar solvent or a low-polar solvent (non-polar solvent) as the main agent. Polar solvents include, for example, water, alcohols, and carboxylic acids. Polar solvents also include moderately polar solvents such as ethyl acetate, acetone, and acetonitrile. Alcohols include, for example, methanol, ethanol, isopropyl alcohol, and butanol. Carboxylic acids include formic acid and acetic acid. Low polarity solvents include, for example, benzene, toluene, and methyl isobutyl ketone. In addition, as the coloration reducing solvent, which is a functional liquid, a liquid monomer exhibiting sufficient component solubility as a deactivating solvent or an extracting solvent can also be appropriately selected and used. Such liquid monomers include, for example, various acrylate monomers.
着色性低下溶媒が失活用の着色性低下溶媒である場合には、当該着色性低下溶媒は、更に、着色性低下成分を含有する。着色性低下成分は、好ましくは、紫外線吸収剤、中和剤、およびラジカルトラップ剤からなる群より選択される少なくとも一つを含む。紫外線吸収剤、中和剤、およびラジカルトラップ剤としては、着色性低下シートＹに関して上記した紫外線吸収剤、中和剤、およびラジカルトラップ剤が挙げられ、好ましくはラジカルトラップ剤が用いられる。
When the coloration-reducing solvent is a deactivating coloration-reducing solvent, the coloration-reducing solvent further contains a coloration-reducing component. The coloring-lowering component preferably contains at least one selected from the group consisting of ultraviolet absorbers, neutralizers, and radical trapping agents. Examples of the ultraviolet absorber, neutralizing agent and radical trapping agent include the ultraviolet absorbing agent, neutralizing agent and radical trapping agent described above with respect to the color-reducing sheet Y, preferably the radical trapping agent.
着色性低下溶媒における着色性低下成分の割合は、好ましくは１質量％以上、より好ましくは５質量％以上であり、また、好ましくは６０質量％以下、好ましくは５０質量％以下である。
The proportion of the coloring-lowering component in the coloring-lowering solvent is preferably 1% by mass or more, more preferably 5% by mass or more, and is preferably 60% by mass or less, preferably 50% by mass or less.
本発明について、以下に実施例を示して具体的に説明するが、本発明は、実施例に限定されない。また、以下に記載されている配合量（含有量）、物性値、パラメータなどの具体的数値は、上述の「発明を実施するための形態」において記載されている、それらに対応する配合量（含有量）、物性値、パラメータなどの上限（「以下」または「未満」として定義されている数値）または下限（「以上」または「超える」として定義されている数値）に代替できる。
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In addition, the specific numerical values such as the compounding amount (content), physical property values, parameters, etc. described below are the corresponding compounding amounts ( content), physical properties, parameters, etc., upper limits (values defined as “less than” or “less than”) or lower limits (values defined as “greater than” or “greater than”).
〈アクリルポリマーＰ１の調製〉
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）６３質量部と、メタクリル酸メチル（ＭＭＡ）９質量部と、アクリル酸２-ヒドロキシエチル（ＨＥＡ）１３質量部と、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１５質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ１を含有する第１ポリマー溶液を得た。第１ポリマー溶液中のアクリルポリマーＰ１の重量平均分子量（Ｍｗ）は、１２０万であった。 <Preparation of acrylic polymer P1 >
63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2- Hydroxyethyl (HEA) 13 parts by mass, N-vinyl-2-pyrrolidone (NVP) 15 parts by mass, and 2,2'-azobisisobutyronitrile (AIBN) 0.2 parts by mass as a polymerization initiator , and 233 parts by mass of ethyl acetate as a solvent were stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). This gave a first polymer solution containing the acrylic polymer P1. The weight average molecular weight (Mw) of acrylic polymer P1 in the first polymer solution was 1.2 million.
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）６３質量部と、メタクリル酸メチル（ＭＭＡ）９質量部と、アクリル酸２-ヒドロキシエチル（ＨＥＡ）１３質量部と、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１５質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ１を含有する第１ポリマー溶液を得た。第１ポリマー溶液中のアクリルポリマーＰ１の重量平均分子量（Ｍｗ）は、１２０万であった。 <Preparation of acrylic polymer P1 >
63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2- Hydroxyethyl (HEA) 13 parts by mass, N-vinyl-2-pyrrolidone (NVP) 15 parts by mass, and 2,2'-azobisisobutyronitrile (AIBN) 0.2 parts by mass as a polymerization initiator , and 233 parts by mass of ethyl acetate as a solvent were stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). This gave a first polymer solution containing the acrylic polymer P1. The weight average molecular weight (Mw) of acrylic polymer P1 in the first polymer solution was 1.2 million.
〈アクリルポリマーＰ２の調製〉
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）９６質量部と、アクリル酸２－ヒドロキシエチル（ＨＥＡ）４質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ２を含有する第２ポリマー溶液を得た。第２ポリマー溶液中のアクリルポリマーＰ２の重量平均分子量（Ｍｗ）は、６０万であった。 <Preparation of acrylic polymer P2 >
96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) are polymerized in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. A mixture containing 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as an initiator and 233 parts by mass of ethyl acetate as a solvent was stirred at 60°C for 7 hours under a nitrogen atmosphere. (polymerization reaction). This gave a second polymer solution containing acrylic polymer P2. The weight average molecular weight (Mw) of acrylic polymer P2 in the second polymer solution was 600,000.
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）９６質量部と、アクリル酸２－ヒドロキシエチル（ＨＥＡ）４質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ２を含有する第２ポリマー溶液を得た。第２ポリマー溶液中のアクリルポリマーＰ２の重量平均分子量（Ｍｗ）は、６０万であった。 <Preparation of acrylic polymer P2 >
96 parts by mass of 2-ethylhexyl acrylate (2EHA) and 4 parts by mass of 2-hydroxyethyl acrylate (HEA) are polymerized in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube. A mixture containing 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as an initiator and 233 parts by mass of ethyl acetate as a solvent was stirred at 60°C for 7 hours under a nitrogen atmosphere. (polymerization reaction). This gave a second polymer solution containing acrylic polymer P2. The weight average molecular weight (Mw) of acrylic polymer P2 in the second polymer solution was 600,000.
〈アクリルポリマーＰ３の調製〉
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）４０質量部と、アクリル酸イソステアリル（ｉＳＴＡ）４０質量部と、アクリル酸４-ヒドロキシブチル（４ＨＢＡ）２質量部と、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１８質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ３を含有する第３ポリマー溶液を得た。第３ポリマー溶液中のアクリルポリマーＰ３の重量平均分子量（Ｍｗ）は、７０万であった。 <Preparation of acrylic polymer P3 >
40 parts by mass of 2-ethylhexyl acrylate (2EHA), 40 parts by mass of isostearyl acrylate (iSTA), and 4 parts of acrylic acid were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. -2 parts by mass of hydroxybutyl (4HBA), 18 parts by mass of N-vinyl-2-pyrrolidone (NVP), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 233 parts by mass of ethyl acetate as a solvent were stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). This gave a third polymer solution containing acrylic polymer P3. The weight average molecular weight (Mw) of acrylic polymer P3 in the third polymer solution was 700,000.
撹拌機、温度計、還流冷却器、および窒素ガス導入管を備える反応容器内で、アクリル酸２－エチルヘキシル（２ＥＨＡ）４０質量部と、アクリル酸イソステアリル（ｉＳＴＡ）４０質量部と、アクリル酸４-ヒドロキシブチル（４ＨＢＡ）２質量部と、Ｎ－ビニル－２－ピロリドン（ＮＶＰ）１８質量部と、重合開始剤としての２,２'－アゾビスイソブチロニトリル（ＡＩＢＮ）０.２質量部と、溶媒としての酢酸エチル２３３質量部とを含む混合物を、６０℃で７時間、窒素雰囲気下で撹拌した（重合反応）。これにより、アクリルポリマーＰ３を含有する第３ポリマー溶液を得た。第３ポリマー溶液中のアクリルポリマーＰ３の重量平均分子量（Ｍｗ）は、７０万であった。 <Preparation of acrylic polymer P3 >
40 parts by mass of 2-ethylhexyl acrylate (2EHA), 40 parts by mass of isostearyl acrylate (iSTA), and 4 parts of acrylic acid were placed in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. -2 parts by mass of hydroxybutyl (4HBA), 18 parts by mass of N-vinyl-2-pyrrolidone (NVP), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and 233 parts by mass of ethyl acetate as a solvent were stirred at 60° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). This gave a third polymer solution containing acrylic polymer P3. The weight average molecular weight (Mw) of acrylic polymer P3 in the third polymer solution was 700,000.
〈粘着性組成物Ｃ１の調製〉
アクリルポリマーＰ１を含有する第１ポリマー溶液に、アクリルポリマーＰ１１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「タケネートＤ１１０Ｎ」，三井化学社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，１質量％酢酸エチル溶液，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤（架橋触媒に対する配位子）としてのアセチルアセトン３質量部と、発色性化合物としてのロイコ色素（商品名「Ｓ－２０５」，山田化学工業社製）２質量部と、光酸発生剤（商品名「ＳＰ－０５６」，ＡＤＥＫＡ社製）７質量部とを加えて混合し、粘着性組成物Ｃ１を調製した。 < Preparation of adhesive composition C1>
In the first polymer solution containing the acrylic polymer P1, 0.25 parts by mass (solid content converted amount), 0.01 parts by mass of dibutyltin dilaurate (trade name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst (solid content equivalent amount), and a crosslinking inhibitor ( 3 parts by mass of acetylacetone as a ligand for the crosslinking catalyst, 2 parts by mass of leuco dye (trade name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) as a color-developing compound, and a photoacid generator (trade name " SP - 056", manufactured by ADEKA Corporation) and 7 parts by mass were added and mixed to prepare adhesive composition C1.
アクリルポリマーＰ１を含有する第１ポリマー溶液に、アクリルポリマーＰ１１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「タケネートＤ１１０Ｎ」，三井化学社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，１質量％酢酸エチル溶液，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤（架橋触媒に対する配位子）としてのアセチルアセトン３質量部と、発色性化合物としてのロイコ色素（商品名「Ｓ－２０５」，山田化学工業社製）２質量部と、光酸発生剤（商品名「ＳＰ－０５６」，ＡＤＥＫＡ社製）７質量部とを加えて混合し、粘着性組成物Ｃ１を調製した。 < Preparation of adhesive composition C1>
In the first polymer solution containing the acrylic polymer P1, 0.25 parts by mass (solid content converted amount), 0.01 parts by mass of dibutyltin dilaurate (trade name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst (solid content equivalent amount), and a crosslinking inhibitor ( 3 parts by mass of acetylacetone as a ligand for the crosslinking catalyst, 2 parts by mass of leuco dye (trade name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) as a color-developing compound, and a photoacid generator (trade name " SP - 056", manufactured by ADEKA Corporation) and 7 parts by mass were added and mixed to prepare adhesive composition C1.
〈粘着性組成物Ｃ２の調製〉
着色性低下成分としてのラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）４質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ２を調製した。 <Preparation of adhesive composition C2 >
Adhesive composition C2 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of a radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was further added as a coloring-reducing component. did.
着色性低下成分としてのラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）４質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ２を調製した。 <Preparation of adhesive composition C2 >
Adhesive composition C2 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of a radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was further added as a coloring-reducing component. did.
〈粘着性組成物Ｃ３の調製〉
着色性低下成分としてのラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）８質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ３を調製した。 <Preparation of adhesive composition C3 >
Adhesive composition C3 was prepared in the same manner as adhesive composition C1 , except that 8 parts by mass of a radical trapping agent (trade name "Tinuvin 249", manufactured by BASF) was further added as a coloring - reducing component. did.
着色性低下成分としてのラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）８質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ３を調製した。 <Preparation of adhesive composition C3 >
Adhesive composition C3 was prepared in the same manner as adhesive composition C1 , except that 8 parts by mass of a radical trapping agent (trade name "Tinuvin 249", manufactured by BASF) was further added as a coloring - reducing component. did.
〈粘着性組成物Ｃ４の調製〉
アクリルポリマーＰ２を含有する第２ポリマー溶液に、アクリルポリマーＰ２１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「コロネートＨＸ」，ヘキサメチレンジイソシアネートのイソシアヌレート体，東ソー社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，１質量％酢酸エチル溶液，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤としてのアセチルアセトン３質量部と、ラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）４質量部とを加えて混合し、粘着性組成物Ｃ４を調製した。 <Preparation of adhesive composition C4 >
In the second polymer solution containing the acrylic polymer P2, an isocyanate cross-linking agent (trade name “Coronate HX”, isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) is added as a cross-linking agent per 100 parts by mass of the acrylic polymer P2. .25 parts by mass (solid content equivalent) and 0.01 mass parts (solid content equivalent) of dibutyltin dilaurate (trade name “OL-1”, 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst ), 3 parts by mass of acetylacetone as a cross-linking inhibitor, and 4 parts by mass of a radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) were added and mixed to prepare adhesive composition C4 .
アクリルポリマーＰ２を含有する第２ポリマー溶液に、アクリルポリマーＰ２１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「コロネートＨＸ」，ヘキサメチレンジイソシアネートのイソシアヌレート体，東ソー社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，１質量％酢酸エチル溶液，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤としてのアセチルアセトン３質量部と、ラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）４質量部とを加えて混合し、粘着性組成物Ｃ４を調製した。 <Preparation of adhesive composition C4 >
In the second polymer solution containing the acrylic polymer P2, an isocyanate cross-linking agent (trade name “Coronate HX”, isocyanurate of hexamethylene diisocyanate, manufactured by Tosoh Corporation) is added as a cross-linking agent per 100 parts by mass of the acrylic polymer P2. .25 parts by mass (solid content equivalent) and 0.01 mass parts (solid content equivalent) of dibutyltin dilaurate (trade name “OL-1”, 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst ), 3 parts by mass of acetylacetone as a cross-linking inhibitor, and 4 parts by mass of a radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) were added and mixed to prepare adhesive composition C4 .
〈粘着性組成物Ｃ５の調製〉
ラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）の配合量を４質量部に代えて８質量部としたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ５を調製した。 <Preparation of adhesive composition C5 >
Adhesive composition C5 was prepared in the same manner as adhesive composition C4 except that the amount of the radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was changed to 8 parts by mass instead of 4 parts by mass. was prepared.
ラジカルトラップ剤（商品名「Ｔｉｎｕｖｉｎ ２４９」，ＢＡＳＦ社製）の配合量を４質量部に代えて８質量部としたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ５を調製した。 <Preparation of adhesive composition C5 >
Adhesive composition C5 was prepared in the same manner as adhesive composition C4 except that the amount of the radical trapping agent (trade name “Tinuvin 249”, manufactured by BASF) was changed to 8 parts by mass instead of 4 parts by mass. was prepared.
〈粘着性組成物Ｃ６の調製〉
アクリルポリマーＰ２を含有する第２ポリマー溶液に、アクリルポリマーＰ２１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「コロネートＨＸ」，東ソー社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤としてのアセチルアセトン３質量部とを加えて混合し、粘着性組成物Ｃ６を調製した。 <Preparation of adhesive composition C6 >
In the second polymer solution containing the acrylic polymer P2, 0.25 parts by mass of an isocyanate cross-linking agent (trade name "Coronate HX", manufactured by Tosoh Corporation) per 100 parts by mass of the acrylic polymer P2 (in terms of solid content) is added as a cross-linking agent. amount), 0.01 parts by mass (in terms of solid content) of dibutyltin dilaurate (trade name “OL-1”, manufactured by Tokyo Fine Chemical Co., Ltd.) as a cross-linking catalyst, and 3 parts by mass of acetylacetone as a cross-linking inhibitor. and mixed together to prepare adhesive composition C6 .
アクリルポリマーＰ２を含有する第２ポリマー溶液に、アクリルポリマーＰ２１００質量部あたり、架橋剤としてのイソシアネート架橋剤（商品名「コロネートＨＸ」，東ソー社製）０.２５質量部（固形分換算量）と、架橋触媒としてのジラウリン酸ジブチルスズ（商品名「ＯＬ－１」，東京ファインケミカル社製）０.０１質量部（固形分換算量）と、架橋抑制剤としてのアセチルアセトン３質量部とを加えて混合し、粘着性組成物Ｃ６を調製した。 <Preparation of adhesive composition C6 >
In the second polymer solution containing the acrylic polymer P2, 0.25 parts by mass of an isocyanate cross-linking agent (trade name "Coronate HX", manufactured by Tosoh Corporation) per 100 parts by mass of the acrylic polymer P2 (in terms of solid content) is added as a cross-linking agent. amount), 0.01 parts by mass (in terms of solid content) of dibutyltin dilaurate (trade name “OL-1”, manufactured by Tokyo Fine Chemical Co., Ltd.) as a cross-linking catalyst, and 3 parts by mass of acetylacetone as a cross-linking inhibitor. and mixed together to prepare adhesive composition C6 .
〈粘着性組成物Ｃ７の調製〉
第２ポリマー溶液の代わりに第３ポリマー溶液を用いたこと以外は、粘着性組成物Ｃ６と同様にして、粘着性組成物Ｃ７を調製した。 <Preparation of adhesive composition C7 >
Adhesive Composition C7 was prepared in the same manner as Adhesive Composition C6, except that a third polymer solution was used in place of the second polymer solution.
第２ポリマー溶液の代わりに第３ポリマー溶液を用いたこと以外は、粘着性組成物Ｃ６と同様にして、粘着性組成物Ｃ７を調製した。 <Preparation of adhesive composition C7 >
Adhesive Composition C7 was prepared in the same manner as Adhesive Composition C6, except that a third polymer solution was used in place of the second polymer solution.
〈粘着性組成物Ｃ８の調製〉
着色性低下成分としての紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）４質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ８を調製した。 <Preparation of adhesive composition C8 >
Adhesive composition C8 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
着色性低下成分としての紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）４質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ８を調製した。 <Preparation of adhesive composition C8 >
Adhesive composition C8 was prepared in the same manner as adhesive composition C1, except that 4 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
〈粘着性組成物Ｃ９の調製〉
着色性低下成分としての紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）８質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ９を調製した。 <Preparation of adhesive composition C9 >
Adhesive composition C9 was prepared in the same manner as adhesive composition C1, except that 8 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
着色性低下成分としての紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）８質量部を更に加えたこと以外は粘着性組成物Ｃ１と同様にして、粘着性組成物Ｃ９を調製した。 <Preparation of adhesive composition C9 >
Adhesive composition C9 was prepared in the same manner as adhesive composition C1, except that 8 parts by mass of an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) was further added as a coloring-reducing component. did.
〈粘着性組成物Ｃ１０の調製〉
ラジカルトラップ剤（Ｔｉｎｕｖｉｎ ２４９）４質量部に代えて紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）４質量部を用いたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ１０を調製した。 <Preparation of adhesive composition C10 >
Radical trapping agent (Tinuvin 249) In place of 4 parts by weight of ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) 4 parts by weight was used in the same manner as adhesive composition C 4 , adhesive Composition C10 was prepared.
ラジカルトラップ剤（Ｔｉｎｕｖｉｎ ２４９）４質量部に代えて紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）４質量部を用いたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ１０を調製した。 <Preparation of adhesive composition C10 >
Radical trapping agent (Tinuvin 249) In place of 4 parts by weight of ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) 4 parts by weight was used in the same manner as adhesive composition C 4 , adhesive Composition C10 was prepared.
〈粘着性組成物Ｃ１１の調製〉
ラジカルトラップ剤（Ｔｉｎｕｖｉｎ ２４９）４質量部に代えて紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）８質量部を用いたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ１１を調製した。 <Preparation of adhesive composition C11 >
Radical trap agent (Tinuvin 249) In place of 4 parts by mass, an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) 8 parts by mass was used. Composition C11 was prepared.
ラジカルトラップ剤（Ｔｉｎｕｖｉｎ ２４９）４質量部に代えて紫外線吸収剤（商品名「Ｔｉｎｕｖｉｎ ５７１」，ＢＡＳＦ社製）８質量部を用いたこと以外は粘着性組成物Ｃ４と同様にして、粘着性組成物Ｃ１１を調製した。 <Preparation of adhesive composition C11 >
Radical trap agent (Tinuvin 249) In place of 4 parts by mass, an ultraviolet absorber (trade name "Tinuvin 571", manufactured by BASF) 8 parts by mass was used. Composition C11 was prepared.
〈可変色粘着シートＸ１の作製〉
片面が離型処理されている厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面上に、粘着性組成物Ｃ１を塗布して塗膜を形成した。次に、この塗膜を、１３２℃で３分間の加熱によって、乾燥させた。これにより、基材フィルム上に厚さ２５μｍの粘着剤層を形成した。次に、基材フィルム上の粘着剤層に、片面が離型処理されている厚さ３８μｍの剥離フィルム（商品名「ＭＲＥ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面を貼り合わせた。その後、６０℃で２４時間、エージング処理し、粘着剤層中の架橋反応を進行させた。以上のようにして、保護フィルム付きの可変色粘着シートＸ１（厚さ２５μｍ）を作製した。可変色粘着シート中のロイコ色素および光酸発生剤については、相対的な配合量（質量部）を表１～４に示す。 <Preparation of variable color adhesive sheet X 1 >
Adhesive composition C1 was applied onto the release - treated surface of a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. The coating was then dried by heating at 132°C for 3 minutes. Thus, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, the release-treated surface of a 38 μm-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together. After that, aging treatment was performed at 60° C. for 24 hours to advance the cross-linking reaction in the pressure-sensitive adhesive layer. As described above, a protective film-attached color-changeable pressure-sensitive adhesive sheet X 1 (thickness: 25 μm) was produced. Tables 1 to 4 show the relative amounts (parts by mass) of the leuco dye and the photoacid generator in the color-changeable pressure-sensitive adhesive sheet.
片面が離型処理されている厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面上に、粘着性組成物Ｃ１を塗布して塗膜を形成した。次に、この塗膜を、１３２℃で３分間の加熱によって、乾燥させた。これにより、基材フィルム上に厚さ２５μｍの粘着剤層を形成した。次に、基材フィルム上の粘着剤層に、片面が離型処理されている厚さ３８μｍの剥離フィルム（商品名「ＭＲＥ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面を貼り合わせた。その後、６０℃で２４時間、エージング処理し、粘着剤層中の架橋反応を進行させた。以上のようにして、保護フィルム付きの可変色粘着シートＸ１（厚さ２５μｍ）を作製した。可変色粘着シート中のロイコ色素および光酸発生剤については、相対的な配合量（質量部）を表１～４に示す。 <Preparation of variable color adhesive sheet X 1 >
Adhesive composition C1 was applied onto the release - treated surface of a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. The coating was then dried by heating at 132°C for 3 minutes. Thus, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, the release-treated surface of a 38 μm-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together. After that, aging treatment was performed at 60° C. for 24 hours to advance the cross-linking reaction in the pressure-sensitive adhesive layer. As described above, a protective film-attached color-changeable pressure-sensitive adhesive sheet X 1 (thickness: 25 μm) was produced. Tables 1 to 4 show the relative amounts (parts by mass) of the leuco dye and the photoacid generator in the color-changeable pressure-sensitive adhesive sheet.
〈可変色粘着シートＲ１の作製〉
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ２を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ１を作製した。 <Preparation of color-changeable adhesive sheet R1 >
A color-changeable pressure-sensitive adhesive sheet R1 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C2 was used instead of the pressure - sensitive adhesive composition C1.
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ２を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ１を作製した。 <Preparation of color-changeable adhesive sheet R1 >
A color-changeable pressure-sensitive adhesive sheet R1 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C2 was used instead of the pressure - sensitive adhesive composition C1.
〈可変色粘着シートＲ２の作製〉
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ３を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ２を作製した。 <Production of color-changeable adhesive sheet R2 >
A color-changeable pressure-sensitive adhesive sheet R2 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure - sensitive adhesive composition C3 was used instead of the pressure - sensitive adhesive composition C1.
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ３を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ２を作製した。 <Production of color-changeable adhesive sheet R2 >
A color-changeable pressure-sensitive adhesive sheet R2 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure - sensitive adhesive composition C3 was used instead of the pressure - sensitive adhesive composition C1.
〈可変色粘着シートＲ３の作製〉
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ８を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ３を作製した。 <Preparation of color - changeable adhesive sheet R3>
A color-changeable pressure - sensitive adhesive sheet R3 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C8 was used instead of the pressure - sensitive adhesive composition C1.
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ８を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ３を作製した。 <Preparation of color - changeable adhesive sheet R3>
A color-changeable pressure - sensitive adhesive sheet R3 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C8 was used instead of the pressure - sensitive adhesive composition C1.
〈可変色粘着シートＲ４の作製〉
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ９を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ４を作製した。 <Production of color-changeable adhesive sheet R4 >
A color-changeable pressure-sensitive adhesive sheet R4 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C9 was used instead of the pressure - sensitive adhesive composition C1.
粘着性組成物Ｃ１の代わりに粘着性組成物Ｃ９を用いたこと以外は可変色粘着シートＸ１と同様にして、保護フィルム付きの可変色粘着シートＲ４を作製した。 <Production of color-changeable adhesive sheet R4 >
A color-changeable pressure-sensitive adhesive sheet R4 with a protective film was prepared in the same manner as the color-changeable pressure - sensitive adhesive sheet X1, except that the pressure-sensitive adhesive composition C9 was used instead of the pressure - sensitive adhesive composition C1.
〈失活用粘着シートＤ１の作製〉
片面が離型処理されている厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面上に、粘着性組成物Ｃ４を塗布して塗膜を形成した。次に、この塗膜を、室温で１０分間放置した後、８０℃で５分間の加熱と、その後の１３０℃で１分間の加熱とによって、乾燥させた。これにより、基材フィルム上に厚さ２５μｍの粘着剤層を形成した。次に、基材フィルム上の粘着剤層に、片面が離型処理されている厚さ３８μｍの剥離フィルム（商品名「ＭＲＥ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面を貼り合わせた。その後、６０℃で２４時間、エージング処理し、粘着剤層中の架橋反応を進行させた。以上のようにして、保護フィルム付きの失活用粘着シートＤ１（厚さ２５μｍ）を作製した。 <Preparation of deactivation adhesive sheet D 1 >
Adhesive composition C4 was applied onto the release-treated surface of a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. Next, the coating film was allowed to stand at room temperature for 10 minutes, then dried by heating at 80° C. for 5 minutes and then heating at 130° C. for 1 minute. Thus, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, the release-treated surface of a 38 μm-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together. After that, aging treatment was performed at 60° C. for 24 hours to advance the cross-linking reaction in the pressure-sensitive adhesive layer. As described above, a deactivating pressure-sensitive adhesive sheet D 1 (thickness: 25 μm) with a protective film was produced.
片面が離型処理されている厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面上に、粘着性組成物Ｃ４を塗布して塗膜を形成した。次に、この塗膜を、室温で１０分間放置した後、８０℃で５分間の加熱と、その後の１３０℃で１分間の加熱とによって、乾燥させた。これにより、基材フィルム上に厚さ２５μｍの粘着剤層を形成した。次に、基材フィルム上の粘着剤層に、片面が離型処理されている厚さ３８μｍの剥離フィルム（商品名「ＭＲＥ＃３８」，ポリエステルフィルム，三菱樹脂社製）の離型処理面を貼り合わせた。その後、６０℃で２４時間、エージング処理し、粘着剤層中の架橋反応を進行させた。以上のようにして、保護フィルム付きの失活用粘着シートＤ１（厚さ２５μｍ）を作製した。 <Preparation of deactivation adhesive sheet D 1 >
Adhesive composition C4 was applied onto the release-treated surface of a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) one side of which was release-treated. A coating was formed. Next, the coating film was allowed to stand at room temperature for 10 minutes, then dried by heating at 80° C. for 5 minutes and then heating at 130° C. for 1 minute. Thus, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, the release-treated surface of a 38 μm-thick release film (trade name “MRE #38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) whose one side is release-treated is applied to the adhesive layer on the base film. pasted together. After that, aging treatment was performed at 60° C. for 24 hours to advance the cross-linking reaction in the pressure-sensitive adhesive layer. As described above, a deactivating pressure-sensitive adhesive sheet D 1 (thickness: 25 μm) with a protective film was produced.
〈失活用粘着シートＤ２の作製〉
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ５を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ２を作製した。 <Preparation of deactivating adhesive sheet D2>
Deactivated adhesive sheet D2 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C5 was used instead of adhesive composition C4 .
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ５を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ２を作製した。 <Preparation of deactivating adhesive sheet D2>
Deactivated adhesive sheet D2 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C5 was used instead of adhesive composition C4 .
〈失活用粘着シートＤ３の作製〉
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ１０を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ３を作製した。 <Preparation of deactivating adhesive sheet D3 >
Deactivated adhesive sheet D3 with a protective film was prepared in the same manner as deactivated adhesive sheet D1 , except that adhesive composition C10 was used instead of adhesive composition C4 .
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ１０を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ３を作製した。 <Preparation of deactivating adhesive sheet D3 >
Deactivated adhesive sheet D3 with a protective film was prepared in the same manner as deactivated adhesive sheet D1 , except that adhesive composition C10 was used instead of adhesive composition C4 .
〈失活用粘着シートＤ４の作製〉
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ１１を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ４を作製した。 <Preparation of deactivation adhesive sheet D4 >
Deactivated adhesive sheet D4 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C11 was used instead of adhesive composition C4 .
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ１１を用いたこと以外は失活用粘着シートＤ１と同様にして、保護フィルム付きの失活用粘着シートＤ４を作製した。 <Preparation of deactivation adhesive sheet D4 >
Deactivated adhesive sheet D4 with a protective film was prepared in the same manner as deactivated adhesive sheet D1, except that adhesive composition C11 was used instead of adhesive composition C4 .
〈抽出用粘着シートＥ１の作製〉
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ６を用いたこと、および、厚さを２５μｍに代えて１００μｍとしたこと以外は、失活用粘着シートＤ１と同様にして、保護フィルム付きの抽出用粘着シートＥ１を作製した。 <Preparation of pressure - sensitive adhesive sheet for extraction E1>
With a protective film in the same manner as the deactivating adhesive sheet D 1 , except that the adhesive composition C 6 was used instead of the adhesive composition C 4 , and the thickness was changed from 25 μm to 100 μm. was prepared .
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ６を用いたこと、および、厚さを２５μｍに代えて１００μｍとしたこと以外は、失活用粘着シートＤ１と同様にして、保護フィルム付きの抽出用粘着シートＥ１を作製した。 <Preparation of pressure - sensitive adhesive sheet for extraction E1>
With a protective film in the same manner as the deactivating adhesive sheet D 1 , except that the adhesive composition C 6 was used instead of the adhesive composition C 4 , and the thickness was changed from 25 μm to 100 μm. was prepared .
〈抽出用粘着シートＥ２の作製〉
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ７を用いたこと、および、厚さを２５μｍに代えて１００μｍとしたこと以外は、失活用粘着シートＤ１と同様にして、保護フィルム付きの抽出用粘着シートＥ２を作製した。 <Preparation of pressure - sensitive adhesive sheet for extraction E2>
With a protective film in the same manner as the deactivating adhesive sheet D 1 , except that the adhesive composition C 7 was used instead of the adhesive composition C 4 , and the thickness was changed from 25 μm to 100 μm. An extraction pressure - sensitive adhesive sheet E2 was produced.
粘着性組成物Ｃ４の代わりに粘着性組成物Ｃ７を用いたこと、および、厚さを２５μｍに代えて１００μｍとしたこと以外は、失活用粘着シートＤ１と同様にして、保護フィルム付きの抽出用粘着シートＥ２を作製した。 <Preparation of pressure - sensitive adhesive sheet for extraction E2>
With a protective film in the same manner as the deactivating adhesive sheet D 1 , except that the adhesive composition C 7 was used instead of the adhesive composition C 4 , and the thickness was changed from 25 μm to 100 μm. An extraction pressure - sensitive adhesive sheet E2 was produced.
〔実施例１〕
可変色粘着シートＸ１と失活用粘着シートＤ１とから、次のようにして積層体Ｌ１を得た。まず、可変色粘着シートＸ１を用意した（第１工程）。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離し、失活用粘着シートＤ１から剥離フィルムを剥離した後、可変色粘着シートＸ１に対して失活用粘着シートＤ１を貼り合わせた（第２工程）。以上のようにして、実施例１の積層体Ｌ１を得た。積層体Ｌ１は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ１（厚さ２５μｍ）と、基材フィルムとを順に備える。積層体Ｌ１は、可変色粘着シートＸ１と失活用粘着シートＤ１との積層シートを含む。 [Example 1]
A laminate L 1 was obtained from the color-changeable adhesive sheet X 1 and the deactivating adhesive sheet D 1 in the following manner. First, the color-changeable pressure-sensitive adhesive sheet X1 was prepared ( first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on eagle glass and peeling off the release film from the deactivating adhesive sheet D1, the deactivating adhesive sheet D1 is applied to the color - changeable adhesive sheet X1. were pasted together (second step). As described above, the laminate L1 of Example 1 was obtained. The laminate L 1 includes, in order, eagle glass, a color-changeable adhesive sheet X 1 (25 μm thick), a disabling adhesive sheet D 1 (25 μm thick), and a base film. Laminate L1 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D1.
可変色粘着シートＸ１と失活用粘着シートＤ１とから、次のようにして積層体Ｌ１を得た。まず、可変色粘着シートＸ１を用意した（第１工程）。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離し、失活用粘着シートＤ１から剥離フィルムを剥離した後、可変色粘着シートＸ１に対して失活用粘着シートＤ１を貼り合わせた（第２工程）。以上のようにして、実施例１の積層体Ｌ１を得た。積層体Ｌ１は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ１（厚さ２５μｍ）と、基材フィルムとを順に備える。積層体Ｌ１は、可変色粘着シートＸ１と失活用粘着シートＤ１との積層シートを含む。 [Example 1]
A laminate L 1 was obtained from the color-changeable adhesive sheet X 1 and the deactivating adhesive sheet D 1 in the following manner. First, the color-changeable pressure-sensitive adhesive sheet X1 was prepared ( first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on eagle glass and peeling off the release film from the deactivating adhesive sheet D1, the deactivating adhesive sheet D1 is applied to the color - changeable adhesive sheet X1. were pasted together (second step). As described above, the laminate L1 of Example 1 was obtained. The laminate L 1 includes, in order, eagle glass, a color-changeable adhesive sheet X 1 (25 μm thick), a disabling adhesive sheet D 1 (25 μm thick), and a base film. Laminate L1 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D1.
〔実施例２〕
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ２を用いたこと以外は、実施例１と同様の各工程を実施して、実施例２の積層体Ｌ２を得た。積層体Ｌ２は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ２と、基材フィルムとを順に備える。積層体Ｌ２は、可変色粘着シートＸ１と失活用粘着シートＤ２との積層シートを含む。 [Example 2]
A laminate L2 of Example 2 was obtained by carrying out the same steps as in Example 1 , except that the deactivated adhesive sheet D2 was used instead of the deactivated adhesive sheet D1 in the second step. . Laminate L2 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D2, and a base film. Laminate L2 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ２を用いたこと以外は、実施例１と同様の各工程を実施して、実施例２の積層体Ｌ２を得た。積層体Ｌ２は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ２と、基材フィルムとを順に備える。積層体Ｌ２は、可変色粘着シートＸ１と失活用粘着シートＤ２との積層シートを含む。 [Example 2]
A laminate L2 of Example 2 was obtained by carrying out the same steps as in Example 1 , except that the deactivated adhesive sheet D2 was used instead of the deactivated adhesive sheet D1 in the second step. . Laminate L2 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D2, and a base film. Laminate L2 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
〔実施例３〕
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ３を用いたこと以外は、実施例１と同様の各工程を実施して、実施例３の積層体Ｌ３を得た。積層体Ｌ３は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ３と、基材フィルムとを順に備える。積層体Ｌ３は、可変色粘着シートＸ１と失活用粘着シートＤ３との積層シートを含む。 [Example 3]
Laminate L3 of Example 3 was obtained by performing the same steps as in Example 1 , except that in the second step, the deactivated adhesive sheet D3 was used instead of the deactivated adhesive sheet D1. . Laminate L3 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film. Laminate L3 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D3 .
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ３を用いたこと以外は、実施例１と同様の各工程を実施して、実施例３の積層体Ｌ３を得た。積層体Ｌ３は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ３と、基材フィルムとを順に備える。積層体Ｌ３は、可変色粘着シートＸ１と失活用粘着シートＤ３との積層シートを含む。 [Example 3]
Laminate L3 of Example 3 was obtained by performing the same steps as in Example 1 , except that in the second step, the deactivated adhesive sheet D3 was used instead of the deactivated adhesive sheet D1. . Laminate L3 comprises , in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film. Laminate L3 includes a laminated sheet of color - changeable adhesive sheet X1 and deactivating adhesive sheet D3 .
〔実施例４〕
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ４を用いたこと以外は、実施例１と同様の各工程を実施して、実施例４の積層体Ｌ４を得た。積層体Ｌ４は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ３と、基材フィルムとを順に備える。積層体Ｌ４は、可変色粘着シートＸ１と失活用粘着シートＤ４との積層シートを含む。 [Example 4]
Laminate L4 of Example 4 was obtained by carrying out the same steps as in Example 1 , except that in the second step, deactivated adhesive sheet D4 was used instead of deactivated adhesive sheet D1. . Laminate L4 comprises, in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film. Laminate L 4 includes a laminate of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 4 .
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ４を用いたこと以外は、実施例１と同様の各工程を実施して、実施例４の積層体Ｌ４を得た。積層体Ｌ４は、イーグルガラスと、可変色粘着シートＸ１と、失活用粘着シートＤ３と、基材フィルムとを順に備える。積層体Ｌ４は、可変色粘着シートＸ１と失活用粘着シートＤ４との積層シートを含む。 [Example 4]
Laminate L4 of Example 4 was obtained by carrying out the same steps as in Example 1 , except that in the second step, deactivated adhesive sheet D4 was used instead of deactivated adhesive sheet D1. . Laminate L4 comprises, in order, eagle glass, color - changeable adhesive sheet X1, disabling adhesive sheet D3 , and a base film. Laminate L 4 includes a laminate of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 4 .
〔比較例１〕
実施例１と同様の第１工程を実施して、比較例１の積層体Ｌ５を得た。積層体Ｌ５は、イーグルガラスと、可変色粘着シートＸ１と、基材フィルムとを順に備える（失活用粘着シートを備えない）。 [Comparative Example 1]
A first step similar to that of Example 1 was carried out to obtain a laminate L5 of Comparative Example 1 . Laminate L 5 comprises, in order, eagle glass, color-changeable adhesive sheet X 1 and substrate film (without disabling adhesive sheet).
実施例１と同様の第１工程を実施して、比較例１の積層体Ｌ５を得た。積層体Ｌ５は、イーグルガラスと、可変色粘着シートＸ１と、基材フィルムとを順に備える（失活用粘着シートを備えない）。 [Comparative Example 1]
A first step similar to that of Example 1 was carried out to obtain a laminate L5 of Comparative Example 1 . Laminate L 5 comprises, in order, eagle glass, color-changeable adhesive sheet X 1 and substrate film (without disabling adhesive sheet).
〔実施例５〕
可変色粘着シートＸ１と失活用粘着シートＤ１とから、次のようにして積層体Ｌ６を得た。まず、実施例１の積層体Ｌ１（イーグルガラス／可変色粘着シートＸ１／失活用粘着シートＤ１／基材フィルム）を用意した。次に、この積層体Ｌ１における失活用粘着シートＤ１から基材フィルムを剥離した。そして、当該剥離によって露出した粘着シート面に、トリアセチルセルロース（ＴＡＣ）フィルム（商品名「ＫＣ２ＵＡ」，厚さ２８μｍ，コニカミノルタ社製）と、紫外線吸収機能を有する粘着テープ（商品名「ＣＳ９９３４Ｕ」，日東電工社製）と、ポリエチレンテレフタレート（ＰＥＴ）フィルム（商品名「Ｇ９８１ Ｅ７５」，厚さ７５μｍ，三菱ケミカル社製）とをこの順で貼り合わせて積層した。以上のようにして、実施例５の積層体Ｌ６を得た。積層体Ｌ６は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ６は、可変色粘着シートＸ１と失活用粘着シートＤ１との積層シートを含む。 [Example 5]
A laminate L6 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D1 in the following manner. First, the laminate L 1 (Eagle glass/color-changeable pressure-sensitive adhesive sheet X 1 /disabling pressure-sensitive adhesive sheet D 1 /base film) of Example 1 was prepared. Next, the base film was peeled off from the deactivated pressure-sensitive adhesive sheet D- 1 in this laminate L- 1 . Then, on the adhesive sheet surface exposed by the peeling, a triacetyl cellulose (TAC) film (trade name “KC2UA”, thickness 28 μm, manufactured by Konica Minolta) and an adhesive tape having an ultraviolet absorption function (trade name “CS9934U”) , manufactured by Nitto Denko) and a polyethylene terephthalate (PET) film (trade name “G981 E75”, thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) were laminated in this order. As described above, the laminate L6 of Example 5 was obtained. Laminate L 6 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), deactivating adhesive sheet D 1 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order. Laminate L 6 includes a laminated sheet of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 1 .
可変色粘着シートＸ１と失活用粘着シートＤ１とから、次のようにして積層体Ｌ６を得た。まず、実施例１の積層体Ｌ１（イーグルガラス／可変色粘着シートＸ１／失活用粘着シートＤ１／基材フィルム）を用意した。次に、この積層体Ｌ１における失活用粘着シートＤ１から基材フィルムを剥離した。そして、当該剥離によって露出した粘着シート面に、トリアセチルセルロース（ＴＡＣ）フィルム（商品名「ＫＣ２ＵＡ」，厚さ２８μｍ，コニカミノルタ社製）と、紫外線吸収機能を有する粘着テープ（商品名「ＣＳ９９３４Ｕ」，日東電工社製）と、ポリエチレンテレフタレート（ＰＥＴ）フィルム（商品名「Ｇ９８１ Ｅ７５」，厚さ７５μｍ，三菱ケミカル社製）とをこの順で貼り合わせて積層した。以上のようにして、実施例５の積層体Ｌ６を得た。積層体Ｌ６は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ６は、可変色粘着シートＸ１と失活用粘着シートＤ１との積層シートを含む。 [Example 5]
A laminate L6 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D1 in the following manner. First, the laminate L 1 (Eagle glass/color-changeable pressure-sensitive adhesive sheet X 1 /disabling pressure-sensitive adhesive sheet D 1 /base film) of Example 1 was prepared. Next, the base film was peeled off from the deactivated pressure-sensitive adhesive sheet D- 1 in this laminate L- 1 . Then, on the adhesive sheet surface exposed by the peeling, a triacetyl cellulose (TAC) film (trade name “KC2UA”, thickness 28 μm, manufactured by Konica Minolta) and an adhesive tape having an ultraviolet absorption function (trade name “CS9934U”) , manufactured by Nitto Denko) and a polyethylene terephthalate (PET) film (trade name “G981 E75”, thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) were laminated in this order. As described above, the laminate L6 of Example 5 was obtained. Laminate L 6 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), deactivating adhesive sheet D 1 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order. Laminate L 6 includes a laminated sheet of color-changeable adhesive sheet X 1 and deactivating adhesive sheet D 1 .
〔実施例６〕
実施例１の積層体Ｌ１の代わりに実施例２の積層体Ｌ２を用いたこと以外は、実施例５と同様の各工程を実施して、実施例６の積層体Ｌ７を得た。積層体Ｌ７は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ２（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ７は、可変色粘着シートＸ１と失活用粘着シートＤ２との積層シートを含む。 [Example 6]
A laminate L7 of Example 6 was obtained by performing the same steps as in Example 5 except that the laminate L2 of Example 2 was used instead of the laminate L1 of Example 1 . . Laminate L 7 is composed of Eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), deactivating adhesive sheet D 2 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order. Laminate L7 includes a laminate of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
実施例１の積層体Ｌ１の代わりに実施例２の積層体Ｌ２を用いたこと以外は、実施例５と同様の各工程を実施して、実施例６の積層体Ｌ７を得た。積層体Ｌ７は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ２（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ７は、可変色粘着シートＸ１と失活用粘着シートＤ２との積層シートを含む。 [Example 6]
A laminate L7 of Example 6 was obtained by performing the same steps as in Example 5 except that the laminate L2 of Example 2 was used instead of the laminate L1 of Example 1 . . Laminate L 7 is composed of Eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), deactivating adhesive sheet D 2 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film. (Base film) are provided in order. Laminate L7 includes a laminate of color - changeable adhesive sheet X1 and deactivating adhesive sheet D2.
〔比較例２〕
実施例１の積層体Ｌ１の代わりに比較例１の積層体Ｌ３を用いたこと以外は、実施例５と同様の各工程を実施して、比較例２の積層体Ｌ８を得た。積層体Ｌ８は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える（失活用粘着シートを備えない）。 [Comparative Example 2]
A laminate L- 8 of Comparative Example 2 was obtained by performing the same steps as in Example 5 except that the laminate L- 3 of Comparative Example 1 was used instead of the laminate L- 1 of Example 1. . Laminate L 8 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film (base film) in this order (disabling adhesive without a seat).
実施例１の積層体Ｌ１の代わりに比較例１の積層体Ｌ３を用いたこと以外は、実施例５と同様の各工程を実施して、比較例２の積層体Ｌ８を得た。積層体Ｌ８は、イーグルガラスと、可変色粘着シートＸ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える（失活用粘着シートを備えない）。 [Comparative Example 2]
A laminate L- 8 of Comparative Example 2 was obtained by performing the same steps as in Example 5 except that the laminate L- 3 of Comparative Example 1 was used instead of the laminate L- 1 of Example 1. . Laminate L 8 includes eagle glass, color-changeable adhesive sheet X 1 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, and PET film (base film) in this order (disabling adhesive without a seat).
〔実施例７〕
可変色粘着シートＸ１と失活用粘着シートＤ３とから、次のようにして積層体Ｌ９を得た。 [Example 7]
A laminate L9 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D3 in the following manner.
可変色粘着シートＸ１と失活用粘着シートＤ３とから、次のようにして積層体Ｌ９を得た。 [Example 7]
A laminate L9 was obtained from the color - changeable adhesive sheet X1 and the deactivating adhesive sheet D3 in the following manner.
まず、可変色粘着シートＸ１を用意した（第１工程）。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。
First, the color-changeable pressure-sensitive adhesive sheet X1 was prepared ( first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.).
次に、イーグルガラス上の可変色粘着シートＸ１に対して紫外線（ＵＶ）を照射した（第２工程）。具体的には、２３℃および相対湿度５０％の環境下において、イーグルガラス上の可変色粘着シートＸ１に対して基材フィルム側（イーグルガラスとは反対の側）からＵＶを照射した。これにより、可変色粘着シートＸ１において、光酸発生剤から酸を発生させ、当該酸によってロイコ色素を発色させた。ＵＶ照射では、クォークテクノロジー社製のＵＶ－ＬＥＤ照射装置（型番「ＱＥＬ－３５０－ＲＵ６Ｗ－ＣＷ－ＭＹ」）における波長３６５ｎｍのＵＶ－ＬＥＤランプを光源として使用し、波長３２０～３９０ｎｍの範囲での照射積算光量を８０００ｍＪ／ｃｍ２とした。
Next, the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass was irradiated with ultraviolet rays (UV) (second step). Specifically, under an environment of 23° C. and a relative humidity of 50%, the color-changeable pressure - sensitive adhesive sheet X1 on eagle glass was irradiated with UV from the base film side (the side opposite to the eagle glass). As a result, in the color-changeable pressure-sensitive adhesive sheet X1, an acid was generated from the photoacid generator, and the leuco dye was colored by the acid. For UV irradiation, a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm. The integrated irradiation light amount was set to 8000 mJ/cm 2 .
次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離し、失活用粘着シートＤ３から剥離フィルムを剥離した後、可変色粘着シートＸ１に対して失活用粘着シートＤ３を貼り合わせた（第３工程）。
Next, after peeling off the base film from the color - changeable adhesive sheet X1 on eagle glass and peeling off the release film from the disabling adhesive sheet D3 , the disabling adhesive sheet D3 is applied to the color - changeable adhesive sheet X1. were pasted together (third step).
次に、この失活用粘着シートＤ３から基材フィルムを剥離した後、当該剥離によって露出した粘着シート面に、ＴＡＣフィルム（商品名「ＫＣ２ＵＡ」，厚さ２８μｍ，コニカミノルタ社製）と、紫外線吸収機能を有する粘着テープ（商品名「ＣＳ９９３４Ｕ」，日東電工社製）と、ＰＥＴフィルム（商品名「Ｇ９８１ Ｅ７５」，厚さ７５μｍ，三菱ケミカル社製）とをこの順で貼り合わせて積層した。
Next, after peeling off the base film from this deactivating adhesive sheet D3 , a TAC film (trade name “KC2UA”, thickness 28 μm, manufactured by Konica Minolta Co., Ltd.) and an ultraviolet An adhesive tape (trade name: "CS9934U", manufactured by Nitto Denko Corporation) having an absorption function and a PET film (trade name: "G981 E75", thickness: 75 µm, manufactured by Mitsubishi Chemical Corporation) were laminated in this order.
以上のようにして、実施例７の積層体Ｌ９を得た。積層体Ｌ９は、イーグルガラスと、着色した可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ３（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ９は、着色した可変色粘着シートＸ１と失活用粘着シートＤ３との積層シートを含む。
As described above, the laminate L9 of Example 7 was obtained. Laminate L 9 includes eagle glass, colored variable color adhesive sheet X 1 (25 μm thick), deactivated adhesive sheet D 3 (25 μm thick), TAC film, and UV-absorbing adhesive tape. A PET film (base film) is provided in order. Laminate L 9 comprises a laminated sheet of colored variable color adhesive sheet X 1 and deactivating adhesive sheet D 3 .
〔実施例８〕
第３工程において失活用粘着シートＤ３の代わりに失活用粘着シートＤ４を用いたこと以外は、実施例７と同様の各工程を実施して、実施例８の積層体Ｌ１０を得た。積層体Ｌ１０は、イーグルガラスと、着色した可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ４（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ１０は、着色した可変色粘着シートＸ１と失活用粘着シートＤ４との積層シートを含む。 [Example 8]
Laminate L10 of Example 8 was obtained by carrying out the same steps as in Example 7, except that the deactivated adhesive sheet D4 was used instead of the deactivated adhesive sheet D3 in the third step. . Laminate L 10 includes eagle glass, colored variable color adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 4 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, A PET film (base film) is provided in order. Laminate L 10 comprises a laminated sheet of colored variable color adhesive sheet X 1 and deactivating adhesive sheet D 4 .
第３工程において失活用粘着シートＤ３の代わりに失活用粘着シートＤ４を用いたこと以外は、実施例７と同様の各工程を実施して、実施例８の積層体Ｌ１０を得た。積層体Ｌ１０は、イーグルガラスと、着色した可変色粘着シートＸ１（厚さ２５μｍ）と、失活用粘着シートＤ４（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える。積層体Ｌ１０は、着色した可変色粘着シートＸ１と失活用粘着シートＤ４との積層シートを含む。 [Example 8]
Laminate L10 of Example 8 was obtained by carrying out the same steps as in Example 7, except that the deactivated adhesive sheet D4 was used instead of the deactivated adhesive sheet D3 in the third step. . Laminate L 10 includes eagle glass, colored variable color adhesive sheet X 1 (thickness 25 μm), deactivation adhesive sheet D 4 (thickness 25 μm), TAC film, UV-absorbing adhesive tape, A PET film (base film) is provided in order. Laminate L 10 comprises a laminated sheet of colored variable color adhesive sheet X 1 and deactivating adhesive sheet D 4 .
〔比較例３〕
第３工程（失活用粘着シートＤ３の貼り合わせ）を実施しなかったこと以外は、実施例７と同様の各工程を実施して、比較例３の積層体Ｌ１１を得た。積層体Ｌ１１は、イーグルガラスと、着色した可変色粘着シートＸ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える（失活用粘着シートを備えない）。 [Comparative Example 3]
A laminate L- 11 of Comparative Example 3 was obtained by carrying out the same steps as in Example 7, except that the third step (bonding of the deactivating pressure-sensitive adhesive sheet D3) was not carried out. The laminate L 11 includes eagle glass, a colored variable-color adhesive sheet X 1 (thickness 25 μm), a TAC film, an ultraviolet-absorbing adhesive tape, and a PET film (base film) in this order. not equipped with a utilization adhesive sheet).
第３工程（失活用粘着シートＤ３の貼り合わせ）を実施しなかったこと以外は、実施例７と同様の各工程を実施して、比較例３の積層体Ｌ１１を得た。積層体Ｌ１１は、イーグルガラスと、着色した可変色粘着シートＸ１（厚さ２５μｍ）と、ＴＡＣフィルムと、紫外線吸収性の粘着テープと、ＰＥＴフィルム（基材フィルム）とを順に備える（失活用粘着シートを備えない）。 [Comparative Example 3]
A laminate L- 11 of Comparative Example 3 was obtained by carrying out the same steps as in Example 7, except that the third step (bonding of the deactivating pressure-sensitive adhesive sheet D3) was not carried out. The laminate L 11 includes eagle glass, a colored variable-color adhesive sheet X 1 (thickness 25 μm), a TAC film, an ultraviolet-absorbing adhesive tape, and a PET film (base film) in this order. not equipped with a utilization adhesive sheet).
〔実施例９〕
可変色粘着シートＸ１と失活用粘着シートＤ１とマスクフィルムとから、次のようにして積層体Ｌ１２を得た。まず、可変色粘着シートＸ１（５０ｍｍ×１００ｍｍ）を用意した（第１工程）。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、同シート上に厚さ２５μｍのマスクフィルム（商品名「ルミラーＳ１０」，５０ｍｍ×５０ｍｍ，透明なポリエステルフィルム，東レ社製）を積層した。次に、失活用粘着シートＤ１から剥離フィルムを剥離した後、可変色粘着シートＸ１に対して失活用粘着シートＤ１（５０ｍｍ×１００ｍｍ）を貼り合わせた（第２工程）。以上のようにして、実施例９の積層体Ｌ１２を得た。積層体Ｌ１２は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、失活用粘着シートＤ１と、基材フィルムとを順に備える。積層体Ｌ１２は、可変色粘着シートＸ１と、マスクフィルムと、失活用粘着シートＤ１との積層シートを含む。 [Example 9]
A laminate L 12 was obtained from the color-changeable adhesive sheet X 1 , the deactivating adhesive sheet D 1 , and the mask film in the following manner. First, a color-changeable pressure-sensitive adhesive sheet X 1 (50 mm×100 mm) was prepared (first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on the eagle glass, a 25 μm-thick mask film (trade name “Lumirror S10”, 50 mm×50 mm, transparent polyester film, Toray) was placed on the same sheet. company) was laminated. Next, after peeling off the release film from the deactivating adhesive sheet D1, the deactivating adhesive sheet D1 (50 mm× 100 mm) was attached to the color - changeable adhesive sheet X1 ( second step). As described above, the laminate L12 of Example 9 was obtained. Laminate L12 comprises, in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D1, and base film. Laminate L12 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D1.
可変色粘着シートＸ１と失活用粘着シートＤ１とマスクフィルムとから、次のようにして積層体Ｌ１２を得た。まず、可変色粘着シートＸ１（５０ｍｍ×１００ｍｍ）を用意した（第１工程）。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、同シート上に厚さ２５μｍのマスクフィルム（商品名「ルミラーＳ１０」，５０ｍｍ×５０ｍｍ，透明なポリエステルフィルム，東レ社製）を積層した。次に、失活用粘着シートＤ１から剥離フィルムを剥離した後、可変色粘着シートＸ１に対して失活用粘着シートＤ１（５０ｍｍ×１００ｍｍ）を貼り合わせた（第２工程）。以上のようにして、実施例９の積層体Ｌ１２を得た。積層体Ｌ１２は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、失活用粘着シートＤ１と、基材フィルムとを順に備える。積層体Ｌ１２は、可変色粘着シートＸ１と、マスクフィルムと、失活用粘着シートＤ１との積層シートを含む。 [Example 9]
A laminate L 12 was obtained from the color-changeable adhesive sheet X 1 , the deactivating adhesive sheet D 1 , and the mask film in the following manner. First, a color-changeable pressure-sensitive adhesive sheet X 1 (50 mm×100 mm) was prepared (first step). Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on the eagle glass, a 25 μm-thick mask film (trade name “Lumirror S10”, 50 mm×50 mm, transparent polyester film, Toray) was placed on the same sheet. company) was laminated. Next, after peeling off the release film from the deactivating adhesive sheet D1, the deactivating adhesive sheet D1 (50 mm× 100 mm) was attached to the color - changeable adhesive sheet X1 ( second step). As described above, the laminate L12 of Example 9 was obtained. Laminate L12 comprises, in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D1, and base film. Laminate L12 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D1.
〔実施例１０〕
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ２（５０ｍｍ×１００ｍｍ）を用いたこと以外は、実施例９と同様の各工程を実施して、実施例１０の積層体Ｌ１３を得た。積層体Ｌ１３は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、失活用粘着シートＤ２と、基材フィルムとを順に備える。積層体Ｌ１３は、可変色粘着シートＸ１と、マスクフィルムと、失活用粘着シートＤ２との積層シートを含む。 [Example 10]
The same steps as in Example 9 were carried out except that the deactivated adhesive sheet D 2 (50 mm × 100 mm) was used instead of the deactivated adhesive sheet D 1 in the second step, and the laminate of Example 10 was obtained. L13 was obtained. Laminate L13 comprises , in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D2, and base film. Laminate L13 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D2.
第２工程において失活用粘着シートＤ１の代わりに失活用粘着シートＤ２（５０ｍｍ×１００ｍｍ）を用いたこと以外は、実施例９と同様の各工程を実施して、実施例１０の積層体Ｌ１３を得た。積層体Ｌ１３は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、失活用粘着シートＤ２と、基材フィルムとを順に備える。積層体Ｌ１３は、可変色粘着シートＸ１と、マスクフィルムと、失活用粘着シートＤ２との積層シートを含む。 [Example 10]
The same steps as in Example 9 were carried out except that the deactivated adhesive sheet D 2 (50 mm × 100 mm) was used instead of the deactivated adhesive sheet D 1 in the second step, and the laminate of Example 10 was obtained. L13 was obtained. Laminate L13 comprises , in order, eagle glass, color - changeable adhesive sheet X1, mask film for partially masking color - changeable adhesive sheet X1, disabling adhesive sheet D2, and base film. Laminate L13 includes a laminate of color - changeable adhesive sheet X1, mask film, and deactivating adhesive sheet D2.
〔比較例４〕
第２工程において、失活用粘着シートＤ１の代わりに厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，５０ｍｍ×１００ｍｍ，ポリエステルフィルム，三菱樹脂社製）を用いたこと以外は実施例９と同様の各工程を実施して、比較例４の積層体Ｌ１４を得た。積層体Ｌ１４は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、基材フィルムとを順に備える（失活用粘着シートを備えない）。 [Comparative Example 4]
Example except that in the second step, a 38 μm thick base film (trade name “MRF #38”, 50 mm × 100 mm, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was used instead of the deactivating adhesive sheet D1. Laminate L14 of Comparative Example 4 was obtained by performing the same steps as in Example 9. Laminate L 14 comprises eagle glass, color-changeable adhesive sheet X 1 , mask film for partially masking color-changeable adhesive sheet X 1 , and base film in order (without deactivating adhesive sheet). .
第２工程において、失活用粘着シートＤ１の代わりに厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，５０ｍｍ×１００ｍｍ，ポリエステルフィルム，三菱樹脂社製）を用いたこと以外は実施例９と同様の各工程を実施して、比較例４の積層体Ｌ１４を得た。積層体Ｌ１４は、イーグルガラスと、可変色粘着シートＸ１と、可変色粘着シートＸ１を部分的にマスクするマスクフィルムと、基材フィルムとを順に備える（失活用粘着シートを備えない）。 [Comparative Example 4]
Example except that in the second step, a 38 μm thick base film (trade name “MRF #38”, 50 mm × 100 mm, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was used instead of the deactivating adhesive sheet D1. Laminate L14 of Comparative Example 4 was obtained by performing the same steps as in Example 9. Laminate L 14 comprises eagle glass, color-changeable adhesive sheet X 1 , mask film for partially masking color-changeable adhesive sheet X 1 , and base film in order (without deactivating adhesive sheet). .
〔実施例１１〕
第２工程において失活用粘着シートＤ１の代わりに抽出用粘着シートＥ１を用いたこと以外は、実施例１と同様の各工程を実施して、実施例１１の積層体Ｌ１５を得た。積層体Ｌ１５は、イーグルガラスと、可変色粘着シートＸ１と、抽出用粘着シートＥ１と、基材フィルムとを順に備える。積層体Ｌ１５は、可変色粘着シートＸ１と、抽出用粘着シートＥ１との積層シートを含む。 [Example 11]
Laminate L15 of Example 11 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E1 was used instead of the deactivating adhesive sheet D1 in the second step. . The laminate L 15 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 1 , and a base film. The laminate L 15 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 1 .
第２工程において失活用粘着シートＤ１の代わりに抽出用粘着シートＥ１を用いたこと以外は、実施例１と同様の各工程を実施して、実施例１１の積層体Ｌ１５を得た。積層体Ｌ１５は、イーグルガラスと、可変色粘着シートＸ１と、抽出用粘着シートＥ１と、基材フィルムとを順に備える。積層体Ｌ１５は、可変色粘着シートＸ１と、抽出用粘着シートＥ１との積層シートを含む。 [Example 11]
Laminate L15 of Example 11 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E1 was used instead of the deactivating adhesive sheet D1 in the second step. . The laminate L 15 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 1 , and a base film. The laminate L 15 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 1 .
〔実施例１２〕
第２工程において失活用粘着シートＤ１の代わりに抽出用粘着シートＥ２を用いたこと以外は、実施例１と同様の各工程を実施して、実施例１２の積層体Ｌ１６を得た。積層体Ｌ１６は、イーグルガラスと、可変色粘着シートＸ１と、抽出用粘着シートＥ２と、基材フィルムとを順に備える。積層体Ｌ１６は、可変色粘着シートＸ１と、抽出用粘着シートＥ２との積層シートを含む。 [Example 12]
A laminate L16 of Example 12 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E2 was used instead of the deactivating adhesive sheet D1 in the second step. . The laminate L 16 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 2 , and a base film. The laminate L 16 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 2 .
第２工程において失活用粘着シートＤ１の代わりに抽出用粘着シートＥ２を用いたこと以外は、実施例１と同様の各工程を実施して、実施例１２の積層体Ｌ１６を得た。積層体Ｌ１６は、イーグルガラスと、可変色粘着シートＸ１と、抽出用粘着シートＥ２と、基材フィルムとを順に備える。積層体Ｌ１６は、可変色粘着シートＸ１と、抽出用粘着シートＥ２との積層シートを含む。 [Example 12]
A laminate L16 of Example 12 was obtained by performing the same steps as in Example 1 except that the extraction adhesive sheet E2 was used instead of the deactivating adhesive sheet D1 in the second step. . The laminate L 16 includes, in order, an eagle glass, a color-changeable adhesive sheet X 1 , an extraction adhesive sheet E 2 , and a base film. The laminate L 16 includes a laminated sheet of the color-changeable adhesive sheet X 1 and the extraction adhesive sheet E 2 .
〔実施例１３〕
次のようにして実施例１３の積層体Ｌ１７を得た。まず、可変色粘着シートＸ１を用意した。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、当該可変色粘着シートＸ１をイーグルガラスとともにエタノール中に浸漬した（着色性低下処理としての浸漬処理）。浸漬時間は２分間とした。次に、イーグルガラス付き可変色粘着シートＸ１をエタノールから取り出し、１３２℃で３分間の加熱によって、乾燥させた。次に、イーグルガラス上の可変色粘着シートＸ１に、厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）を貼り合わせた。以上のようにして、実施例１３の積層体Ｌ１７を得た。積層体Ｌ１７は、イーグルガラスと、エタノールへの浸漬を経た可変色粘着シートＸ１と、基材フィルムとを順に備える。 [Example 13]
A laminate L17 of Example 13 was obtained as follows. First , a variable color pressure-sensitive adhesive sheet X1 was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass, the color-changeable pressure - sensitive adhesive sheet X1 was immersed in ethanol together with the eagle glass (immersion treatment as a treatment for reducing coloring property). The immersion time was 2 minutes. Next, the color-changeable pressure - sensitive adhesive sheet X1 with eagle glass was removed from ethanol and dried by heating at 132° C. for 3 minutes. Next, a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was attached to the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass. As described above, a laminate L17 of Example 13 was obtained. The laminate L 17 comprises, in order, eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a base film.
次のようにして実施例１３の積層体Ｌ１７を得た。まず、可変色粘着シートＸ１を用意した。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、当該可変色粘着シートＸ１をイーグルガラスとともにエタノール中に浸漬した（着色性低下処理としての浸漬処理）。浸漬時間は２分間とした。次に、イーグルガラス付き可変色粘着シートＸ１をエタノールから取り出し、１３２℃で３分間の加熱によって、乾燥させた。次に、イーグルガラス上の可変色粘着シートＸ１に、厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）を貼り合わせた。以上のようにして、実施例１３の積層体Ｌ１７を得た。積層体Ｌ１７は、イーグルガラスと、エタノールへの浸漬を経た可変色粘着シートＸ１と、基材フィルムとを順に備える。 [Example 13]
A laminate L17 of Example 13 was obtained as follows. First , a variable color pressure-sensitive adhesive sheet X1 was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass, the color-changeable pressure - sensitive adhesive sheet X1 was immersed in ethanol together with the eagle glass (immersion treatment as a treatment for reducing coloring property). The immersion time was 2 minutes. Next, the color-changeable pressure - sensitive adhesive sheet X1 with eagle glass was removed from ethanol and dried by heating at 132° C. for 3 minutes. Next, a 38 μm-thick base film (trade name “MRF#38”, polyester film, manufactured by Mitsubishi Plastics Co., Ltd.) was attached to the color-changeable pressure - sensitive adhesive sheet X1 on the eagle glass. As described above, a laminate L17 of Example 13 was obtained. The laminate L 17 comprises, in order, eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a base film.
〔実施例１４〕
着色性低下処理においてエタノールの代わりに酢酸エチルを用いたこと以外は実施例１３と同様にして、実施例１４の積層体Ｌ１８を得た。積層体Ｌ１８は、イーグルガラスと、酢酸エチルへの浸漬を経た可変色粘着シートＸ１と、基材フィルムとを順に備える。 [Example 14]
A laminate L18 of Example 14 was obtained in the same manner as in Example 13, except that ethyl acetate was used in place of ethanol in the color reduction treatment. Laminate L 18 comprises, in order, eagle glass, a color-changing adhesive sheet X 1 that has undergone immersion in ethyl acetate, and a base film.
着色性低下処理においてエタノールの代わりに酢酸エチルを用いたこと以外は実施例１３と同様にして、実施例１４の積層体Ｌ１８を得た。積層体Ｌ１８は、イーグルガラスと、酢酸エチルへの浸漬を経た可変色粘着シートＸ１と、基材フィルムとを順に備える。 [Example 14]
A laminate L18 of Example 14 was obtained in the same manner as in Example 13, except that ethyl acetate was used in place of ethanol in the color reduction treatment. Laminate L 18 comprises, in order, eagle glass, a color-changing adhesive sheet X 1 that has undergone immersion in ethyl acetate, and a base film.
〔実施例１５〕
次のようにして実施例１５の積層体Ｌ１９を得た。まず、可変色粘着シートＸ１（５０ｍｍ×１００ｍｍ）を用意した。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、同シート上に厚さ２５μｍのマスクフィルム（商品名「ルミラーＳ１０」，５０ｍｍ×５０ｍｍ，透明なポリエステルフィルム，東レ社製）を積層した。次に、当該マスクフィルムによって表面（イーグルガラス側表面とは反対側の表面）が部分的にマスクされた可変色粘着シートＸ１をイーグルガラスとともにエタノール中に浸漬させた（着色性低下処理としての浸漬処理）。浸漬時間は２分間とした。次に、イーグルガラス付き可変色粘着シートＸ１（表面がマスクフィルムによって部分的にマスクされている）をエタノールから取り出し、１３２℃で３分間の加熱によって、乾燥させた。次に、イーグルガラス上の可変色粘着シートＸ１において露出する領域（マスクフィルムによってはマスクされていない領域）に、厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）を貼り合わせた。以上のようにして、実施例１５の積層体Ｌ１９を得た。積層体Ｌ１９は、イーグルガラスと、エタノールへの浸漬を経た可変色粘着シートＸ１と、同シート上のマスクフィルムおよび基材フィルムとを、順に備える。積層体Ｌ１９は、エタノールへの浸漬を経た可変色粘着シートＸ１と、マスクフィルムとの積層シートを含む。 [Example 15]
A laminate L19 of Example 15 was obtained as follows. First, a variable color adhesive sheet X 1 (50 mm×100 mm) was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on the eagle glass, a 25 μm-thick mask film (trade name “Lumirror S10”, 50 mm×50 mm, transparent polyester film, Toray) was placed on the same sheet. company) was laminated. Next, the color-changeable pressure - sensitive adhesive sheet X1 whose surface (the surface opposite to the eagle glass side surface) was partially masked by the mask film was immersed in ethanol together with the eagle glass (as a coloration reduction treatment, immersion treatment). The immersion time was 2 minutes. Next, the color-changeable pressure-sensitive adhesive sheet X 1 with eagle glass (the surface was partially masked with a mask film) was taken out of the ethanol and dried by heating at 132° C. for 3 minutes. Next, a base film with a thickness of 38 μm (trade name “MRF # 38”, polyester film, Mitsubishi Resin Co., Ltd.) was pasted together. As described above, the laminate L19 of Example 15 was obtained. Laminate L 19 comprises, in order, Eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a mask film and a base film on the same sheet. Laminate L 19 includes a laminated sheet of color-changeable adhesive sheet X 1 that has undergone ethanol immersion and a mask film.
次のようにして実施例１５の積層体Ｌ１９を得た。まず、可変色粘着シートＸ１（５０ｍｍ×１００ｍｍ）を用意した。具体的には、可変色粘着シートＸ１から剥離フィルムを剥がした後、同シートをイーグルガラス（厚さ０.５５ｍｍ，松浪硝子社製）に貼り合わせた。次に、イーグルガラス上の可変色粘着シートＸ１から基材フィルムを剥離した後、同シート上に厚さ２５μｍのマスクフィルム（商品名「ルミラーＳ１０」，５０ｍｍ×５０ｍｍ，透明なポリエステルフィルム，東レ社製）を積層した。次に、当該マスクフィルムによって表面（イーグルガラス側表面とは反対側の表面）が部分的にマスクされた可変色粘着シートＸ１をイーグルガラスとともにエタノール中に浸漬させた（着色性低下処理としての浸漬処理）。浸漬時間は２分間とした。次に、イーグルガラス付き可変色粘着シートＸ１（表面がマスクフィルムによって部分的にマスクされている）をエタノールから取り出し、１３２℃で３分間の加熱によって、乾燥させた。次に、イーグルガラス上の可変色粘着シートＸ１において露出する領域（マスクフィルムによってはマスクされていない領域）に、厚さ３８μｍの基材フィルム（商品名「ＭＲＦ＃３８」，ポリエステルフィルム，三菱樹脂社製）を貼り合わせた。以上のようにして、実施例１５の積層体Ｌ１９を得た。積層体Ｌ１９は、イーグルガラスと、エタノールへの浸漬を経た可変色粘着シートＸ１と、同シート上のマスクフィルムおよび基材フィルムとを、順に備える。積層体Ｌ１９は、エタノールへの浸漬を経た可変色粘着シートＸ１と、マスクフィルムとの積層シートを含む。 [Example 15]
A laminate L19 of Example 15 was obtained as follows. First, a variable color adhesive sheet X 1 (50 mm×100 mm) was prepared. Specifically, after peeling off the release film from the color-changeable pressure - sensitive adhesive sheet X1, the same sheet was attached to Eagle Glass (thickness: 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). Next, after peeling off the base film from the color - changeable adhesive sheet X1 on the eagle glass, a 25 μm-thick mask film (trade name “Lumirror S10”, 50 mm×50 mm, transparent polyester film, Toray) was placed on the same sheet. company) was laminated. Next, the color-changeable pressure - sensitive adhesive sheet X1 whose surface (the surface opposite to the eagle glass side surface) was partially masked by the mask film was immersed in ethanol together with the eagle glass (as a coloration reduction treatment, immersion treatment). The immersion time was 2 minutes. Next, the color-changeable pressure-sensitive adhesive sheet X 1 with eagle glass (the surface was partially masked with a mask film) was taken out of the ethanol and dried by heating at 132° C. for 3 minutes. Next, a base film with a thickness of 38 μm (trade name “MRF # 38”, polyester film, Mitsubishi Resin Co., Ltd.) was pasted together. As described above, the laminate L19 of Example 15 was obtained. Laminate L 19 comprises, in order, Eagle glass, a color-changeable adhesive sheet X 1 that has undergone ethanol immersion, and a mask film and a base film on the same sheet. Laminate L 19 includes a laminated sheet of color-changeable adhesive sheet X 1 that has undergone ethanol immersion and a mask film.
〔参考例１〕
可変色粘着シートＸ１の代わりに可変色粘着シートＲ１を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例１の積層体Ｌ２１を得た。積層体Ｌ２１は、イーグルガラスと、可変色粘着シートＲ１と、基材フィルムとを順に備える。 [Reference Example 1]
A laminate L21 of Reference Example 1 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R1 was used instead of the color - changeable adhesive sheet X1. Laminate L21 includes Eagle glass, color-changeable pressure-sensitive adhesive sheet R1 , and base film in this order.
可変色粘着シートＸ１の代わりに可変色粘着シートＲ１を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例１の積層体Ｌ２１を得た。積層体Ｌ２１は、イーグルガラスと、可変色粘着シートＲ１と、基材フィルムとを順に備える。 [Reference Example 1]
A laminate L21 of Reference Example 1 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R1 was used instead of the color - changeable adhesive sheet X1. Laminate L21 includes Eagle glass, color-changeable pressure-sensitive adhesive sheet R1 , and base film in this order.
〔参考例２〕
可変色粘着シートＸ１の代わりに可変色粘着シートＲ２を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例２の積層体Ｌ２２を得た。積層体Ｌ２２は、イーグルガラスと、可変色粘着シートＲ２と、基材フィルムとを順に備える。 [Reference example 2]
A laminate L22 of Reference Example 2 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R2 was used instead of the color - changeable adhesive sheet X1. Laminate L22 comprises, in order, Eagle glass, color-changeable adhesive sheet R2 , and base film.
可変色粘着シートＸ１の代わりに可変色粘着シートＲ２を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例２の積層体Ｌ２２を得た。積層体Ｌ２２は、イーグルガラスと、可変色粘着シートＲ２と、基材フィルムとを順に備える。 [Reference example 2]
A laminate L22 of Reference Example 2 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R2 was used instead of the color - changeable adhesive sheet X1. Laminate L22 comprises, in order, Eagle glass, color-changeable adhesive sheet R2 , and base film.
〔参考例３〕
可変色粘着シートＸ１の代わりに可変色粘着シートＲ３を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例３の積層体Ｌ２３を得た。積層体Ｌ２３は、イーグルガラスと、可変色粘着シートＲ３と、基材フィルムとを順に備える。 [Reference Example 3]
A laminate L23 of Reference Example 3 was obtained by performing the same step as the first step of Example 1, except that the color-changeable adhesive sheet R3 was used instead of the color - changeable adhesive sheet X1. Laminate L 23 includes Eagle glass, color-changeable adhesive sheet R 3 and base film in this order.
可変色粘着シートＸ１の代わりに可変色粘着シートＲ３を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例３の積層体Ｌ２３を得た。積層体Ｌ２３は、イーグルガラスと、可変色粘着シートＲ３と、基材フィルムとを順に備える。 [Reference Example 3]
A laminate L23 of Reference Example 3 was obtained by performing the same step as the first step of Example 1, except that the color-changeable adhesive sheet R3 was used instead of the color - changeable adhesive sheet X1. Laminate L 23 includes Eagle glass, color-changeable adhesive sheet R 3 and base film in this order.
〔参考例４〕
可変色粘着シートＸ１の代わりに可変色粘着シートＲ４を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例４の積層体Ｌ２４を得た。積層体Ｌ２４は、イーグルガラスと、可変色粘着シートＲ４と、基材フィルムとを順に備える。 [Reference Example 4]
A laminate L24 of Reference Example 4 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R4 was used instead of the color - changeable adhesive sheet X1. Laminate L 24 comprises, in order, eagle glass, color-changeable adhesive sheet R 4 and base film.
可変色粘着シートＸ１の代わりに可変色粘着シートＲ４を用いたこと以外は実施例１の第１工程と同様の工程を実施して、参考例４の積層体Ｌ２４を得た。積層体Ｌ２４は、イーグルガラスと、可変色粘着シートＲ４と、基材フィルムとを順に備える。 [Reference Example 4]
A laminate L24 of Reference Example 4 was obtained by performing the same step as the first step of Example 1 except that the color-changeable adhesive sheet R4 was used instead of the color - changeable adhesive sheet X1. Laminate L 24 comprises, in order, eagle glass, color-changeable adhesive sheet R 4 and base film.
〈初期透過率〉
実施例１～１０,１３～１５、比較例１～４、および参考例１～４の各積層体について、作製から２５℃で２４時間が経過した後、波長４００～７００ｎｍでの平均透過率を測定した（第１の透過率測定）。この透過率測定には、透過率測定装置（商品名「Ｕ４１５０形分光光度計」，日立ハイテクサイエンス社製）を使用した。装置内では、積層体のイーグルガラスが光源側に位置し且つ同積層体の基材フィルムがディテクター側に位置するように、積層体を配置した。また、本測定では、イーグルガラスのみについて同一条件で測定して得られた透過率スペクトルをベースラインとして用いた。測定された平均透過率を初期透過率Ｔ０（％）として、表１～４,６,７に示す。 <Initial transmittance>
For each laminate of Examples 1 to 10, 13 to 15, Comparative Examples 1 to 4, and Reference Examples 1 to 4, after 24 hours at 25 ° C. from the production, the average transmittance at a wavelength of 400 to 700 nm was measured. was measured (first transmittance measurement). A transmittance measuring device (trade name “U4150 spectrophotometer”, manufactured by Hitachi High-Tech Science Co., Ltd.) was used for this transmittance measurement. In the apparatus, the stack was positioned so that the eagle glass of the stack was on the light source side and the base film of the stack was on the detector side. In addition, in this measurement, the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as a baseline. Tables 1 to 4, 6, and 7 show the measured average transmittance as initial transmittance T 0 (%).
実施例１～１０,１３～１５、比較例１～４、および参考例１～４の各積層体について、作製から２５℃で２４時間が経過した後、波長４００～７００ｎｍでの平均透過率を測定した（第１の透過率測定）。この透過率測定には、透過率測定装置（商品名「Ｕ４１５０形分光光度計」，日立ハイテクサイエンス社製）を使用した。装置内では、積層体のイーグルガラスが光源側に位置し且つ同積層体の基材フィルムがディテクター側に位置するように、積層体を配置した。また、本測定では、イーグルガラスのみについて同一条件で測定して得られた透過率スペクトルをベースラインとして用いた。測定された平均透過率を初期透過率Ｔ０（％）として、表１～４,６,７に示す。 <Initial transmittance>
For each laminate of Examples 1 to 10, 13 to 15, Comparative Examples 1 to 4, and Reference Examples 1 to 4, after 24 hours at 25 ° C. from the production, the average transmittance at a wavelength of 400 to 700 nm was measured. was measured (first transmittance measurement). A transmittance measuring device (trade name “U4150 spectrophotometer”, manufactured by Hitachi High-Tech Science Co., Ltd.) was used for this transmittance measurement. In the apparatus, the stack was positioned so that the eagle glass of the stack was on the light source side and the base film of the stack was on the detector side. In addition, in this measurement, the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as a baseline. Tables 1 to 4, 6, and 7 show the measured average transmittance as initial transmittance T 0 (%).
<積層体Ｌ１～Ｌ５,Ｌ２１～Ｌ２４の透過率変化>
第１の透過率測定を経た実施例１～４、比較例１および参考例１～４の各積層体について、以下のようにして、紫外線照射による透過率変化を調べた。 <Transmittance change of laminates L 1 to L 5 and L 21 to L 24 >
For each laminate of Examples 1 to 4, Comparative Example 1, and Reference Examples 1 to 4, which had undergone the first transmittance measurement, changes in transmittance due to ultraviolet irradiation were examined as follows.
第１の透過率測定を経た実施例１～４、比較例１および参考例１～４の各積層体について、以下のようにして、紫外線照射による透過率変化を調べた。 <Transmittance change of laminates L 1 to L 5 and L 21 to L 24 >
For each laminate of Examples 1 to 4, Comparative Example 1, and Reference Examples 1 to 4, which had undergone the first transmittance measurement, changes in transmittance due to ultraviolet irradiation were examined as follows.
まず、積層体に対して紫外線（ＵＶ）を照射した（第１のＵＶ照射）。具体的には、２３℃および相対湿度５０％の環境下において、積層体における可変色粘着シートに対して基材フィルム側からＵＶを照射した。これにより、可変色粘着シートにおいて、光酸発生剤から酸を発生させ、当該酸によってロイコ色素を発色させた。ＵＶ照射では、クォークテクノロジー社製のＵＶ－ＬＥＤ照射装置（型番「ＱＥＬ－３５０－ＲＵ６Ｗ－ＣＷ－ＭＹ」）における波長３６５ｎｍのＵＶ－ＬＥＤランプを光源として使用し、波長３２０～３９０ｎｍの範囲での照射積算光量を８０００ｍＪ／ｃｍ２とした。
First, the laminate was irradiated with ultraviolet rays (UV) (first UV irradiation). Specifically, under an environment of 23° C. and a relative humidity of 50%, the color-changeable pressure-sensitive adhesive sheet in the laminate was irradiated with UV from the base film side. As a result, in the color-changeable pressure-sensitive adhesive sheet, an acid was generated from the photoacid generator, and the leuco dye was colored by the acid. For UV irradiation, a UV-LED lamp with a wavelength of 365 nm in a Quark Technology UV-LED irradiation device (model number “QEL-350-RU6W-CW-MY”) is used as a light source, and the wavelength is in the range of 320 to 390 nm. The integrated irradiation light amount was set to 8000 mJ/cm 2 .
次に、積層体の、波長４００～７００ｎｍでの平均透過率を、測定した（第２の透過率測定）。本測定における使用装置および条件は、第１の透過率測定における使用装置および条件と同じである。測定された平均透過率を透過率Ｔ１（％）として表１に示す。初期透過率Ｔ０と透過率Ｔ１との差ΔＴ（＝Ｔ０－Ｔ１）も、表１に示す。実施例１～４の積層体Ｌ１～Ｌ４は、比較例１の積層体Ｌ５よりも、ΔＴが有意に小さく、良好な変色抑制性を示した。また、比較例１の積層体Ｌ５（可変色粘着シート内に着色性低下成分が配合されていない）と参考例１～４の積層体Ｌ２１～Ｌ２４（可変色粘着シート内に着色性低下成分が配合されている）との透過率Ｔ１の差は、着色性低下成分の着色性低下性能を示す。すなわち、光酸発生剤（第１化合物）および発色性化合物（第２化合物）と着色性低下成分とが共存する、積層体Ｌ２１～Ｌ２４の可変色粘着シートＲ１～Ｒ４（第１の系）では、着色性低下成分が着色性低下性能を発揮するため、当該第１の系における紫外線照射（外部刺激付与）による透過率の低下ΔＴは、着色性低下成分が存在しないこと以外は積層体Ｌ２１～Ｌ２４の可変色粘着シートＲ１,Ｒ２（第１の系）と同じ積層体Ｌ５の可変色粘着シートＸ１（第２の系）における紫外線照射（外部刺激付与）による透過率の低下ΔＴ’より小さい。このように、可変色粘着シートにおいては、着色処理前から光酸発生剤（第１化合物）および発色性化合物（第２化合物）と着色性低下成分とが共存する場合、当該可変色粘着シートは着色能力が低くて着色しにくいことが分かる（参考例１～４）。これに対し、所定領域を着色させた後の可変色粘着シートに対して事後的に着色性低下成分を浸透させることにより、前記所定領域については、その着色能力を十分に発揮させて良好に着色させられるとともに、非着色領域（透明領域）については、変色しにくくさせて変色を抑制できる（本発明）。
Next, the laminate was measured for average transmittance at a wavelength of 400 to 700 nm (second transmittance measurement). The apparatus and conditions used in this measurement are the same as the apparatus and conditions used in the first transmittance measurement. Table 1 shows the measured average transmittance as transmittance T 1 (%). Table 1 also shows the difference ΔT (=T 0 −T 1 ) between the initial transmittance T 0 and the transmittance T 1 . The laminates L 1 to L 4 of Examples 1 to 4 had significantly smaller ΔT than the laminate L 5 of Comparative Example 1, and exhibited good discoloration suppression properties. In addition, the laminate L 5 of Comparative Example 1 (the color-reducing component is not blended in the color-changeable pressure-sensitive adhesive sheet) and the laminates L 21 to L 24 of Reference Examples 1-4 (the color-changeable pressure-sensitive adhesive sheet contains The difference in transmittance T1 from the sample containing the color-lowering component indicates the color-lowering performance of the color-lowering component. That is, the variable color adhesive sheets R 1 to R 4 ( first system), since the coloring-reducing component exerts coloring-reducing performance, the transmittance decrease ΔT due to ultraviolet irradiation (external stimulus application) in the first system is UV irradiation (applying external stimulus) to the color-changeable adhesive sheets R 1 and R 2 (first system) of the laminates L 21 to L 24 and the color-changeable adhesive sheet X 1 (second system) of the same laminate L 5 is less than the decrease in transmittance ΔT' due to . As described above, in the color-changeable pressure-sensitive adhesive sheet, when the photoacid generator (first compound) and the color-developing compound (second compound) coexist with the color-reducing component before the coloring treatment, the color-changeable pressure-sensitive adhesive sheet is It can be seen that the coloring ability is low and coloring is difficult (Reference Examples 1 to 4). On the other hand, by impregnating the color-changing pressure-sensitive adhesive sheet after the predetermined region has been colored with the color-reducing component, the predetermined region can be sufficiently colored by exhibiting its coloring ability. In addition, the non-colored area (transparent area) can be prevented from being discolored (present invention).
<積層体Ｌ６～Ｌ１１の透過率変化>
第１の透過率測定を経た実施例５～８および比較例２,３の各積層体について、以下のようにして、耐候性試験による透過率変化を調べた。 <Transmittance change of laminates L6 to L11 >
The laminates of Examples 5 to 8 and Comparative Examples 2 and 3, which had undergone the first transmittance measurement, were examined for change in transmittance by a weather resistance test as follows.
第１の透過率測定を経た実施例５～８および比較例２,３の各積層体について、以下のようにして、耐候性試験による透過率変化を調べた。 <Transmittance change of laminates L6 to L11 >
The laminates of Examples 5 to 8 and Comparative Examples 2 and 3, which had undergone the first transmittance measurement, were examined for change in transmittance by a weather resistance test as follows.
まず、耐候試験装置（商品名「スーパーキセノンウェザーメーターＳＸ７５」，スガ試験機社製）のチャンバ内に積層体を配置した。具体的には、チャンバ内において、積層体の基材フィルムが光源（スーパーキセノンランプ）側に位置するように、積層体を配置した。次に、５５℃および相対湿度５５％の環境下において、積層体における可変色粘着シートに対し、スーパーキセノンランプ（波長３００～４００ｎｍ）により、２４時間、光照射した。
First, the laminate was placed in the chamber of a weather resistance test device (trade name "Super Xenon Weather Meter SX75", manufactured by Suga Test Instruments Co., Ltd.). Specifically, the laminate was placed in the chamber such that the base film of the laminate was positioned on the light source (super xenon lamp) side. Next, in an environment of 55° C. and 55% relative humidity, the color-changeable pressure-sensitive adhesive sheet in the laminate was irradiated with light from a super xenon lamp (wavelength 300-400 nm) for 24 hours.
次に、積層体の、波長４００～７００ｎｍでの平均透過率を、測定した（第３の透過率測定）。測定された平均透過率を透過率Ｔ２（％）として表２,３に示す。表２,３には、初期透過率Ｔ０と透過率Ｔ２との差ΔＴ（＝Ｔ０－Ｔ２）も示す。表２に示すように、実施例５,６の積層体Ｌ６,Ｌ７は、比較例２の積層体Ｌ８よりも、ΔＴが有意に小さく、良好な変色抑制性を示した。表３に示すように、実施例７,８の積層体Ｌ９,Ｌ１０は、比較例３の積層体Ｌ１１よりも、ΔＴの絶対値が有意に小さく、良好な変色抑制性を示した。
Next, the laminate was measured for average transmittance at wavelengths of 400 to 700 nm (third transmittance measurement). Tables 2 and 3 show the measured average transmittance as transmittance T 2 (%). Tables 2 and 3 also show the difference ΔT (=T 0 -T 2 ) between the initial transmittance T 0 and the transmittance T 2 . As shown in Table 2, the laminates L 6 and L 7 of Examples 5 and 6 had a significantly smaller ΔT than the laminate L 8 of Comparative Example 2 and exhibited good discoloration suppressing properties. As shown in Table 3, the laminates L 9 and L 10 of Examples 7 and 8 had a significantly smaller absolute value of ΔT than the laminate L 11 of Comparative Example 3, and exhibited good discoloration suppression properties. .
<積層体Ｌ１２～Ｌ１４の透過率変化>
第１の透過率測定を経た実施例９,１０および比較例４の各積層体について、以下のようにして、紫外線照射による透過率変化を調べた。 <Transmittance change of laminates L 12 to L 14 >
Regarding the laminates of Examples 9 and 10 and Comparative Example 4 that had undergone the first transmittance measurement, changes in transmittance due to ultraviolet irradiation were examined as follows.
第１の透過率測定を経た実施例９,１０および比較例４の各積層体について、以下のようにして、紫外線照射による透過率変化を調べた。 <Transmittance change of laminates L 12 to L 14 >
Regarding the laminates of Examples 9 and 10 and Comparative Example 4 that had undergone the first transmittance measurement, changes in transmittance due to ultraviolet irradiation were examined as follows.
まず、積層体に対して紫外線（ＵＶ）を照射した。ＵＶ照射の方法および条件は、第１のＵＶ照射に関して上述したのと同様である。次に、積層体における、マスクフィルムが配置されている領域（マスク領域）と、マスクフィルムが配置されていない領域（非マスク領域）とのそれぞれについて、波長４００～７００ｎｍでの平均透過率を、測定した。本測定における使用装置および条件は、第１および第２の透過率測定における使用装置および条件と同じである。測定された平均透過率を透過率Ｔ１（％）として表４に示す。表４には、マスク領域と非マスク領域との透過率Ｔ１の差（領域間透過率差）も示す。比較例４の積層体Ｌ１４では、領域間透過率差が実質的に生じなかった。すなわち、比較例４の積層体Ｌ１４では、非マスク領域は、マスク領域と同様に、着色性が実質的には低下しなかった。これに対し、実施例９,１０の積層体Ｌ１２,Ｌ１３では、有意な領域間透過率差が生じた。すなわち、実施例９,１０の積層体Ｌ１２,Ｌ１３では、マスク領域の着色性が実質的に低下せず且つ非マスク領域の着色性が有意に低下した（実施例９,１０の積層体Ｌ１２,Ｌ１３は、比較例４の積層体Ｌ１４よりも、非マスク領域において、良好な変色抑制性を示した）。すなわち、実施例９,１０の積層体Ｌ１２,Ｌ１３の可変色粘着シートにおいては、着色領域（マスク領域）の十分な着色性を維持しつつ、非着色領域（非マスク領域）の変色を抑制できた。
First, the laminate was irradiated with ultraviolet rays (UV). The UV irradiation method and conditions are the same as described above for the first UV irradiation. Next, the average transmittance at a wavelength of 400 to 700 nm for each of the regions where the mask film is arranged (mask region) and the region where the mask film is not arranged (non-mask region) in the laminate is It was measured. The apparatus and conditions used in this measurement are the same as those used in the first and second transmittance measurements. Table 4 shows the measured average transmittance as transmittance T 1 (%). Table 4 also shows the difference in transmittance T1 between masked and unmasked areas (inter - regional transmittance difference). In the laminate L14 of Comparative Example 4, substantially no inter-region transmittance difference occurred. That is, in the laminate L14 of Comparative Example 4 , the non-masked region did not substantially deteriorate in colorability as in the masked region. On the other hand, in the laminates L 12 and L 13 of Examples 9 and 10, a significant inter-regional transmittance difference occurred. That is, in the laminates L 12 and L 13 of Examples 9 and 10, the colorability of the masked regions did not substantially decrease and the colorability of the non-masked regions significantly decreased (the laminates of Examples 9 and 10 L 12 and L 13 exhibited better discoloration suppression in the non-masked region than laminate L 14 of Comparative Example 4). That is, in the color-changeable pressure-sensitive adhesive sheets of the laminates L12 and L13 of Examples 9 and 10 , the coloration of the non-colored regions (non-masked regions) was prevented while maintaining the sufficient colorability of the colored regions (masked regions). I was able to suppress it.
<積層体Ｌ１５,Ｌ１６,Ｌ５の透過率変化>
実施例１１,１２および比較例１の各積層体について、以下のようにして、紫外線照射後の透過率の変化を調べた。 <Transmittance change of laminates L 15 , L 16 and L 5 >
For each of the laminates of Examples 11 and 12 and Comparative Example 1, change in transmittance after UV irradiation was examined as follows.
実施例１１,１２および比較例１の各積層体について、以下のようにして、紫外線照射後の透過率の変化を調べた。 <Transmittance change of laminates L 15 , L 16 and L 5 >
For each of the laminates of Examples 11 and 12 and Comparative Example 1, change in transmittance after UV irradiation was examined as follows.
まず、作製直後の積層体に対して紫外線を照射し（第２のＵＶ照射）、その後、当該積層体の、波長４００～７００ｎｍでの平均透過率を測定した（第４の透過率測定）。作製から２５℃で４８時間後の別の積層体に対して紫外線を照射し（第３のＵＶ照射）、その後、当該積層体の、波長４００～７００ｎｍでの平均透過率を測定した（第５の透過率測定）。第２工程での貼り合わせから８５℃で４８時間後の別の積層体に対して紫外線を照射し（第４のＵＶ照射）、その後、当該積層体の、波長４００～７００ｎｍでの平均透過率を測定した（第６の透過率測定）。第２～第４のＵＶ照射における使用装置および条件は、第１のＵＶ照射における使用装置および条件と同じである。第４～第６の透過率測定における使用装置および条件は、第１の透過率測定における使用装置および条件と同じである。第４の透過率測定で測定された平均透過率を透過率Ｔ３（％）とし、第５の透過率測定で測定された平均透過率を透過率Ｔ４（％）とし、第６の透過率測定で測定された平均透過率を透過率Ｔ５（％）として、表５に示す。実施例１１,１２の積層体Ｌ１５,Ｌ１６は、比較例１の積層体Ｌ５よりも、透過率差Ｔ４－Ｔ３も透過率差Ｔ５－Ｔ３も有意に大きく、有意な着色性の低下（変色抑制性）を示した。特に、実施例１１の積層体Ｌ１６は、より高温において可変色粘着シートの着色性低下の程度が高く（即ち、透過率差Ｔ５－Ｔ３が大きく）、優れた変色抑制性を示した。
First, the laminate immediately after production was irradiated with ultraviolet rays (second UV irradiation), and then the average transmittance of the laminate was measured at a wavelength of 400 to 700 nm (fourth transmittance measurement). Another laminate after 48 hours from the production at 25 ° C. was irradiated with ultraviolet rays (third UV irradiation), and then the average transmittance of the laminate at a wavelength of 400 to 700 nm was measured (fifth transmittance measurement). Another laminate after 48 hours at 85 ° C. from the bonding in the second step is irradiated with ultraviolet rays (fourth UV irradiation), and then the laminate has an average transmittance at a wavelength of 400 to 700 nm. was measured (sixth transmittance measurement). The equipment and conditions used for the second to fourth UV irradiations are the same as those used for the first UV irradiation. The equipment and conditions used in the fourth to sixth transmittance measurements are the same as those used in the first transmittance measurement. Let the average transmittance measured in the fourth transmittance measurement be the transmittance T 3 (%), let the average transmittance measured in the fifth transmittance measurement be the transmittance T 4 (%), and let the sixth transmittance Table 5 shows the average transmittance measured by transmittance measurement as transmittance T 5 (%). In the laminates L 15 and L 16 of Examples 11 and 12, both the transmittance difference T 4 −T 3 and the transmittance difference T 5 −T 3 are significantly larger than the laminate L 5 of Comparative Example 1. A decrease in colorability (discoloration suppression property) was exhibited. In particular, the laminate L 16 of Example 11 had a high degree of deterioration in the colorability of the color-changeable pressure-sensitive adhesive sheet at higher temperatures (that is, the transmittance difference T 5 -T 3 was large), and exhibited excellent discoloration suppression properties. .
<積層体Ｌ１７～Ｌ１９の透過率変化>
実施例１３～１５の各積層体について、以下のようにして、着色性低下処理（浸漬処理）による透過率の変化を調べた。 <Transmittance change of laminates L 17 to L 19 >
For each of the laminates of Examples 13 to 15, change in transmittance due to coloration reducing treatment (immersion treatment) was examined as follows.
実施例１３～１５の各積層体について、以下のようにして、着色性低下処理（浸漬処理）による透過率の変化を調べた。 <Transmittance change of laminates L 17 to L 19 >
For each of the laminates of Examples 13 to 15, change in transmittance due to coloration reducing treatment (immersion treatment) was examined as follows.
積層体の製造過程の途中で、可変色粘着シートＸ１（片面に基材フィルムを伴う）をイーグルガラスに貼り合わせて得られる中間積層体について、波長４００～７００ｎｍでの平均透過率を測定した（第７の透過率測定）。また、着色性低下処理（浸漬処理）を経て作製された積層体に対して紫外線を照射し（第５のＵＶ照射）、その後、当該積層体の、波長４００～７００ｎｍでの平均透過率を測定した（第８の透過率測定）。実施例１５の積層体Ｌ１９については、マスクフィルムが配置されている領域（マスク領域）と、マスクフィルムが配置されていない領域（非マスク領域）とのそれぞれについて、第８の透過率測定を実施した。第５のＵＶ照射における使用装置および条件は、第１のＵＶ照射における使用装置および条件と同じである。第７・第８の透過率測定における使用装置および条件は、第１の透過率測定における使用装置および条件と同じである。第７の透過率測定で測定された平均透過率を透過率Ｔ６（％）とし、第８の透過率測定で測定された平均透過率を透過率Ｔ７（％）として、表６,７に示す。表６には、透過率Ｔ６と透過率Ｔ７との差ΔＴ（＝Ｔ７－Ｔ６）も示す。また、表６には、比較例１の積層体Ｌ５について表１に示す透過率測定結果（Ｔ０，Ｔ１，Ｔ０－Ｔ１）も比較のために示す。表６に示すように、実施例１３,１４の積層体Ｌ１７,Ｌ１８は、比較例１の積層体Ｌ５よりも、ΔＴが有意に小さく、良好な変色抑制性を示した。一方、実施例１５の積層体Ｌ１９については、マスク領域と非マスク領域との透過率Ｔ７の差（領域間透過率差）も、表７に示す。また、表７には、比較例４の積層体Ｌ１４について表４に示す透過率測定結果（Ｔ０，Ｔ１，マスク領域と非マスク領域との透過率差）も比較のために示す。比較例４の積層体Ｌ１４では、領域間透過率差が実質的に生じなかったのに対し、実施例１５の積層体Ｌ１９では、有意な領域間透過率差が生じた。すなわち、実施例１５の積層体Ｌ１９では、マスク領域の着色性が実質的に低下せず且つ非マスク領域の着色性が有意に低下した（実施例１５の積層体Ｌ１９は、比較例４の積層体Ｌ１４よりも、非マスク領域において、良好な変色抑制性を示した）。すなわち、実施例１５の積層体Ｌ１９の可変色粘着シートにおいては、着色領域（マスク領域）の十分な着色性を維持しつつ、非着色領域（非マスク領域）の変色を抑制できた。
During the manufacturing process of the laminate, the average transmittance at a wavelength of 400 to 700 nm was measured for the intermediate laminate obtained by laminating the color-changeable adhesive sheet X 1 (with a base film on one side) to Eagle Glass. (7th transmittance measurement). In addition, the laminate prepared through the coloring property reduction treatment (immersion treatment) is irradiated with ultraviolet rays (fifth UV irradiation), and then the average transmittance of the laminate at a wavelength of 400 to 700 nm is measured. (eighth transmittance measurement). For the laminate L 19 of Example 15, an eighth transmittance measurement was performed for each of the region where the mask film was arranged (mask region) and the region where the mask film was not arranged (non-mask region). Carried out. The equipment and conditions used in the fifth UV irradiation are the same as those used in the first UV irradiation. The apparatus and conditions used in the seventh and eighth transmittance measurements are the same as the apparatus and conditions used in the first transmittance measurement. Let the average transmittance measured in the seventh transmittance measurement be the transmittance T 6 (%), and let the average transmittance measured in the eighth transmittance measurement be the transmittance T 7 (%), Tables 6 and 7 shown in Table 6 also shows the difference ΔT (=T 7 -T 6 ) between the transmittances T 6 and T 7 . Table 6 also shows the transmittance measurement results (T 0 , T 1 , T 0 −T 1 ) shown in Table 1 for the laminate L 5 of Comparative Example 1 for comparison. As shown in Table 6, the laminates L 17 and L 18 of Examples 13 and 14 had significantly smaller ΔT than the laminate L 5 of Comparative Example 1, and exhibited good discoloration suppressing properties. On the other hand, for the laminate L19 of Example 15, Table 7 also shows the difference in transmittance T7 between the masked area and the non-masked area (transmittance difference between areas). Table 7 also shows the transmittance measurement results (T 0 , T 1 , transmittance difference between the masked area and the non-masked area) shown in Table 4 for the laminate L14 of Comparative Example 4 for comparison. In the laminate L- 14 of Comparative Example 4, substantially no difference in transmittance between regions occurred, while in the laminate L- 19 of Example 15, a significant difference in transmittance between regions occurred. That is, in the laminate L- 19 of Example 15, the colorability of the masked region was not substantially reduced, and the coloring of the non-masked region was significantly reduced (the laminate L- 19 of Example 15 was the same as that of Comparative Example 4). showed better discoloration suppression in the non-masked area than the laminate L14). That is, in the color-changeable pressure-sensitive adhesive sheet of laminate L19 of Example 15 , it was possible to suppress the discoloration of the non-colored region (non-masked region) while maintaining sufficient colorability in the colored region (masked region).
上述の実施形態は本発明の例示であり、当該実施形態によって本発明を限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記の請求の範囲に含まれる。
The above-described embodiments are examples of the present invention, and the present invention should not be construed to be limited by the embodiments. Variations of the invention that are obvious to those skilled in the art are included in the following claims.
本発明の可変色粘着シートの変色抑制方法および積層シートは、例えば、ディスプレイパネルの製造過程で用いることができる。
The method for suppressing discoloration of the color-changeable pressure-sensitive adhesive sheet and the laminated sheet of the present invention can be used, for example, in the manufacturing process of display panels.
Ｘ 可変色粘着シート
Ｙ 着色性低下シート
１１ 第１領域（着色済領域）
１２ 第２領域（非着色済領域）
２１ 第１部材
２２ 第２部材
Ｌ 積層シート X Color-changeable adhesive sheet Y Color-loweringsheet 11 First region (colored region)
12 Second area (non-colored area)
21First member 22 Second member L Laminated sheet
Ｙ 着色性低下シート
１１ 第１領域（着色済領域）
１２ 第２領域（非着色済領域）
２１ 第１部材
２２ 第２部材
Ｌ 積層シート X Color-changeable adhesive sheet Y Color-lowering
12 Second area (non-colored area)
21
Claims (12)
- 外部刺激に因る着色性を有する可変色粘着シートであって、着色済領域と非着色済領域とを含む可変色粘着シートを、用意する第１工程と、
前記可変色粘着シートの前記着色性を低下させるための着色性低下メディアを、前記可変色粘着シートに接触させる、第２工程とを含む、可変色粘着シートの変色抑制方法。 a first step of preparing a color-changeable pressure-sensitive adhesive sheet having colorability due to an external stimulus, the color-changeable pressure-sensitive adhesive sheet including a colored region and a non-colored region;
A method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet, comprising a second step of contacting the color-changeable pressure-sensitive adhesive sheet with a colorability-reducing medium for reducing the colorability of the color-changeable pressure-sensitive adhesive sheet. - 前記可変色粘着シートが、外部刺激を受けて第１反応を生ずる第１化合物と、前記第１反応の生成物との第２反応によって発色する第２化合物とを含有する、請求項１に記載の可変色粘着シートの変色抑制方法。 2. The color-changeable adhesive sheet according to claim 1, wherein said color-changeable pressure-sensitive adhesive sheet contains a first compound that undergoes a first reaction upon receiving an external stimulus, and a second compound that develops color through a second reaction with a product of said first reaction. and a method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet.
- 前記第１化合物が光酸発生剤であり、前記第２化合物が、酸との反応により発色する発色性化合物である、請求項２に記載の可変色粘着シートの変色抑制方法。 The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 2, wherein the first compound is a photoacid generator and the second compound is a color-developing compound that develops color upon reaction with an acid.
- 前記第２工程では、前記可変色粘着シートから前記第１化合物を前記着色性低下メディアに抽出するか、または、
前記着色性低下メディアが、前記着色性を低下させるための着色性低下成分を含有し、前記第２工程では、前記着色性低下成分を前記着色性低下メディアから前記可変色粘着シートに導入する、請求項２に記載の可変色粘着シートの変色抑制方法。 In the second step, the first compound is extracted from the color-changeable pressure-sensitive adhesive sheet into the coloring-reduced medium, or
The reduced coloring medium contains a coloring reducing component for reducing the coloring, and in the second step, the coloring reducing component is introduced from the reduced coloring medium to the color-changeable pressure-sensitive adhesive sheet. The method for suppressing discoloration of the color-changeable pressure-sensitive adhesive sheet according to claim 2. - 前記第１化合物、前記第２化合物、および前記着色性低下成分が共存する第１の系における前記外部刺激付与による透過率の低下ΔＴ１が、前記着色性低下成分が存在しないこと以外は前記第１の系と同じ第２の系における前記外部刺激付与と同じ外部刺激付与による透過率の低下ΔＴ２より小さい、請求項４に記載の可変色粘着シートの変色抑制方法。 The transmittance decrease ΔT1 due to the application of the external stimulus in the first system in which the first compound, the second compound, and the coloring-reducing component coexist is 5. The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 4, wherein the decrease in transmittance ΔT2 due to the application of the same external stimulus as the application of the external stimulus in the second system, which is the same as the system of (1), is smaller than the decrease ΔT2 in transmittance.
- 前記着色性低下成分が、紫外線吸収剤、中和剤、およびラジカルトラップ剤からなる群より選択される少なくとも一つを含む、請求項５に記載の可変色粘着シートの変色抑制方法。 The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 5, wherein the coloring-reducing component contains at least one selected from the group consisting of an ultraviolet absorber, a neutralizing agent, and a radical trapping agent.
- 前記着色性低下メディアが着色性低下シートであり、前記第２工程では、前記着色性低下シートを前記可変色粘着シートに貼り合わせる、請求項１に記載の可変色粘着シートの変色抑制方法。 The method for suppressing discoloration of a color-changeable adhesive sheet according to claim 1, wherein the color-reduced medium is a color-reduced sheet, and in the second step, the color-reduced sheet is attached to the color-changeable adhesive sheet.
- 前記第２工程では、前記可変色粘着シートの前記着色済領域の少なくとも一部と前記着色性低下シートとの間にマスク材を介在させた状態で、前記着色性低下シートを前記可変色粘着シートに貼り合わせる、請求項７に記載の可変色粘着シートの変色抑制方法。 In the second step, the reduced colorability sheet is attached to the color-changeable pressure-sensitive adhesive sheet while a mask material is interposed between at least a part of the colored region of the color-changeable pressure-sensitive adhesive sheet and the reduced colorability sheet. The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 7, wherein
- 前記着色性低下シートが、極性基含有ポリマーを含有する、請求項７に記載の可変色粘着シートの変色抑制方法。 The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 7, wherein the color-reducing sheet contains a polar group-containing polymer.
- 前記着色性低下シートが粘着シートである、請求項７に記載の可変色粘着シートの変色抑制方法。 The method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 7, wherein the color-reducing sheet is a pressure-sensitive adhesive sheet.
- 前記着色性低下メディアが着色性低下溶媒である、請求項１に記載の変色抑制方法。 The method for suppressing discoloration according to claim 1, wherein the coloring-reducing medium is a coloring-reducing solvent.
- 請求項７に記載の可変色粘着シートの変色抑制方法によって得られる積層シートであって、
前記可変色粘着シートと、
前記可変色粘着シートに貼り合わされた前記着色性低下シートとを備える、積層シート。 A laminated sheet obtained by the method for suppressing discoloration of a color-changeable pressure-sensitive adhesive sheet according to claim 7,
the variable color adhesive sheet;
A laminate sheet comprising the color-reducing sheet attached to the color-changeable pressure-sensitive adhesive sheet.
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| CN202280018456.3A CN116964168A (en) | 2021-03-05 | 2022-03-01 | Method for inhibiting discoloration of color-changeable adhesive sheet, and laminate |
| KR1020237029354A KR20230154822A (en) | 2021-03-05 | 2022-03-01 | Method for suppressing discoloration of variable color adhesive sheets and laminated sheets |
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| JP2022027086A JP2022135979A (en) | 2021-03-05 | 2022-02-24 | Discoloration prevention method of variable color adhesive sheet and laminate sheet |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153377A (en) * | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
| JPH05323492A (en) * | 1992-05-26 | 1993-12-07 | Fuji Photo Film Co Ltd | Picture forming material |
| WO2020188985A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive sheet, production method for adhesive sheet, production method for intermediate laminate, and intermediate laminate |
| WO2020189390A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
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| SG11202110096QA (en) | 2019-03-15 | 2021-10-28 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153377A (en) * | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
| JPH05323492A (en) * | 1992-05-26 | 1993-12-07 | Fuji Photo Film Co Ltd | Picture forming material |
| WO2020188985A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive sheet, production method for adhesive sheet, production method for intermediate laminate, and intermediate laminate |
| WO2020189390A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
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