WO2022054633A1 - Color-changeable adhesive sheet - Google Patents
Color-changeable adhesive sheet Download PDFInfo
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- WO2022054633A1 WO2022054633A1 PCT/JP2021/031865 JP2021031865W WO2022054633A1 WO 2022054633 A1 WO2022054633 A1 WO 2022054633A1 JP 2021031865 W JP2021031865 W JP 2021031865W WO 2022054633 A1 WO2022054633 A1 WO 2022054633A1
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- sensitive adhesive
- pressure
- adhesive layer
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- meth
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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 variable color adhesive sheet.
- a display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover member.
- a transparent adhesive sheet is used for bonding the elements included in the laminated structure.
- Patent Document 1 specifically describes an adhesive sheet having a colored portion containing a carbon black pigment.
- a coloring component may be formed in an arbitrary shape at an arbitrary place. In such a case, the visibility and the shielding property may deteriorate with time.
- the pressure-sensitive adhesive layer can be locally discolored after being attached to an adherend, and a variable color suitable for imparting designability, shielding property, and antireflection property to an arbitrary portion.
- a variable color suitable for imparting designability, shielding property, and antireflection property to an arbitrary portion.
- the present invention [1] includes a pressure-sensitive adhesive layer that can be discolored by an external stimulus, and the first discoloration width W1 determined by the following test 1 and the second discoloration width W2 determined by the following test 2 are expressed by the following formula (1). ) Is a variable color adhesive sheet.
- Step A External stimulus is linearly applied to the pressure-sensitive adhesive layer.
- Step B After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- Step C After step A and step B of the test 1, heat treatment is performed at 85 ° C. for 120 hours.
- Step D After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- the present invention [2] includes the variable color pressure-sensitive adhesive sheet according to the above [1], wherein the first color change width W1 and the third color change width W3 obtained by the following test 3 satisfy the following formula (2). I'm out.
- Step E After step A and step B of ⁇ Test 1> above, heat treatment is performed at 85 ° C. for 240 hours.
- Step F After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- the present invention [3] includes the variable color pressure-sensitive adhesive sheet according to the above [1] or [2], wherein the pressure-sensitive adhesive layer has a thickness of 10 ⁇ m or more and 300 ⁇ m or less.
- the present invention [4] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [3], further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer. ..
- the peeling test under the peeling conditions of 23 ° C., a peeling angle of 180 ° and a peeling speed of 300 mm / min is performed on the glass plate.
- variable color adhesive sheet of the present invention includes an adhesive layer that can be discolored by an external stimulus. Therefore, after the variable color pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer can be locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. With such a variable color pressure-sensitive adhesive sheet, the presence or absence of foreign matter and air bubbles between the variable color pressure-sensitive adhesive sheet and the adherend can be inspected after the bonding and before the formation of the discolored portion of the pressure-sensitive adhesive layer.
- variable color pressure-sensitive adhesive sheet the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer satisfy 0.5 ⁇ W2 / W1 ⁇ 2.
- Such a variable color pressure-sensitive adhesive sheet is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed in the pressure-sensitive adhesive layer by applying an external stimulus. Suitable for imparting antireflection properties.
- FIG. 1 is a schematic cross-sectional view of an embodiment of the variable color pressure-sensitive adhesive sheet of the present invention.
- FIG. 2 is a schematic cross-sectional view of a modified example of the variable color pressure-sensitive adhesive sheet of the present invention (when the pressure-sensitive adhesive sheet is a single-sided pressure-sensitive adhesive sheet with a base material).
- 3A to 3C show an example of how to use the variable color adhesive sheet of the present invention.
- FIG. 3A shows a step of preparing a variable color adhesive sheet and a member as an adherend.
- FIG. 3B shows a process of joining members to each other via a variable color adhesive sheet.
- FIG. 3C shows a step of forming a discolored portion in the pressure-sensitive adhesive layer of the variable-color pressure-sensitive adhesive sheet.
- 3 is a TEM image of the pressure-sensitive adhesive layer of Example 7.
- variable color pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer that can be discolored by an external stimulus, and the first color change width W1 determined by the following test 1 and the second color change width W2 obtained by the following test 2 have the following formulas. Satisfy (1).
- the first discoloration width W1 is obtained by the following ⁇ Test 1>.
- Step A External stimulus is linearly applied to the pressure-sensitive adhesive layer.
- Step B After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- the second discoloration width W2 is obtained by the following ⁇ Test 2>.
- Step C After step A and step B of ⁇ Test 1> above, heat treatment is performed at 85 ° C. for 120 hours.
- Step D After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- variable color adhesive sheet includes an adhesive layer that can be discolored by an external stimulus. Therefore, after the variable color pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer can be locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. With such a variable color pressure-sensitive adhesive sheet, the presence or absence of foreign matter and air bubbles between the variable color pressure-sensitive adhesive sheet and the adherend can be inspected after the bonding and before the formation of the discolored portion of the pressure-sensitive adhesive layer.
- variable color pressure-sensitive adhesive sheet the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer satisfy the above formula (1).
- Such a variable color pressure-sensitive adhesive sheet is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed in the pressure-sensitive adhesive layer by applying an external stimulus. Suitable for imparting antireflection properties.
- variable color adhesive sheet may be arranged on the light emitting side (image display side) of the pixel panel in the display panel.
- metal wiring may be provided at a fine pitch on the pixel panel provided in the display panel. Then, from the viewpoint of suppressing external light reflection in the metal wiring, a colored portion may be provided with a pattern shape corresponding to such metal wiring.
- variable color adhesive sheet since the first color change width W1 and the second color change width W2 satisfy the above formula (1), the shielding property and the antireflection property can be improved. As a result, it is possible to improve the visibility of the display panel provided with the metal wiring while suppressing the reflection of external light on the metal wiring.
- first method a method for adjusting the first discoloration width W1 and the second discoloration width W2 so as to satisfy the above formula (1)
- first method a method using a metal complex (described later)
- adhesion a method of increasing the elastic modulus of the agent layer, a method of using a color component in the pressure-sensitive adhesive layer bonded to another component, a method of providing a coloring component on an island portion of a sea-island structure utilizing incompatibility or low compatibility. (Second method) can be mentioned.
- Examples of the method for increasing the elastic modulus of the pressure-sensitive adhesive layer include a method using a polyfunctional monomer as a monomer component, a method using a cross-linking agent, and a method of combining these.
- a colored component in the pressure-sensitive adhesive layer bonded to another component for example, as a colored component, a colored polymer in which a component capable of developing a predetermined color is linked / bonded to a polymer in the layer is used.
- a method to be used a method in which the coloring component and the polymer component are initially separate components, but a method in which the coloring component is bonded to the polymer by a reaction, and a method of combining these.
- a method of providing a coloring component on an island portion of a sea island structure utilizing incompatibility or low compatibility for example, a polymer having high compatibility with the coloring component and a polymer having low compatibility and having high compatibility are used.
- a sea-island structure that becomes an island a method of providing a coloring component on the island can be mentioned.
- the third color change width W3 is obtained by the following ⁇ Test 3>.
- Step E After step A and step B of ⁇ Test 1> above, heat treatment is performed at 85 ° C. for 240 hours.
- Step F After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
- first discoloration width W1 and the third discoloration width W3 satisfy the above formula (2), further designability, shielding property, and antireflection property can be imparted to any place.
- the above-mentioned first color change width W1 and the above-mentioned second color change width W2 are described above. It is the same as the method of adjusting so as to satisfy the equation (1).
- the average transmittance T1, the average transmittance T2, and the color difference variable color pressure-sensitive adhesive sheet preferably have the average transmittance T1 determined by the following test 4 and the average transmittance T2 determined by the following test 5 according to the following formula (3). ), And preferably the following formula (4).
- the average transmittance T1 is obtained by the following ⁇ Test 4>.
- Step G The pressure-sensitive adhesive layer is irradiated with light in the wavelength band of 300 nm to 400 nm.
- Step H The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
- the average transmittance T1 is, for example, 10% or more, preferably 15% or more.
- the average transmittance T1 is, for example, 40% or less, preferably 30% or less. The method for measuring the average transmittance T1 will be described in more detail in the weather resistance test described later.
- the average transmittance T2 is obtained by the following ⁇ Test 5>.
- Step I After step G of ⁇ Test 4> above, the pressure-sensitive adhesive layer is irradiated with a xenon lamp having an illuminance of 120 W in the wavelength range of 300 nm to 400 nm for 24 hours with a super xenon weather meter.
- Step J The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
- the average transmittance T2 is, for example, 15% or more, preferably 24% or more.
- the average transmittance T2 is, for example, 50% or less, preferably 40% or less.
- the method for measuring the average transmittance T2 will be described in more detail in the weather resistance test described later.
- variable color adhesive sheet satisfies the above formula (3) or the above formula (4), the weather resistance is excellent.
- a method for adjusting the average transmittance T1 and the average permeability T2 so as to satisfy the above formula (3) or the above formula (4) for example, a method for reducing oxygen permeability to the pressure-sensitive adhesive layer and an antioxidant are used. Examples thereof include a method of adding to the pressure-sensitive adhesive layer and a method of laminating a base material or a pressure-sensitive adhesive layer containing an ultraviolet absorber.
- the color difference measured by the weather resistance test described later is, for example, 30 or less, preferably 28 or less, more preferably 25 or less, and further preferably 20 or less from the viewpoint of weather resistance.
- the pressure-sensitive adhesive sheet S which satisfies the above formula (1) and preferably satisfies the above formulas (2) to (4), will be described.
- the adhesive sheet S as a method of adjusting the first color change width W1 and the second color change width W2 so as to satisfy the above formula (1), the above-mentioned first method (first embodiment) and the first method.
- the method 2 second embodiment
- the present invention is not limited thereto.
- the pressure-sensitive adhesive sheet S includes a pressure-sensitive adhesive layer 10.
- the adhesive sheet S has a sheet shape having a predetermined thickness and extends in a direction (plane direction) orthogonal to the thickness direction.
- the pressure-sensitive adhesive sheet S is used, for example, as a transparent pressure-sensitive adhesive sheet arranged on the image display side of the pixel panel in a display panel (for example, having a laminated structure including a pixel panel and a cover member).
- the pressure-sensitive adhesive layer 10 is a pressure-sensitive adhesive layer having transparency (visible light transmission) formed from the pressure-sensitive adhesive composition.
- the tacky composition comprises a base polymer, a compound that develops color by reaction with an acid, and an acid generator. In the first embodiment, the tacky composition further comprises a metal complex.
- the base polymer is an adhesive component for developing adhesiveness in the adhesive layer 10.
- the base polymer exhibits rubber elasticity at room temperature.
- examples of the base polymer include acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and tackiness in the pressure-sensitive adhesive layer 10, an acrylic polymer is preferably used as the base polymer.
- the content ratio of the base polymer in the pressure-sensitive adhesive layer 10 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70, from the viewpoint of appropriately expressing the function of the base polymer in the pressure-sensitive adhesive layer 10. It is mass% or more.
- the acrylic polymer is, for example, a polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more.
- (Meta) acrylic acid means acrylic acid and / or methacrylic acid.
- Examples of the (meth) acrylic acid alkyl ester include linear or branched (meth) acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms.
- Examples of such (meth) acrylic acid alkyl esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth) acrylic acid.
- Acrylic acid can be mentioned.
- the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
- an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferably used, and more preferably, it has methyl acrylate and an alkyl group having 2 to 12 carbon atoms.
- Acrylic acid alkyl ester is used in combination, and more preferably, methyl acrylate and 2-ethylhexyl acrylate are used in combination.
- the ratio of the (meth) acrylic acid alkyl ester in the monomer component is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the pressure-sensitive adhesive layer 10. Is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
- the monomer component may contain a copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester.
- the copolymerizable monomer include a monomer having a polar group (monomer containing a polar group).
- the polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing a cross-linking point into the acrylic polymer and ensuring the cohesive force of the acrylic polymer.
- the polar group-containing monomer examples include a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer.
- the copolymerizable monomer preferably contains at least one selected from the group consisting of a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer. More preferably, the copolymerizable monomer comprises a hydroxyl group-containing monomer and / or a monomer having a nitrogen atom-containing ring.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (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 can be mentioned.
- 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 monomer component is, for example, 1% by mass or more, preferably 3% by mass or more, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring the cohesive force in the pressure-sensitive adhesive layer 10. More preferably, it is 5% by mass or more.
- the same ratio is, for example, from the viewpoint of adjusting the viscosity of the polymerization reaction solution during the polymerization of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). , 30% by mass or less, preferably 20% by mass or less.
- Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, and N-vinylpyrazine.
- N-vinyl-2-caprolactam N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione
- N-vinylpyrazole N-vinylisoxazole
- N -Vinylthiazole N-vinylisothiazole
- monomer having a nitrogen atom-containing ring N-vinyl-2-pyrrolidone is preferably used.
- the proportion of the monomer having a nitrogen atom-containing ring in the monomer component is, for example, 1% by mass from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10 and the adhesion to the adherend in the pressure-sensitive adhesive layer 10. As mentioned above, it is preferably 3% by mass or more, and more preferably 5% by mass or more. The same ratio is, for example, 30 mass from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). % Or less, preferably 20% by mass or less.
- carboxy group-containing monomer examples include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
- the ratio of the carboxy group-containing monomer in the monomer component is determined from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring the cohesive force in the pressure-sensitive adhesive layer 10, and ensuring the adhesion to the adherend in the pressure-sensitive adhesive layer 10. For example, it is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more. The same ratio is, for example, 30% by mass or less, preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of corrosion of the adherend by acid.
- the monomer component may contain other copolymerizable monomers.
- other copolymerizable monomers include acid anhydride monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, amide group-containing monomers, monomers having a succinimide skeleton, and maleimides.
- acid anhydride monomers sulfonic acid group-containing monomers
- phosphate group-containing monomers phosphate group-containing monomers
- epoxy group-containing monomers epoxy group-containing monomers
- cyano group-containing monomers epoxy group-containing monomers
- amide group-containing monomers monomers having a succinimide skeleton
- maleimides examples include itaconimides, alkoxy group-containing monomers, vinyl esters, vinyl ethers, and aromatic vinyl compounds.
- Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride.
- sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, and sulfopropyl (meth).
- examples include acrylate and (meth) acryloyloxynaphthalene sulfonic acid.
- Examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
- epoxy group-containing monomer examples include epoxy group-containing acrylates such as glycidyl (meth) acrylate and -2-ethyl glycidyl ether (meth) acrylate, allyl glycidyl ether, and glycidyl ether (meth) acrylate. ..
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- amide group-containing monomer examples include N-vinylcarboxylic acid amides, N-hydroxyalkyl (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N. -(Meta) Acryloylmorpholine can be mentioned.
- N-vinylcarboxylic acid amides include (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkyl (meth) acrylamide, and N-vinylacetamide.
- N, N-dialkyl (meth) acrylamide examples include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, and N, N-diisopropyl ( Examples include meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, and N, N-di (t-butyl) (meth) acrylamide.
- N-alkyl (meth) acrylamide examples include N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. ..
- N-hydroxyalkyl (meth) acrylamide examples include N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (1-hydroxypropyl) (meth).
- Acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, and N- (4-hydroxybutyl) Examples examples include (meth) acrylamide.
- N-alkoxyalkyl (meth) acrylamide examples include N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
- Examples of the monomer having a succinimide skeleton include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyhexamethylene succinimide. Can be mentioned.
- maleimides examples include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide.
- Examples of the itaconimides include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and , N-laurylitaconimide.
- Examples of the alkoxy group-containing monomer include (meth) acrylate alkoxyalkyls and (meth) acrylate alkoxyalkylene glycols.
- Examples of the (meth) acrylate alkoxyalkyls include (meth) acrylate 2-methoxyethyl, (meth) acrylate 3-methoxypropyl, (meth) acrylate 2-ethoxyethyl, and (meth) acrylate propoxyethyl. , (Meth) butoxyethyl acrylate, and (meth) ethoxypropyl acrylate.
- Examples of the (meth) acrylate alkoxyalkylene glycols include (meth) methoxyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate.
- vinyl esters examples include vinyl acetate and vinyl propionate.
- vinyl ethers examples include methyl vinyl ether and ethyl vinyl ether.
- aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, and vinyltoluene.
- olefins examples include ethylene, butadiene, isoprene, and isobutylene.
- the copolymerizable monomer may be used alone or in combination of two or more.
- Acrylic polymer can be formed by polymerizing the above monomer components.
- the polymerization method include solution polymerization, bulk polymerization, and emulsion polymerization, and solution polymerization is preferable.
- solution polymerization for example, a monomer component and a polymerization initiator are mixed with a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, an acrylic polymer solution containing an acrylic polymer can be obtained by undergoing a polymerization reaction of the monomer components in the reaction solution.
- 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 with respect to 100 parts by mass of the monomer component.
- the amount used is, for example, 1 part by mass or less.
- thermal polymerization initiator examples include an azo-based polymerization initiator and a peroxide-based polymerization initiator.
- examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azobis (2-methylpropionic acid) dimethyl.
- 4,4'-Azobis-4-cyanovaleric acid 4,4'-Azobis-4-cyanovaleric acid, azobisisobutyvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2) -Imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, and 2,2'-azobis (N, N'-dimethyleneisobutyramidin) dihydrochloride Can be mentioned.
- the peroxide-based polymerization initiator include dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
- the weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 300,000 or more, and more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10.
- the weight average molecular weight is, for example, 5,000,000 or less, preferably 3,000,000 or less, and more preferably 2000000 or less.
- the weight average molecular weight of the acrylic polymer is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
- the glass transition temperature (Tg) of the base polymer is, for example, 0 ° C. or lower, preferably ⁇ 10 ° C. or lower, 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 Fox formula below can be used.
- the Fox formula is a relational expression between the glass transition temperature Tg of the polymer and the glass transition temperature Tgi of the homopolymer of the monomer 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 temperature of the homopolymer formed from the monomer i. (° C) is indicated.
- Literature values can be used for the glass transition temperature of homopolymers, for example, "Polymer Handbook” (4th edition, John Willey & Sons, Inc., 1999) and "New Polymer Bunko 7 Introduction to Synthetic Resins for Paints". (Kyozo Kitaoka, Polymer Publishing Association, 1995) lists the glass transition temperatures of various homopolymers.
- the glass transition temperature of the homopolymer of the monomer can also be obtained by the method specifically described in JP-A-2007-51271. The above is the same for the glass transition temperature of the hard segment and the soft segment described later.
- Examples of the compound (color-developing compound) that develops color by reaction with an acid include leuco-based dye, triarylmethane-based dye, diphenylmethane-based dye, fluorane-based dye, spiropyran-based dye, and rhodamine-based dye.
- the color-developing compound may be used alone or in combination of two or more.
- leuco-based dyes examples include 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] and 3-dibutylamino.
- Examples of the triarylmethane dye include p, p', p "-tris-dimethylaminotriphenylmethane.
- Examples of the diphenylmethane dye include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl.
- Examples of the fluorin-based dye include 3-diethylamino-6-methyl-7-chlorofluorane.
- Examples of the spiropyran-based dye include 3-methylspirodinaphthopyrane.
- Examples of the dye system include rhodamine-B-anilinolactum.
- the color-developing compound is preferably a leuco-based dye, more preferably 2'-anilino-6'-(N-ethyl-N-). Isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] is used.
- the blending amount of the color-developing compound with respect to 100 parts by mass of the base polymer is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more.
- the blending amount is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.
- a photoacid generator that generates an acid by being irradiated with active energy rays is preferably used.
- the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy ray as an external stimulus can be discolored.
- an acid is generated from the photoacid generator, and the color-developing compound is developed by this acid.
- the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays is colored, for example, into a blackish color according to the color development of the color-developing compound.
- the type of active energy ray as an external stimulus is determined by the type of photoacid generator (specifically, the wavelength of the active energy ray in which the photoacid generator generates acid).
- the active energy ray include ultraviolet rays, visible light, infrared rays, X-rays, ⁇ rays, ⁇ rays, and ⁇ rays. From the viewpoint of variety of equipment used and ease of handling, the active energy ray preferably includes ultraviolet rays.
- Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays.
- Onium compounds are provided, for example, in the form of onium salts of onium cations and anions.
- Examples of onium cations include iodonium and sulfonium.
- 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 generator may be used alone or in combination of two or more.
- the photoacid generator preferably includes an onium salt (onium compound) composed of sulfonium and C4 F 9 HSO 3- .
- the blending amount of the acid generator with respect to 100 parts by mass of the base polymer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 6 parts by mass or more.
- the blending amount is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.
- the blending amount of the acid generator with respect to 100 parts by mass of the color-developing compound is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 300 parts by mass or more, and further preferably 330 parts by mass or more. be.
- the blending amount is, for example, 1000 parts by mass or less, preferably 700 parts by mass or less, and more preferably 500 parts by mass or less.
- the metal complex is blended in order to adjust the first discoloration width W1 and the second discoloration width W2 so as to satisfy the above formula (1).
- the movement of coloring components such as leuco-based dyes is suppressed by the coordination bond with the metal complex.
- a metal complex is one in which a ligand is coordinated with a metal ion.
- the metals that make up the metal ions are according to the IUPAC Periodic Table of the Elements (version date 19 February 2010). The same shall apply hereinafter.
- Group 1 alkali metals, Group 2 alkaline earth metals, Group 3 ⁇ Group 12 transition metals can be mentioned.
- the metal is preferably Mg from the viewpoint of the strong coordination of the group 2 alkaline earth metal, the group 3 to group 12 transition metal, and the leuco dye to the carboxyl group of the chromogen. From the viewpoint of the contribution of (magnesium) and the amphoteric counterion formed with the leuco-based dye by the metal complex, Zn (zinc) can be mentioned.
- Examples of the ligand include a monodentate ligand and a bidentate ligand.
- Examples of the monodentate ligand include hydroxo (OH ⁇ ), halogen (eg, chloro (Cl ⁇ )), and cyano (CN ⁇ ).
- Bidentate ligands include, for example, ethylenediamine, bipyridine, phenanthroline, and salicylic acid.
- zinc salicylate specifically, zinc salicylate trihydrate
- the metal complex may be used alone or in combination of two or more.
- the blending amount of the metal complex with respect to 100 parts by mass of the base polymer is, for example, 0.1 part by mass or more, preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8. It is more than a mass part.
- the blending amount is, for example, 5 parts by mass or less, preferably 2 parts by mass or less.
- the blending amount of the metal complex with respect to 100 parts by mass of the color-developing compound is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and more preferably 40 parts by mass or more.
- the blending amount is, for example, 100 parts by mass or less, preferably 80 parts by mass or less.
- the adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer.
- a cross-linking agent examples include an isocyanate cross-linking agent, an epoxy cross-linking agent, an oxazoline cross-linking agent, an aziridine cross-linking agent, a carbodiimide cross-linking agent, and a metal chelate cross-linking agent.
- the cross-linking agent may be used alone or in combination of two or more.
- Examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalin diisocyanate, and triphenylmethane tri. Examples thereof include isocyanate and polymethylene polyphenyl isocyanate. Further, examples of the isocyanate cross-linking agent include derivatives of these isocyanates.
- isocyanate derivatives include isocyanurate-modified products and polyol-modified products.
- isocyanate cross-linking agents include coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh), coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh), and coronate HX (hexa).
- Examples thereof include isocyanurate form of methylene diisocyanate (manufactured by Toso) and Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate, manufactured by Mitsui Kagaku).
- epoxy cross-linking agent examples 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, and trimethylolpropane.
- Triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N', N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane Can be mentioned.
- cross-linking agent examples include an isocyanate cross-linking agent, and more preferably a trimethylolpropane adduct body of xylylene diisocyanate.
- the blending amount of the cross-linking agent is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably, with respect to 100 parts by mass of the base polymer. Is 0.07 parts by mass or more.
- the blending amount of the cross-linking agent with respect to 100 parts by mass of the base polymer is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably. It is 3 parts by mass or less.
- a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
- the cross-linking catalyst include a metal-based cross-linking catalyst.
- the metal-based cross-linking catalyst include dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, and butyl tin oxide.
- the cross-linking catalyst is preferably dibutyltin dilaurate.
- the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more with respect to 100 parts by mass of the base polymer. The amount used is, for example, 1 part by mass or less.
- an isocyanate cross-linking agent (specifically, a trimethylolpropane adduct of xylylene diisocyanate) is blended as a cross-linking agent, and a metal-based cross-linking catalyst (specifically, dibutyltin dilaurate) is used as a cross-linking catalyst.
- a metal-based cross-linking catalyst specifically, dibutyltin dilaurate
- acetylacetone When acetylacetone is added, acetylacetone coordinates with dibutyltin dilaurate. Thereby, the progress of the crosslinking reaction can be suppressed before the adhesive composition is applied onto the release film (or the base material 20) to form a coating film. Further, as will be described in detail later, acetylacetone can be removed and the crosslinking reaction can proceed by heating and drying at the time of forming the coating film.
- the amount of acetylacetone used is, for example, 100 parts by mass or more, preferably 10,000 parts by mass or more, based on 100 parts by mass of the cross-linking catalyst.
- the amount used is, for example, 50,000 parts by mass or less.
- the adhesive composition may contain other components, if necessary.
- Other components include, for example, polymerizable compounds and cured products thereof, photopolymerization initiators, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents. Can be mentioned.
- Examples of the polymerizable compound include a monomer having one polymerizable functional group (ethylenically unsaturated double bond) (monofunctional monomer) and a monomer having a plurality of polymerizable functional groups (polyfunctional monomer). Be done.
- Examples of the monofunctional monomer include monofunctional (meth) acrylate.
- Examples of the polyfunctional monomer include polyfunctional (meth) acrylate.
- the adhesive composition preferably further contains a photopolymerization initiator.
- the tacky composition comprises a base polymer, a compound that develops color by reaction with an acid, an acid generator, a metal complex, a cross-linking agent to be blended if necessary, a cross-linking catalyst to be blended if necessary, and a cross-linking catalyst to be blended if necessary. It is obtained by blending the acetylacetone to be added and other components to be blended as necessary in the above-mentioned ratios.
- the pressure-sensitive adhesive sheet S can be produced, for example, by applying the above-mentioned adhesive composition on a release film (first release film) to form a coating film, and then drying the coating film (in FIG. 1, virtual).
- the adhesive sheet S is arranged on the release film L indicated by the line).
- Examples of the release film include a flexible plastic film.
- Examples of the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film.
- the thickness of the release film is, for example, 3 ⁇ m or more. The same thickness is, for example, 200 ⁇ m or less.
- the surface of the release film is preferably mold-released.
- Examples of the method of applying the adhesive composition include roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, and lip coat. , And die coat.
- the drying temperature of the coating film is, for example, 50 ° C. or higher.
- the impression temperature is, for example, 200 ° C. or lower.
- the drying time is, for example, 5 seconds or more.
- the drying time is, for example, 20 minutes or less.
- the cross-linking reaction proceeds at the same time as the above drying or by subsequent aging.
- the aging conditions are appropriately set depending on the type of the cross-linking agent.
- the aging temperature is, for example, 20 ° C. or higher.
- the aging temperature is, for example, 160 ° C. or lower.
- the aging time is, for example, 1 minute or more.
- the aging time is, for example, 7 days or less.
- the adhesive composition contains acetylacetone (in other words, when acetylacetone is coordinated to dibutyltin dilaurate), the acetylacetone coordinated to dibutyltin dilaurate is removed at the time of drying. This allows the cross-linking reaction to proceed.
- a release film may be further laminated on the pressure-sensitive adhesive layer 10 on the first release film.
- the second release film is, for example, a flexible plastic film that has been subjected to a surface release treatment.
- the same film as described above for the first release film can be used.
- the pressure-sensitive adhesive sheet S whose adhesive surface is covered and protected by the release film can be manufactured.
- Each release film is peeled off from the pressure-sensitive adhesive sheet S as needed when using the pressure-sensitive adhesive sheet S.
- the thickness of the pressure-sensitive adhesive layer 10 is, for example, 10 ⁇ m or more, preferably 15 ⁇ m or more, from the viewpoint of ensuring sufficient adhesiveness to the adherend. From the viewpoint of handleability of the pressure-sensitive adhesive sheet S, the thickness of the pressure-sensitive adhesive layer 10 is, for example, 300 ⁇ m or less, preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the haze of the pressure-sensitive adhesive layer 10 is, for example, 3% or less, preferably 2% or less, and more preferably 1% or less. Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend.
- the haze of the pressure-sensitive adhesive layer 10 can be measured using a haze meter in accordance with JIS K7136 (2000). Examples of the haze meter include "NDH2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. and "HM-150 type” manufactured by Murakami Color Technology Research Institute.
- the average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 nm to 700 nm is, for example, 80% or more, preferably 85% or more, and more preferably 90%. That is all.
- Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend.
- the pressure-sensitive adhesive layer 10 is applied to the glass plate.
- the adhesive strength shown is, for example, 1.0 N / 25 mm or more, preferably 5.0 N / 25 mm or more.
- the adhesive strength is preferably 50 N / 25 mm or less, more preferably 40 N / 25 mm or less, and further preferably 20 N / 25 mm or less.
- the shear storage elastic modulus at 25 ° C. which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is preferably 0.1 ⁇ 105 Pa or more. More preferably, it is 0.5 ⁇ 10 5 Pa or more, and even more preferably 1 ⁇ 10 5 Pa or more.
- the shear storage elastic modulus is preferably 10 ⁇ 10 5 Pa or less, more preferably 5 ⁇ 10 5 Pa or less, and further preferably 3 ⁇ 10 5 Pa or less.
- the polymer component (base polymer) of the pressure-sensitive adhesive layer 10 has a sphere-type microphase-separated structure.
- the sphere-type microphase-separated structure specifically has a sea-island structure, in which spherical dispersed phases (islands) are dispersed in a matrix (sea).
- the dispersed phase is compatible with the color-developing compound, and the matrix is not compatible with the color-developing compound.
- the color-developing compound tends to stay on the islands after the discolored portion is formed on the pressure-sensitive adhesive layer 10 (that is, after the color-developing compound is developed by an external stimulus).
- Suitable for suppressing the movement (diffusion, etc.) of color-developing compounds within By suppressing the movement of the color-developing compound, deterioration of the discolored portion (bleeding, fading, non-uniformity of color, etc.) is suppressed.
- the polymer component includes, for example, a polymer (first polymer) having a soft segment forming a matrix and a hard segment forming a dispersed phase in the molecule.
- first polymer include a block polymer having a first polymer block as a soft segment and a second polymer block as a hard segment.
- the block polymer may have a plurality of first polymer blocks having different monomer compositions, or may have a plurality of second polymer blocks having different monomer compositions (in this case, the block polymer may have a plurality of second polymer blocks having different monomer compositions. It is a multi-block copolymer in which the number of block types based on the above is 3 or more).
- the first polymer examples include a graft polymer having a polymer main chain as a soft segment and a polymer side chain as a hard segment.
- the graft polymer may have a plurality of polymer side chains having different monomer compositions, or may have a plurality of polymer blocks having different monomer compositions in the polymer main chain.
- the polymer component may contain one kind of first polymer or may contain a plurality of kinds of first polymers.
- the polymer component may contain a polymer other than the first polymer (second polymer).
- the polymer component may include a second polymer that forms a matrix with the soft segments of the first polymer, or may include a second polymer that forms a dispersed phase with the hard segments of the first polymer.
- the polymer component may contain one kind of second polymer or a plurality of kinds of second polymers.
- the hard segment forming the island portion is a monomer solution (when a monomer solution cannot be prepared at 25 ° C., a polymer solution) in which the colorant is determined to have compatibility by the compatibility determination test described later with respect to Examples. ), which is a segment containing 80% by mass or more of the same monomer composition.
- the color-developing compound has compatibility with the islands formed from such hard segments.
- the glass transition temperature of this hard segment is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 50 ° C. or higher.
- the soft segment forming the sea portion is a monomer solution in which the colorant is determined to be incompatible by the compatibility determination test described later with respect to the examples (when the monomer solution cannot be prepared at 25 ° C., m). It is a segment containing 80% by mass or more of the same monomer composition as the polymer solution).
- the color-developing compound has no compatibility with the second phase formed from such soft segments.
- the glass transition temperature of this soft segment is preferably 0 ° C. or lower, more preferably less than 0 ° C., still more preferably ⁇ 30 ° C. or lower, and particularly preferably ⁇ 50 ° C. or lower. From the viewpoint of ensuring the adhesive strength of the pressure-sensitive adhesive layer 10, the mass ratio of the soft segment in the polymer component is preferably larger than the mass ratio of the hard segment.
- a rubber polymer and / or an acrylic polymer is preferably used from the viewpoint of ease of forming a sea-island structure.
- a styrene copolymer is preferably used as the rubber polymer.
- the styrene copolymer include styrene-isoprene-styrene copolymer (SIS), SIS hydrogenated additive, styrene-ethylene-butylene copolymer (SEB), and styrene-butadiene-styrene copolymer (SBS).
- SBS hydrogenated additives, styrene-isobutylene-styrene copolymer (SIBS), and styrene-butadiene-styrene-butadiene (SBSB).
- styrene forms a hard segment and unsaturated hydrocarbons copolymerizing with styrene form a soft segment.
- the rubber polymer may be used alone or in combination of two or more.
- the styrene content in the styrene copolymer is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more.
- the styrene content in the styrene copolymer is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
- the above-mentioned (meth) acrylic acid alkyl ester and the copolymerizable monomer for the acrylic polymer in the first embodiment are used. Can be done.
- an acrylic acid alkyl ester forming a hard segment an acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms is preferably used, and more preferably, methyl acrylate, methyl methacrylate, and acrylic. At least one selected from the group consisting of n-butyl acid acid is used.
- an acrylic acid alkyl ester having an alkyl group having 7 to 20 carbon atoms is preferably used, and more preferably 2-ethylhexyl acrylate, dodecyl acrylate, and the like. And at least one selected from the group consisting of octadecyl acrylate is used.
- an aromatic vinyl compound is preferably used, and styrene is more preferably used.
- the polymer component preferably contains a styrene-isoprene-styrene copolymer as the first polymer and a styrene-n-butyl acrylate copolymer as the second polymer.
- the amount of the styrene-n-butyl acrylate copolymer with respect to 100 parts by mass of the styrene-isoprene-styrene copolymer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.
- the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S of the second embodiment may or may not contain the metal complex described above with respect to the first embodiment.
- each of the pressure-sensitive adhesive sheets S of the first and second embodiments may be a single-sided pressure-sensitive adhesive sheet with a base material provided with a base material 20 in addition to the pressure-sensitive adhesive layer 10.
- the pressure-sensitive adhesive sheet S specifically includes a pressure-sensitive adhesive layer 10 and a base material 20 arranged on one side in the thickness direction D thereof.
- the base material 20 comes into contact with one surface of the pressure-sensitive adhesive layer 10 in the thickness direction D.
- the base material 20 is an element that functions as a transparent support.
- the base material 20 is, for example, a flexible plastic film.
- the constituent material of the plastic film include polyolefin, polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonate.
- the polyolefin include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, and the like.
- the plastic material of the base material 20 is preferably polyester, more preferably polyethylene terephthalate.
- the base material 20 has transparency.
- the haze of the base material 20 is, for example, 3% or less, preferably 2% or less, and more preferably 1% or less.
- the haze of the base material 20 can be measured using a haze meter in accordance with JIS K7136 (2000).
- the surface of the base material 20 on the pressure-sensitive adhesive layer 10 side may be subjected to a physical treatment, a chemical treatment, or an undercoat treatment for enhancing the adhesion to the pressure-sensitive adhesive layer 10.
- Physical treatments include, for example, corona treatment and plasma treatment.
- Examples of the chemical treatment include acid treatment and alkali treatment.
- the thickness of the base material 20 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, from the viewpoint of ensuring the strength for the base material 20 to function as a support. Further, from the viewpoint of realizing appropriate flexibility in the pressure-sensitive adhesive sheet S, the thickness of the base material 20 is, for example, 200 ⁇ m or less, preferably 150 ⁇ m or less, and more preferably 100 ⁇ m or less.
- the pressure-sensitive adhesive sheet S shown in FIG. 2 can be manufactured in the same manner as the above-mentioned manufacturing method except that the base material 20 is used instead of the first release film, for example.
- 3A to 3C show an example of how to use each of the adhesive sheets S according to the first and second embodiments.
- This method includes a preparation step, a joining step, and a discolored portion forming step.
- the adhesive sheet S, the first member 31, and the second member 32 are prepared.
- the first member 31 is, for example, a display panel.
- the first member 31 may be another electronic device or an optical device.
- the second member 32 is, for example, a transparent base material. Examples of the transparent base material include a transparent plastic base material and a transparent glass base material.
- the first member 31 and the second member 32 are joined via the adhesive sheet S.
- the laminated body W is obtained.
- the adhesive sheet S is arranged so as to be in contact with one surface in the thickness direction of the first member 31, and the second member 32 is arranged so as to be in contact with one surface in the thickness direction of the adhesive sheet S. ..
- an external stimulus is applied to the pressure-sensitive adhesive layer 10 in the laminated body W to form the discolored portion 11 in the pressure-sensitive adhesive layer 10.
- the active energy as an external stimulus to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32 via a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10. Irradiate the line. As a result, the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored.
- the pressure-sensitive adhesive layer 10 contains a color-developing compound as described above. Therefore, after the pressure-sensitive adhesive sheet S is attached to the adherend (members 31, 32 in the present embodiment), the pressure-sensitive adhesive layer 10 is locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer 10. be able to.
- the pressure-sensitive adhesive sheet S capable of forming the discolored portion 11 on the pressure-sensitive adhesive layer 10 after being bonded to the adherend the pressure-sensitive adhesive sheet S and the adherend are formed after the bonding and before the discolored portion 11 of the pressure-sensitive adhesive layer 10 is formed. The presence or absence of foreign matter and air bubbles can be inspected between.
- the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer 10 satisfy the above formula (1).
- Such a pressure-sensitive adhesive sheet S is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed on the pressure-sensitive adhesive layer 10 by applying an external stimulus. Suitable for imparting antireflection properties.
- the adhesive sheet S may be arranged on the light emitting side (image display side) of the pixel panel in the display panel.
- the discolored portion 11 is provided with a pattern shape corresponding to (that is, facing) the conductor layer as the metal wiring formed on the pixel panel included in the display panel. Thereby, the reflection of external light in the conductor layer can be suppressed.
- the width of the conductor layer is, for example, 10 ⁇ m or more.
- the width of the conductor layer is, for example, 300 ⁇ m or less.
- the conductor layer is preferably formed at a fine pitch.
- the distance between the conductor layers is, for example, 10 ⁇ m or more.
- the same interval is, for example, 100,000 ⁇ m or less.
- the line width of the discolored portion 11 corresponds to the width of the conductor layer described above. Specifically, the line width of the discolored portion 11 is, for example, 10 ⁇ m or more. The line width is, for example, 300 ⁇ m or less. Further, the interval between the discolored portions 11 is, for example, 10 ⁇ m or more. The same interval is, for example, 100,000 ⁇ m or less.
- the shielding property and the antireflection property can be improved. As a result, it is possible to improve the visibility of the display panel provided with the metal wiring while suppressing the reflection of external light on the metal wiring.
- the feature of the present invention is to adjust W2 / W1 described above, preferably to adjust W3 / W1. That is, the mode of use of the variable color film of the present invention is not limited to forming a linear colored portion (color-developing portion), and various colored portions can be formed. More specifically, examples of the colored portion that can be formed include a linear shape, a point shape, a rectangular shape, a circular shape, an elliptical shape, and an indefinite shape.
- the present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
- the specific numerical values such as the blending amount (content), the physical property value, the parameter, etc. described below are the blending amounts corresponding to them described in the above-mentioned "form for carrying out the invention” (forms for carrying out the invention). It can be replaced with an upper limit (numerical value defined as “less than or equal to” or “less than”) or a lower limit (numerical value defined as "greater than or equal to” or “greater than or equal to”) such as content), physical property value, and parameter.
- Example 1 ⁇ Preparation of adhesive composition> The following components were uniformly mixed with the above polymer solution containing the acrylic polymer of Production Example 1 per 100 parts by mass of the acrylic polymer (base polymer) to prepare an adhesive composition.
- the adhesive composition was applied to a release film (trade name "MRF # 38", polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Plastics Co., Ltd.) having one side as a release surface to form a coating film.
- this coating film was dried at 132 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m.
- a release film (trade name "MRF # 38", polyester film, thickness 38 ⁇ m, manufactured by Mitsubishi Plastics Co., Ltd.) having a release surface on one side was attached to this pressure-sensitive adhesive layer. Then, it was aged at 60 ° C. for 24 hours, and the crosslinking reaction was allowed to proceed in the pressure-sensitive adhesive layer.
- the adhesive sheet of Example 1 was produced.
- the composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 1 is shown in Table 1 in units of mass (the same applies to Examples 1 to 3 and Comparative Example 1 described later).
- Example 2 and 3 and Comparative Example 1 Each of the pressure-sensitive adhesive sheets of Examples 2 and 3 and Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1. However, the composition of the adhesive composition was changed to the amount shown in Table 1.
- Example 4 ⁇ Preparation of adhesive composition> The following components are uniformly mixed per 100 parts by mass of a styrene-isoprene-styrene block copolymer (trade name "Quintac 3520", styrene content ratio 15% by mass, manufactured by Nippon Zeon Corporation) as the first polymer (base polymer).
- the adhesive composition was prepared.
- Second polymer styrene-acrylic block copolymer (trade name "FBP-001", manufactured by Fujikura Kasei Co., Ltd.) 5 parts by mass
- a coating film is coated with an adhesive composition on the release-treated surface of a 38 ⁇ m-thick base film (trade name “MRF # 38”, polyester film, manufactured by Mitsubishi Plastics) whose one side is mold-released. Formed. The coating was then dried by heating at 132 ° C. for 3 minutes. As a result, a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m was formed on the base film. Next, on the pressure-sensitive adhesive layer on the base film, a release-treated surface of a 38 ⁇ m-thick release film (trade name “MRE # 38”, polyester film, manufactured by Mitsubishi Resin Co., Ltd.) whose one side is mold-released is applied. I pasted them together.
- MRF # 38 polyester film, manufactured by Mitsubishi Plastics
- the pressure-sensitive adhesive sheet of Example 4 was produced.
- the composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 4 is shown in Table 2 in units of mass (the same applies to Examples 5 to 7 described later).
- Example 5 to 7 Each of the pressure-sensitive adhesive sheets of Examples 5 to 7 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 4. However, the blending amount of the second polymer was changed to the amount shown in Table 2.
- the adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the glass in an environment of 23 ° C. and a relative humidity of 50% (adhesive by the UV irradiation).
- the leuco-based dye in the layer was reacted with the photoacid generator).
- a UV-LED lamp having a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source, and the integrated irradiation amount is 8000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 320 nm to 390 nm).
- a sample for weather resistance test was prepared.
- UVA-TAC A film having a TAC film (KC2UA, manufactured by Konica Minolta) and a hard coat layer in order (a hard coat layer (thickness: 7 ⁇ m) is formed on one surface of KC2UA (thickness: 25 ⁇ m) by a hard coat treatment).
- KC2UA manufactured by Konica Minolta
- a hard coat layer thinness: 7 ⁇ m
- CS9934U Adhesive tape with UV absorption function, product name "CS9934U", thickness 100 ⁇ m, manufactured by Nitto Denko Corporation
- the weather resistance test sample it was installed in a transmittance measuring device (U4150 type spectrophotometer, manufactured by Hitachi High-Tech Science Co., Ltd.) so that light was applied from the eagle glass side. Then, the average transmittance and the values of L * , a * , and b * at wavelengths of 400 nm to 700 nm were measured.
- a transmittance measuring device U4150 type spectrophotometer, manufactured by Hitachi High-Tech Science Co., Ltd.
- the weather resistance test sample was irradiated with a super xenon lamp having an illuminance of 120 W in the wavelength range of 300 nm to 400 nm for 24 hours using a super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. As a result, a sample for weather resistance test after irradiation for 24 hours was obtained.
- the average transmittance (T2) of the weather resistance test sample after 24-hour irradiation at a wavelength of 400 nm to 700 nm, L * (L 2 * ) for the weather resistance test sample after 24-hour irradiation, and 24-hour irradiation were measured, respectively.
- Table 1 shows the results of T1, T2, and the color difference ( ⁇ E).
- a linear discolored portion was formed on the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with ultraviolet rays through a photomask having a linear opening.
- the photomask was formed from a dry film photoresist placed on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask was 200 ⁇ m.
- a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY" manufactured by Quark Technology Co., Ltd. is used as a light source through a photo mask and a base film.
- the pressure-sensitive adhesive layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (the integrated irradiation light amount in the wavelength range of 320 nm to 390 nm).
- the line width of the linear discolored portion formed on the pressure-sensitive adhesive layer was measured (measurement of the first discolored width W1). Specifically, first, the linear discolored portion formed on the adhesive layer is observed with a digital microscope (trade name "VHX-900", manufactured by KEYENCE), and a part of the discolored portion and its vicinity are included. The area to be used was photographed at a magnification of 50 times. Next, the captured image was binarized by image analysis software. Next, in the image after the binarization process, the line width (first color change width W1) of the linear color change portion was measured.
- the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 85 ° C. for 120 hours (first durability test).
- the specific measurement method is the same as the measurement method described above for the measurement of the first color change width W1.
- the rate of change (W2 / W1) is shown in Tables 1 and 2.
- the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 7 and Comparative Example 1 were formed in the same manner as in the above method except that the second durability test was performed instead of the first durability test.
- the line width of the linear discolored part was examined.
- the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 85 ° C. for 240 hours.
- the rate of change (third color change width W3 / first color change width W1) is shown in Tables 1 and 2.
- the micro-phase separation structure was confirmed for the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7 as follows. First, a sample for observation with a transmission electron microscope (TEM) was prepared. Specifically, the pressure-sensitive adhesive layer was stained and then rapidly frozen, and flakes were cut out from the pressure-sensitive adhesive layer using an ultramicrotome (manufactured by Leica). Then, the flakes were observed and photographed using a transmission electron microscope (trade name "HT7820", manufactured by Hitachi High-Technologies Corporation). Next, the obtained TEM image was analyzed by image analysis software and binarized. The microphase separation of the pressure-sensitive adhesive layer in Example 7 is typically shown in FIG.
- TEM transmission electron microscope
- each of the pressure-sensitive adhesive sheets of Examples 4 to 7 a sphere-type microphase-separated structure could be confirmed.
- the matrix (sea part) formed by the isoprene block (soft segment) of the first polymer is filled with the styrene (hard segment) of the first polymer and the second polymer (styrene-n-butyl acrylate copolymer).
- styrene styrene, n-butyl acrylate, methyl methacrylate (MMA), acrylic acid, N-vinyl-2-pyrrolidone (NVP), 2-methoxyethyl acrylate (2MEA), Solutions of methyl acrylate, 2-ethylhexyl acrylate (2EHA), lauryl acrylate (dodecyl acrylate), and stearyl acrylate (octadecyl acrylate) were prepared.
- MMA methyl methacrylate
- NDP N-vinyl-2-pyrrolidone
- MEA 2-methoxyethyl acrylate
- Solutions of methyl acrylate, 2-ethylhexyl acrylate (2EHA), lauryl acrylate (dodecyl acrylate), and stearyl acrylate (octadecyl acrylate) were prepared.
- the color-developing compound and the photoacid generator were dissolved in each solution of styrene, n-butyl acrylate, MMA, acrylic acid, NVP, 2MEA, and methyl acrylate without causing turbidity or precipitation (compound). C showed compatibility). On the other hand, the color-developing compound and the photoacid generator caused turbidity or precipitation with respect to each solution of 2EHA, lauryl acrylate, and stearyl acrylate, respectively (Compound C did not show compatibility).
- a polyisoprene solution was prepared as the polymer solution (the isoprene monomer solution could not be prepared because the isoprene is too volatile).
- a mixture containing 7.8 g of the polymer solution and 0.2 g of compound C (color-developing compound or photoacid generator) was stirred in a 50 mL screw tube (the ratio of compound C was 2.5% by mass). (Second stirring).
- the conditions for the second stirring are the same as the conditions for the first stirring described above. It was confirmed by observation after the second stirring that the color-developing compound and the photoacid generator each produced turbidity or precipitation with respect to the polymer solution (Compound C did not show compatibility).
- the compound C is added. It was determined to have compatibility. Further, with respect to a phase in which a segment containing 80% by mass or more of the same monomer composition as the above-mentioned monomer solution in which compound C does not exhibit compatibility is formed in a microphase separation structure by a polymer component having the segment, compound C is used. Was determined to be incompatible.
- the color-developing compound and the photoacid generator used in Examples 4 to 7 each have an island portion formed by a hard segment (HS) containing styrene and n-butyl acrylate in a microphase-separated structure.
- HS hard segment
- the proportion of the monomer (styrene, n-butyl acrylate) in which compound C is compatible is 80% by mass or more.
- the color-developing compound and the photoacid generator used in Examples 4 to 7 are not compatible with the sea portion formed by the soft segment (SS) containing isoprene in the microphase-separated structure, respectively (Example).
- SS soft segment
- the proportion of isoprene in which compound C is incompatible is 80% by mass or more).
- the adhesive sheet was attached to eagle glass (thickness 0.55 mm, manufactured by Matsunami Glass Co., Ltd.) to prepare a measurement sample (first measurement sample).
- the average transmittance at a wavelength of 400 nm to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (first transmittance measurement).
- the total light transmittance of the measurement sample at a wavelength of 400 nm to 700 nm is measured at a pitch of 1 nm with the measurement sample installed in the device so that the measurement sample is exposed to light from the eagle glass side. did.
- a sample similar to the above-mentioned first measurement sample was prepared.
- the sample was irradiated with ultraviolet rays.
- the adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the glass in an environment of 23 ° C. and a relative humidity of 50% (adhesive by the UV irradiation).
- the leuco-based dye in the layer was reacted with the photoacid generator).
- a UV-LED lamp having a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY" manufactured by Quark Technology Co., Ltd.
- the integrated irradiation amount is 8000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 320 nm to 390 nm). As described above, a measurement sample (second measurement sample) was prepared.
- the average transmittance at a wavelength of 400 nm to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (second transmittance measurement). Regarding the specific measurement method and conditions, the second transmittance measurement is the same as the first transmittance measurement described above.
- Table 2 shows the measured average transmittance T2 (average transmittance at a wavelength of 400 nm to 700 nm after UV irradiation) of the pressure-sensitive adhesive layer. Table 2 also shows the ratio of the average transmittance T2 to the above-mentioned average transmittance T1.
- variable color adhesive sheet of the present invention is used, for example, in the process of manufacturing a display panel for bonding elements included in a laminated structure of a display panel.
- Adhesive sheet (variable color adhesive sheet) 10 Adhesive layer 11 Discolored part 20 Base material 31 First member 32 Second member
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Abstract
This color-changeable adhesive sheet comprises an adhesive layer (10) capable of changing colors via an external stimulation. A first color change width W1 and a second color change width W2 satisfy formula (1). (1): 0.5 < W2/W1 < 2
Description
本発明は、可変色粘着シートに関する。
The present invention relates to a variable color adhesive sheet.
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、透明な粘着シートが用いられる。
A display panel such as an organic EL panel has a laminated structure including a pixel panel and a cover member. In the process of manufacturing such a display panel, for example, a transparent adhesive sheet is used for bonding the elements included in the laminated structure.
また、ディスプレイパネルにおける画素パネルの光出射側(画像表示側)に配置される透明粘着シートとして、同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の着色部分が予め形成されている粘着シートを用いることが、提案されている。そのような粘着シートは、例えば下記の特許文献1に記載されている。特許文献1には、具体的には、カーボンブラック顔料を含有する着色部分を有する粘着シートが記載されている。
Further, as a transparent adhesive sheet arranged on the light emitting side (image display side) of the pixel panel in the display panel, a colored portion for imparting design, shielding, antireflection, etc. to a predetermined portion of the sheet is previously provided. It has been proposed to use the formed pressure-sensitive adhesive sheet. Such an adhesive sheet is described in, for example, Patent Document 1 below. Patent Document 1 specifically describes an adhesive sheet having a colored portion containing a carbon black pigment.
しかしながら、ディスプレイパネルの製造過程において、着色部分が予め形成されている粘着シートを用いる場合、被着体に対する粘着シートの貼り合わせの後に、被着体と粘着シートの着色部分との間における異物および気泡の有無を適切に検査できない。ディスプレイパネル製造過程における粘着シートの貼り合わせには、貼り合わせ後に被着体と粘着シートとの間における異物および気泡の有無を適切に検査できることが求められる。
However, in the process of manufacturing a display panel, when an adhesive sheet having a colored portion formed in advance is used, foreign matter and foreign matter between the adherend and the colored portion of the adhesive sheet are formed after the adhesive sheet is attached to the adherend. The presence or absence of air bubbles cannot be properly inspected. In the bonding of adhesive sheets in the process of manufacturing a display panel, it is required to be able to appropriately inspect the presence or absence of foreign matter and air bubbles between the adherend and the adhesive sheet after bonding.
また、意匠性、遮蔽性、および、反射防止性などを付与する観点から、任意の箇所に、着色成分を任意の形状で形成する場合がある。そして、このような場合には、経時により、視認性や遮蔽性が低下する場合がある。
Further, from the viewpoint of imparting designability, shielding property, antireflection property, etc., a coloring component may be formed in an arbitrary shape at an arbitrary place. In such a case, the visibility and the shielding property may deteriorate with time.
本発明は、被着体への貼合わせ後に粘着剤層を局所的に変色可能であって、任意の箇所に意匠性、遮蔽性、および、反射防止性を付与するのに適した、可変色粘着シートを提供する。
INDUSTRIAL APPLICABILITY According to the present invention, the pressure-sensitive adhesive layer can be locally discolored after being attached to an adherend, and a variable color suitable for imparting designability, shielding property, and antireflection property to an arbitrary portion. Provide an adhesive sheet.
本発明[1]は、外部刺激によって変色可能な粘着剤層を備え、下記試験1により求められる第1変色幅W1、および、下記試験2により求められる第2変色幅W2が、下記式(1)を満たす、可変色粘着シートである。
The present invention [1] includes a pressure-sensitive adhesive layer that can be discolored by an external stimulus, and the first discoloration width W1 determined by the following test 1 and the second discoloration width W2 determined by the following test 2 are expressed by the following formula (1). ) Is a variable color adhesive sheet.
0.5<W2/W1<2 (1)
0.5 <W2 / W1 <2 (1)
<試験1>
ステップA:粘着剤層に対して外部刺激を線状に付与する。
ステップB:ステップAの後に、粘着剤層内に形成された変色領域の幅を測定する。
<試験2>
ステップC:前記試験1のステップA、ステップBの後に、85℃で120時間加熱処理する。
ステップD:ステップCの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 1>
Step A: External stimulus is linearly applied to the pressure-sensitive adhesive layer.
Step B: After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
<Test 2>
Step C: After step A and step B of thetest 1, heat treatment is performed at 85 ° C. for 120 hours.
Step D: After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
ステップA:粘着剤層に対して外部刺激を線状に付与する。
ステップB:ステップAの後に、粘着剤層内に形成された変色領域の幅を測定する。
<試験2>
ステップC:前記試験1のステップA、ステップBの後に、85℃で120時間加熱処理する。
ステップD:ステップCの後に、粘着剤層内に形成された変色領域の幅を測定する。 <
Step A: External stimulus is linearly applied to the pressure-sensitive adhesive layer.
Step B: After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
<Test 2>
Step C: After step A and step B of the
Step D: After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
本発明[2]は、前記第1変色幅W1、および、下記試験3により求められる第3変色幅W3が、下記式(2)を満たす、上記[1]に記載の可変色粘着シートを含んでいる。
The present invention [2] includes the variable color pressure-sensitive adhesive sheet according to the above [1], wherein the first color change width W1 and the third color change width W3 obtained by the following test 3 satisfy the following formula (2). I'm out.
0.5<W3/W1<2 (2)
0.5 <W3 / W1 <2 (2)
<試験3>
ステップE:上記の<試験1>のステップA、ステップBの後に、85℃で240時間加熱処理する。
ステップF:ステップEの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 3>
Step E: After step A and step B of <Test 1> above, heat treatment is performed at 85 ° C. for 240 hours.
Step F: After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
ステップE:上記の<試験1>のステップA、ステップBの後に、85℃で240時間加熱処理する。
ステップF:ステップEの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 3>
Step E: After step A and step B of <
Step F: After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
本発明[3]は、前記粘着剤層が、10μm以上300μm以下の厚みを有する、上記[1]または[2]に記載の可変色粘着シートを含んでいる。
The present invention [3] includes the variable color pressure-sensitive adhesive sheet according to the above [1] or [2], wherein the pressure-sensitive adhesive layer has a thickness of 10 μm or more and 300 μm or less.
本発明[4]は、前記粘着剤層の厚み方向一方側に配置された基材をさらに備える、上記[1]~[3]のいずれか一つに記載の可変色粘着シートを含んでいる。
The present invention [4] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [3], further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer. ..
本発明[5]は、前記粘着剤層を、ガラス板に対して貼着した後、23℃、剥離角度180°および剥離速度300mm/分の剥離条件での剥離試験において、前記ガラス板に対して示す粘着力が、1.0N/25mm以上50N/25mm以下である、上記[1]~[4]のいずれか一つに記載の可変色粘着シートを含んでいる。
In the present invention [5], after the pressure-sensitive adhesive layer is attached to a glass plate, the peeling test under the peeling conditions of 23 ° C., a peeling angle of 180 ° and a peeling speed of 300 mm / min is performed on the glass plate. The variable color adhesive sheet according to any one of the above [1] to [4], wherein the adhesive strength shown in the above is 1.0 N / 25 mm or more and 50 N / 25 mm or less.
本発明の可変色粘着シートは、外部刺激によって変色可能な粘着剤層を備える。そのため、可変色粘着シートを被着体に貼り合わせた後、粘着剤層における変色予定部分に対して、外部刺激を付与することにより、粘着剤層を局所的に変色させることができる。このような可変色粘着シートでは、貼り合わせ後であって粘着剤層の変色部分形成前に、可変色粘着シートと被着体との間における異物および気泡の有無を検査できる。
The variable color adhesive sheet of the present invention includes an adhesive layer that can be discolored by an external stimulus. Therefore, after the variable color pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer can be locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. With such a variable color pressure-sensitive adhesive sheet, the presence or absence of foreign matter and air bubbles between the variable color pressure-sensitive adhesive sheet and the adherend can be inspected after the bonding and before the formation of the discolored portion of the pressure-sensitive adhesive layer.
また、可変色粘着シートでは、粘着剤層の第1変色幅W1および第2変色幅W2が、0.5<W2/W1<2を満たす。このような可変色粘着シートは、外部刺激付与によって粘着剤層に変色部分が形成された後に当該変色部分の劣化を抑制するに適し、従って、任意の箇所に、意匠性、遮蔽性、および、反射防止性を付与するのに適する。
Further, in the variable color pressure-sensitive adhesive sheet, the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer satisfy 0.5 <W2 / W1 <2. Such a variable color pressure-sensitive adhesive sheet is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed in the pressure-sensitive adhesive layer by applying an external stimulus. Suitable for imparting antireflection properties.
1.第1変色幅W1および第2変色幅W2
本発明の可変色粘着シートは、外部刺激によって変色可能な粘着剤層を備え、下記試験1により求められる第1変色幅W1、および、下記試験2により求められる第2変色幅W2が、下記式(1)を満たす。 1. 1. First color change width W1 and second color change width W2
The variable color pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer that can be discolored by an external stimulus, and the first color change width W1 determined by the followingtest 1 and the second color change width W2 obtained by the following test 2 have the following formulas. Satisfy (1).
本発明の可変色粘着シートは、外部刺激によって変色可能な粘着剤層を備え、下記試験1により求められる第1変色幅W1、および、下記試験2により求められる第2変色幅W2が、下記式(1)を満たす。 1. 1. First color change width W1 and second color change width W2
The variable color pressure-sensitive adhesive sheet of the present invention includes a pressure-sensitive adhesive layer that can be discolored by an external stimulus, and the first color change width W1 determined by the following
0.5<W2/W1<2 (1)
0.5 <W2 / W1 <2 (1)
第1変色幅W1は、下記の<試験1>により求められる。
The first discoloration width W1 is obtained by the following <Test 1>.
<試験1>
ステップA:粘着剤層に対して外部刺激を線状に付与する。
ステップB:ステップAの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 1>
Step A: External stimulus is linearly applied to the pressure-sensitive adhesive layer.
Step B: After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
ステップA:粘着剤層に対して外部刺激を線状に付与する。
ステップB:ステップAの後に、粘着剤層内に形成された変色領域の幅を測定する。 <
Step A: External stimulus is linearly applied to the pressure-sensitive adhesive layer.
Step B: After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
第2変色幅W2は、下記の<試験2>により求められる。
The second discoloration width W2 is obtained by the following <Test 2>.
<試験2>
ステップC:上記の<試験1>のステップA、ステップBの後に、85℃で120時間加熱処理する。
ステップD:ステップCの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 2>
Step C: After step A and step B of <Test 1> above, heat treatment is performed at 85 ° C. for 120 hours.
Step D: After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
ステップC:上記の<試験1>のステップA、ステップBの後に、85℃で120時間加熱処理する。
ステップD:ステップCの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 2>
Step C: After step A and step B of <
Step D: After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
可変色粘着シートは、上記のように、外部刺激によって変色可能な粘着剤層を備える。そのため、可変色粘着シートを被着体に貼り合わせた後、粘着剤層における変色予定部分に対して、外部刺激を付与することにより、粘着剤層を局所的に変色させることができる。このような可変色粘着シートでは、貼り合わせ後であって粘着剤層の変色部分形成前に、可変色粘着シートと被着体との間における異物および気泡の有無を検査できる。
As described above, the variable color adhesive sheet includes an adhesive layer that can be discolored by an external stimulus. Therefore, after the variable color pressure-sensitive adhesive sheet is attached to the adherend, the pressure-sensitive adhesive layer can be locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. With such a variable color pressure-sensitive adhesive sheet, the presence or absence of foreign matter and air bubbles between the variable color pressure-sensitive adhesive sheet and the adherend can be inspected after the bonding and before the formation of the discolored portion of the pressure-sensitive adhesive layer.
また、可変色粘着シートでは、粘着剤層の第1変色幅W1および第2変色幅W2が上記式(1)を満たす。このような可変色粘着シートは、外部刺激付与によって粘着剤層に変色部分が形成された後に当該変色部分の劣化を抑制するに適し、従って、任意の箇所に、意匠性、遮蔽性、および、反射防止性を付与するのに適する。
Further, in the variable color pressure-sensitive adhesive sheet, the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer satisfy the above formula (1). Such a variable color pressure-sensitive adhesive sheet is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed in the pressure-sensitive adhesive layer by applying an external stimulus. Suitable for imparting antireflection properties.
この可変色粘着シートの使用方法の一例として、可変色粘着シートを、ディスプレイパネルにおける画素パネルの光出射側(画像表示側)に配置する場合がある。
As an example of how to use this variable color adhesive sheet, the variable color adhesive sheet may be arranged on the light emitting side (image display side) of the pixel panel in the display panel.
詳しくは、ディスプレイパネルに備えられた画素パネル上に、ファインピッチで金属配線を設ける場合がある。そして、金属配線での外光反射を抑制する観点から、このような金属配線に対応するパターン形状で着色部分を設ける場合がある。
Specifically, metal wiring may be provided at a fine pitch on the pixel panel provided in the display panel. Then, from the viewpoint of suppressing external light reflection in the metal wiring, a colored portion may be provided with a pattern shape corresponding to such metal wiring.
この可変色粘着シートでは、第1変色幅W1、および、第2変色幅W2が、上記式(1)を満たすため、遮蔽性、および、反射防止性を向上できる。その結果、金属配線での外光反射を抑制しつつ、金属配線が設けられたディスプレイパネルの視認性を向上できる。
In this variable color adhesive sheet, since the first color change width W1 and the second color change width W2 satisfy the above formula (1), the shielding property and the antireflection property can be improved. As a result, it is possible to improve the visibility of the display panel provided with the metal wiring while suppressing the reflection of external light on the metal wiring.
また、第1変色幅W1、および、第2変色幅W2が、上記式(1)を満たすように調整する方法としては、例えば、金属錯体(後述)を用いる方法(第1の方法)、粘着剤層の弾性率を高める方法、粘着剤層中の着色成分が他の成分に結合されたものを用いる方法、非相溶性または低相溶性を利用した海島構造の島部に着色成分を設ける方法(第2の方法)が挙げられる。
Further, as a method for adjusting the first discoloration width W1 and the second discoloration width W2 so as to satisfy the above formula (1), for example, a method using a metal complex (described later) (first method), adhesion. A method of increasing the elastic modulus of the agent layer, a method of using a color component in the pressure-sensitive adhesive layer bonded to another component, a method of providing a coloring component on an island portion of a sea-island structure utilizing incompatibility or low compatibility. (Second method) can be mentioned.
粘着剤層の弾性率を高める方法としては、例えば、モノマー成分として多官能モノマーを用いる方法、架橋剤を用いる方法、および、これらの複合方法が挙げられる。
Examples of the method for increasing the elastic modulus of the pressure-sensitive adhesive layer include a method using a polyfunctional monomer as a monomer component, a method using a cross-linking agent, and a method of combining these.
粘着剤層中の着色成分が他の成分に結合されたものを用いる方法としては、例えば、着色成分として、層中のポリマーに所定の色に発色可能な成分が連結・結合された着色ポリマーを用いる方法、当初は着色成分とポリマー成分が別々の成分であるが、反応により着色成分をポリマーに結合させる方法、および、これらの複合方法が挙げられる。
As a method of using a colored component in the pressure-sensitive adhesive layer bonded to another component, for example, as a colored component, a colored polymer in which a component capable of developing a predetermined color is linked / bonded to a polymer in the layer is used. Examples thereof include a method to be used, a method in which the coloring component and the polymer component are initially separate components, but a method in which the coloring component is bonded to the polymer by a reaction, and a method of combining these.
非相溶性または低相溶性を利用した海島構造の島部に着色成分を設ける方法としては、例えば、着色成分と相溶性の高いポリマーと、相溶性の低いポリマーを用い且つ相溶性が高いポリマーが島部となる海島構造として、着色成分を島部に設ける方法が挙げられる。
As a method of providing a coloring component on an island portion of a sea island structure utilizing incompatibility or low compatibility, for example, a polymer having high compatibility with the coloring component and a polymer having low compatibility and having high compatibility are used. As a sea-island structure that becomes an island, a method of providing a coloring component on the island can be mentioned.
2.第1変色幅W1および第3変色幅W3
可変色粘着シートは、好ましくは、第1変色幅W1、および、下記試験3により求められる第3変色幅W3が、下記式(2)を満たす。 2. 2. 1st color change width W1 and 3rd color change width W3
In the variable color adhesive sheet, preferably, the first color change width W1 and the third color change width W3 obtained by the following test 3 satisfy the following formula (2).
可変色粘着シートは、好ましくは、第1変色幅W1、および、下記試験3により求められる第3変色幅W3が、下記式(2)を満たす。 2. 2. 1st color change width W1 and 3rd color change width W3
In the variable color adhesive sheet, preferably, the first color change width W1 and the third color change width W3 obtained by the following test 3 satisfy the following formula (2).
0.5<W3/W1<2 (2)
0.5 <W3 / W1 <2 (2)
第3変色幅W3は、下記の<試験3>により求められる。
The third color change width W3 is obtained by the following <Test 3>.
<試験3>
ステップE:上記の<試験1>のステップA、ステップBの後に、85℃で240時間加熱処理する。
ステップF:ステップEの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 3>
Step E: After step A and step B of <Test 1> above, heat treatment is performed at 85 ° C. for 240 hours.
Step F: After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
ステップE:上記の<試験1>のステップA、ステップBの後に、85℃で240時間加熱処理する。
ステップF:ステップEの後に、粘着剤層内に形成された変色領域の幅を測定する。 <Test 3>
Step E: After step A and step B of <
Step F: After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
第1変色幅W1および第3変色幅W3が、上記式(2)を満たせば、任意の箇所に、より一層、意匠性、遮蔽性、および、反射防止性を付与できる。
If the first discoloration width W1 and the third discoloration width W3 satisfy the above formula (2), further designability, shielding property, and antireflection property can be imparted to any place.
また、第1変色幅W1、および、第3変色幅W3が、上記式(2)を満たすように調整する方法としては、上記した第1変色幅W1、および、第2変色幅W2が、上記式(1)を満たすように調整する方法と同様である。
Further, as a method of adjusting the first color change width W1 and the third color change width W3 so as to satisfy the above formula (2), the above-mentioned first color change width W1 and the above-mentioned second color change width W2 are described above. It is the same as the method of adjusting so as to satisfy the equation (1).
3.平均透過率T1、平均透過率T2、および色差
可変色粘着シートは、好ましくは、下記試験4により求められる平均透過率T1、および、下記試験5により求められる平均透過率T2が、下記式(3)を満たし、好ましくは、下記式(4)を満たす。 3. 3. The average transmittance T1, the average transmittance T2, and the color difference variable color pressure-sensitive adhesive sheet preferably have the average transmittance T1 determined by the following test 4 and the average transmittance T2 determined by the following test 5 according to the following formula (3). ), And preferably the following formula (4).
可変色粘着シートは、好ましくは、下記試験4により求められる平均透過率T1、および、下記試験5により求められる平均透過率T2が、下記式(3)を満たし、好ましくは、下記式(4)を満たす。 3. 3. The average transmittance T1, the average transmittance T2, and the color difference variable color pressure-sensitive adhesive sheet preferably have the average transmittance T1 determined by the following test 4 and the average transmittance T2 determined by the following test 5 according to the following formula (3). ), And preferably the following formula (4).
0.2<T2/T1<3 (3)
0.2<T2/T1<2 (4) 0.2 <T2 / T1 <3 (3)
0.2 <T2 / T1 <2 (4)
0.2<T2/T1<2 (4) 0.2 <T2 / T1 <3 (3)
0.2 <T2 / T1 <2 (4)
平均透過率T1は、下記の<試験4>により求められる。
The average transmittance T1 is obtained by the following <Test 4>.
<試験4>
ステップG:粘着剤層に、300nm~400nmの波長帯の光を照射する。
ステップH:粘着剤層の、波長400nm~700nmにおける平均透過率を測定する。 <Test 4>
Step G: The pressure-sensitive adhesive layer is irradiated with light in the wavelength band of 300 nm to 400 nm.
Step H: The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
ステップG:粘着剤層に、300nm~400nmの波長帯の光を照射する。
ステップH:粘着剤層の、波長400nm~700nmにおける平均透過率を測定する。 <Test 4>
Step G: The pressure-sensitive adhesive layer is irradiated with light in the wavelength band of 300 nm to 400 nm.
Step H: The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
平均透過率T1は、例えば、10%以上、好ましくは、15%以上である。平均透過率T1は、例えば、40%以下、好ましくは、30%以下である。平均透過率T1の測定方法について、より詳しくは、後述する耐候性試験において詳述する。
The average transmittance T1 is, for example, 10% or more, preferably 15% or more. The average transmittance T1 is, for example, 40% or less, preferably 30% or less. The method for measuring the average transmittance T1 will be described in more detail in the weather resistance test described later.
平均透過率T2は、下記の<試験5>により求められる。
The average transmittance T2 is obtained by the following <Test 5>.
<試験5>
ステップI:上記の<試験4>のステップGの後に、粘着剤層に、スーパーキセノンウェザーメーターで、波長300nm~400nmの範囲における照度が120Wであるキセノンランプを24時間照射する。
ステップJ:粘着剤層の、波長400nm~700nmにおける平均透過率を測定する。 <Test 5>
Step I: After step G of <Test 4> above, the pressure-sensitive adhesive layer is irradiated with a xenon lamp having an illuminance of 120 W in the wavelength range of 300 nm to 400 nm for 24 hours with a super xenon weather meter.
Step J: The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
ステップI:上記の<試験4>のステップGの後に、粘着剤層に、スーパーキセノンウェザーメーターで、波長300nm~400nmの範囲における照度が120Wであるキセノンランプを24時間照射する。
ステップJ:粘着剤層の、波長400nm~700nmにおける平均透過率を測定する。 <Test 5>
Step I: After step G of <Test 4> above, the pressure-sensitive adhesive layer is irradiated with a xenon lamp having an illuminance of 120 W in the wavelength range of 300 nm to 400 nm for 24 hours with a super xenon weather meter.
Step J: The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 nm to 700 nm is measured.
平均透過率T2は、例えば、15%以上、好ましくは、24%以上である。平均透過率T2は、例えば、50%以下、好ましくは、40%以下である。平均透過率T2の測定方法について、より詳しくは、後述する耐候性試験において詳述する。
The average transmittance T2 is, for example, 15% or more, preferably 24% or more. The average transmittance T2 is, for example, 50% or less, preferably 40% or less. The method for measuring the average transmittance T2 will be described in more detail in the weather resistance test described later.
可変色粘着シートが上記式(3)または上記式(4)を満たせば、耐候性に優れる。平均透過率T1および平均透過T2が、上記式(3)または上記式(4)を満たすように調整する方法としては、例えば、粘着剤層への酸素透過性を小さくする方法、酸化防止剤を粘着剤層に添加する方法、および、紫外線吸収剤を含有する基材や粘着剤層を積層する方法が挙げられる。
If the variable color adhesive sheet satisfies the above formula (3) or the above formula (4), the weather resistance is excellent. As a method for adjusting the average transmittance T1 and the average permeability T2 so as to satisfy the above formula (3) or the above formula (4), for example, a method for reducing oxygen permeability to the pressure-sensitive adhesive layer and an antioxidant are used. Examples thereof include a method of adding to the pressure-sensitive adhesive layer and a method of laminating a base material or a pressure-sensitive adhesive layer containing an ultraviolet absorber.
また、後述する耐候性試験により測定される色差は、耐候性の観点から、例えば、30以下、好ましくは、28以下、より好ましくは、25以下、さらに好ましくは、20以下である。
Further, the color difference measured by the weather resistance test described later is, for example, 30 or less, preferably 28 or less, more preferably 25 or less, and further preferably 20 or less from the viewpoint of weather resistance.
4.可変色粘着シート
上記式(1)を満たし、好ましくは、上記式(2)~上記式(4)を満たす可変色粘着シートの一例としての、粘着シートSについて説明する。粘着シートSにおいては、第1変色幅W1、および、第2変色幅W2を、上記式(1)を満たすように調整する方法として、上記の第1の方法(第1の実施形態)および第2の方法(第2の実施形態)を採用しているが、これらに限定されない。 4. Variable Color Adhesive Sheet The pressure-sensitive adhesive sheet S, which satisfies the above formula (1) and preferably satisfies the above formulas (2) to (4), will be described. In the adhesive sheet S, as a method of adjusting the first color change width W1 and the second color change width W2 so as to satisfy the above formula (1), the above-mentioned first method (first embodiment) and the first method. Although the method 2 (second embodiment) is adopted, the present invention is not limited thereto.
上記式(1)を満たし、好ましくは、上記式(2)~上記式(4)を満たす可変色粘着シートの一例としての、粘着シートSについて説明する。粘着シートSにおいては、第1変色幅W1、および、第2変色幅W2を、上記式(1)を満たすように調整する方法として、上記の第1の方法(第1の実施形態)および第2の方法(第2の実施形態)を採用しているが、これらに限定されない。 4. Variable Color Adhesive Sheet The pressure-sensitive adhesive sheet S, which satisfies the above formula (1) and preferably satisfies the above formulas (2) to (4), will be described. In the adhesive sheet S, as a method of adjusting the first color change width W1 and the second color change width W2 so as to satisfy the above formula (1), the above-mentioned first method (first embodiment) and the first method. Although the method 2 (second embodiment) is adopted, the present invention is not limited thereto.
粘着シートSは、図1に示すように、粘着剤層10を備える。粘着シートSは、所定の厚みのシート形状を有し、厚み方向と直交する方向(面方向)に延びる。粘着シートSは、例えば、ディスプレイパネル(例えば、画素パネルおよびカバー部材を含む積層構造を有する)における画素パネルの画像表示側に配置される透明粘着シートとして、用いられる。
As shown in FIG. 1, the pressure-sensitive adhesive sheet S includes a pressure-sensitive adhesive layer 10. The adhesive sheet S has a sheet shape having a predetermined thickness and extends in a direction (plane direction) orthogonal to the thickness direction. The pressure-sensitive adhesive sheet S is used, for example, as a transparent pressure-sensitive adhesive sheet arranged on the image display side of the pixel panel in a display panel (for example, having a laminated structure including a pixel panel and a cover member).
粘着剤層10は、粘着性組成物から形成された、透明性(可視光透過性)を有する感圧接着剤層である。粘着性組成物は、ベースポリマーと、酸との反応により発色する化合物と、酸発生剤とを含む。第1の実施形態では、粘着性組成物は、金属錯体を更に含む。
The pressure-sensitive adhesive layer 10 is a pressure-sensitive adhesive layer having transparency (visible light transmission) formed from the pressure-sensitive adhesive composition. The tacky composition comprises a base polymer, a compound that develops color by reaction with an acid, and an acid generator. In the first embodiment, the tacky composition further comprises a metal complex.
ベースポリマーは、粘着剤層10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。粘着剤層10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、アクリルポリマーが用いられる。
The base polymer is an adhesive component for developing adhesiveness in the adhesive layer 10. The base polymer exhibits rubber elasticity at room temperature. Examples of the base polymer include acrylic polymers, rubber polymers, polyester polymers, urethane polymers, polyether polymers, silicone polymers, polyamide polymers, and fluoropolymers. From the viewpoint of ensuring good transparency and tackiness in the pressure-sensitive adhesive layer 10, an acrylic polymer is preferably used as the base polymer.
粘着剤層10におけるベースポリマーの含有割合は、粘着剤層10でのベースポリマーの機能を適切に発現させる観点から、例えば、50質量%以上、好ましくは、60質量%以上、より好ましくは、70質量%以上である。
The content ratio of the base polymer in the pressure-sensitive adhesive layer 10 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70, from the viewpoint of appropriately expressing the function of the base polymer in the pressure-sensitive adhesive layer 10. It is mass% or more.
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を重合することにより得られるポリマーである。「(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。
The acrylic polymer is, for example, a polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester in a proportion of 50% by mass or more. "(Meta) 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、(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、アクリル酸メチルと、炭素数2~12のアルキル基を有するアクリル酸アルキルエステルとが併用され、さらに好ましくは、アクリル酸メチルと、アクリル酸2-エチルヘキシルとが併用される。
Examples of the (meth) acrylic acid alkyl ester include linear or branched (meth) acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms. Examples of such (meth) acrylic acid alkyl esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, and (meth) acrylic acid. Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, (meth) ) Hexyl acrylate, (meth) heptyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) octyl acrylate, (meth) isooctyl acrylate, (meth) nonyl acrylate, (meth) isononyl acrylate, ( Meta) decyl acrylate, (meth) isodecyl acrylate, (meth) undecyl acrylate, (meth) dodecyl acrylate, (meth) isotridecyl acrylate, (meth) tetradecyl acrylate, (meth) isotetradecyl acrylate, Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, nonadecil (meth) acrylate, and (meth) acrylate. Acrylic acid can be mentioned. The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more. 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, it has methyl acrylate and an alkyl group having 2 to 12 carbon atoms. Acrylic acid alkyl ester is used in combination, and more preferably, methyl acrylate 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、粘着剤層10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、例えば、50質量%以上、好ましくは、60質量%以上、より好ましくは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, for example, 50% by mass or more, preferably 60% by mass or more, more preferably, from the viewpoint of appropriately expressing basic properties such as adhesiveness in the pressure-sensitive adhesive layer 10. Is 70% by mass or more. The same ratio is, for example, 99% by mass or less.
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(極性基含有モノマー)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 monomer component may contain a copolymerizable monomer copolymerizable with the (meth) acrylic acid alkyl ester. Examples of the copolymerizable monomer include a monomer having a polar group (monomer containing a polar group). The polar group-containing monomer is useful for modifying the acrylic polymer, such as introducing a cross-linking point into the acrylic polymer and ensuring the cohesive force of the acrylic polymer.
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。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。
Examples of the polar group-containing monomer include a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer. The copolymerizable monomer preferably contains at least one selected from the group consisting of a hydroxyl group-containing monomer, a monomer having a nitrogen atom-containing ring, and a carboxy group-containing monomer. More preferably, the copolymerizable monomer comprises 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 the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (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 can be mentioned. As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
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、粘着剤層10における凝集力の確保の観点からは、例えば、1質量%以上、好ましくは、3質量%以上、より好ましくは、5質量%以上である。同割合は、アクリルポリマー重合時の重合反応溶液の粘度調整、および、アクリルポリマーの極性(粘着剤層10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)の調整の観点からは、例えば、30質量%以下、好ましくは、20質量%以下である。
The ratio of the hydroxyl group-containing monomer in the monomer component is, for example, 1% by mass or more, preferably 3% by mass or more, from the viewpoint of introducing a crosslinked structure into the acrylic polymer and ensuring the cohesive force in the pressure-sensitive adhesive layer 10. More preferably, it is 5% by mass or more. The same ratio is, for example, from the viewpoint of adjusting the viscosity of the polymerization reaction solution during the polymerization of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). , 30% by mass or less, preferably 20% by mass or less.
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 the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, and N-vinylpyrazine. N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloyl piperidine, N- (meth) acryloylpyrrolidin, N-vinylmorpholin, N-vinyl. -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione, N-vinylpyrazole, N-vinylisoxazole, N -Vinylthiazole and N-vinylisothiazole can be mentioned. As the monomer having a nitrogen atom-containing ring, N-vinyl-2-pyrrolidone is preferably used.
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、粘着剤層10における凝集力の確保、および、粘着剤層10における対被着体密着力の確保の観点からは、例えば、1質量%以上、好ましくは、3質量%以上、より好ましくは、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(粘着剤層10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)の調整の観点からは、例えば、30質量%以下、好ましくは、20質量%以下である。
The proportion of the monomer having a nitrogen atom-containing ring in the monomer component is, for example, 1% by mass from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10 and the adhesion to the adherend in the pressure-sensitive adhesive layer 10. As mentioned above, it is preferably 3% by mass or more, and more preferably 5% by mass or more. The same ratio is, for example, 30 mass from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and adjusting the polarity of the acrylic polymer (related to the compatibility between various additive components in the pressure-sensitive adhesive layer 10 and the acrylic polymer). % Or less, preferably 20% by mass or less.
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。
Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
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、粘着剤層10における凝集力の確保、および、粘着剤層10における対被着体密着力の確保の観点からは、例えば、1質量%以上、好ましくは、3質量%以上、より好ましくは、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、例えば、30質量%以下、好ましくは、20質量%以下である。
The ratio of the carboxy group-containing monomer in the monomer component is determined from the viewpoint of introducing a crosslinked structure into the acrylic polymer, ensuring the cohesive force in the pressure-sensitive adhesive layer 10, and ensuring the adhesion to the adherend in the pressure-sensitive adhesive layer 10. For example, it is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more. The same ratio is, for example, 30% by mass or less, preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and avoiding the risk of corrosion of the adherend by acid.
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。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、アミド基含有モノマー、スクシンイミド骨格を有するモノマー、マレイミド類、イタコンイミド類、アルコキシ基含有モノマー、ビニルエステル類、ビニルエーテル類、および、芳香族ビニル化合物が挙げられる。
The monomer component may contain other copolymerizable monomers. Examples of other copolymerizable monomers include acid anhydride monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, epoxy group-containing monomers, cyano group-containing monomers, amide group-containing monomers, monomers having a succinimide skeleton, and maleimides. Examples include itaconimides, alkoxy group-containing monomers, vinyl esters, vinyl ethers, and aromatic vinyl compounds.
酸無水物モノマーとしては、例えば、無水マレイン酸および無水イタコン酸が挙げられる。
Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride.
スルホン酸基含有モノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、および、(メタ)アクリロイルオキシナフタレンスルホン酸が挙げられる。
Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, and sulfopropyl (meth). Examples include acrylate and (meth) acryloyloxynaphthalene sulfonic acid.
リン酸基含有モノマーとしては、例えば、2-ヒドロキシエチルアクリロイルホスフェートが挙げられる。
Examples of the phosphate group-containing monomer include 2-hydroxyethylacryloyl phosphate.
エポキシ基含有モノマーとしては、例えば、(メタ)アクリル酸グリシジルおよび(メタ)アクリル酸-2-エチルグリシジルエーテルなどのエポキシ基含有アクリレート、アリルグリシジルエーテル、および、(メタ)アクリル酸グリシジルエーテルが挙げられる。
Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as glycidyl (meth) acrylate and -2-ethyl glycidyl ether (meth) acrylate, allyl glycidyl ether, and glycidyl ether (meth) acrylate. ..
シアノ基含有モノマーとしては、例えば、アクリロニトリルおよびメタクリロニトリルが挙げられる。
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
アミド基含有モノマーとしては、例えば、N-ビニルカルボン酸アミド類、N-ヒドロキシアルキル(メタ)アクリルアミド、N-アルコキシアルキル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、および、N-(メタ)アクリロイルモルホリンが挙げられる。
Examples of the amide group-containing monomer include N-vinylcarboxylic acid amides, N-hydroxyalkyl (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N. -(Meta) Acryloylmorpholine can be mentioned.
N-ビニルカルボン酸アミド類としては、例えば、(メタ)アクリルアミド、N,N-ジアルキル(メタ)アクリルアミド、N-アルキル(メタ)アクリルアミド、および、N-ビニルアセトアミドが挙げられる。
Examples of N-vinylcarboxylic acid amides include (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkyl (meth) acrylamide, and N-vinylacetamide.
N,N-ジアルキル(メタ)アクリルアミドとしては、例えば、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、および、N,N-ジ(t-ブチル)(メタ)アクリルアミドが挙げられる。
Examples of N, N-dialkyl (meth) acrylamide include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, and N, N-diisopropyl ( Examples include meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, and N, N-di (t-butyl) (meth) acrylamide.
N-アルキル(メタ)アクリルアミドとしては、例えば、N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、および、N-n-ブチル(メタ)アクリルアミドが挙げられる。
Examples of N-alkyl (meth) acrylamide include N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. ..
N-ヒドロキシアルキル(メタ)アクリルアミドとしては、例えば、N-(2-ヒドロキシエチル)(メタ)アクリルアミド、N-(2-ヒドロキシプロピル)(メタ)アクリルアミド、N-(1-ヒドロキシプロピル)(メタ)アクリルアミド、N-(3-ヒドロキシプロピル)(メタ)アクリルアミド、N-(2-ヒドロキシブチル)(メタ)アクリルアミド、N-(3-ヒドロキシブチル)(メタ)アクリルアミド、およびN-(4-ヒドロキシブチル)(メタ)アクリルアミドが挙げられる。N-アルコキシアルキル(メタ)アクリルアミドとしては、例えば、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、および、N-ブトキシメチル(メタ)アクリルアミドが挙げられる。
Examples of N-hydroxyalkyl (meth) acrylamide include N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (1-hydroxypropyl) (meth). Acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, and N- (4-hydroxybutyl) Examples include (meth) acrylamide. Examples of N-alkoxyalkyl (meth) acrylamide include N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide.
スクシンイミド骨格を有するモノマーとしては、例えば、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、および、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミドが挙げられる。
Examples of the monomer having a succinimide skeleton include N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyhexamethylene succinimide. Can be mentioned.
マレイミド類としては、例えば、N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、および、N-フェニルマレイミドが挙げられる。
Examples of maleimides include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide.
イタコンイミド類としては、例えば、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、および、N-ラウリルイタコンイミドが挙げられる。
Examples of the itaconimides include N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and , N-laurylitaconimide.
アルコキシ基含有モノマーとしては、例えば、(メタ)アクリル酸アルコキシアルキル類および(メタ)アクリル酸アルコキシアルキレングリコール類が挙げられる。(メタ)アクリル酸アルコキシアルキル類としては、例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、および、(メタ)アクリル酸エトキシプロピルが挙げられる。(メタ)アクリル酸アルコキシアルキレングリコール類としては、例えば、(メタ)アクリル酸メトキシエチレングリコール、および、(メタ)アクリル酸メトキシポリプロピレングリコールが挙げられる。
Examples of the alkoxy group-containing monomer include (meth) acrylate alkoxyalkyls and (meth) acrylate alkoxyalkylene glycols. Examples of the (meth) acrylate alkoxyalkyls include (meth) acrylate 2-methoxyethyl, (meth) acrylate 3-methoxypropyl, (meth) acrylate 2-ethoxyethyl, and (meth) acrylate propoxyethyl. , (Meth) butoxyethyl acrylate, and (meth) ethoxypropyl acrylate. Examples of the (meth) acrylate alkoxyalkylene glycols include (meth) methoxyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate.
ビニルエステル類としては、例えば、酢酸ビニルおよびプロピオン酸ビニルが挙げられる。
Examples of vinyl esters include vinyl acetate and vinyl propionate.
ビニルエーテル類としては、例えば、メチルビニルエーテルおよびエチルビニルエーテルが挙げられる。
Examples of vinyl ethers include methyl vinyl ether and ethyl vinyl ether.
芳香族ビニル化合物としては、例えば、スチレン、α-メチルスチレン、および、ビニルトルエンが挙げられる。オレフィン類としては、例えば、エチレン、ブタジエン、イソプレン、および、イソブチレンが挙げられる。
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene. Examples of olefins include ethylene, butadiene, isoprene, and isobutylene.
共重合性モノマーは、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 copolymerizable monomer may be used alone or in combination of two or more.
アクリルポリマーは、上記のモノマー成分を重合させることによって形成することができる。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。溶液重合では、例えば、モノマー成分と重合開始剤とを溶媒に配合して反応溶液を調製した後、その反応溶液を加熱する。そして、反応溶液中でのモノマー成分の重合反応を経ることによって、アクリルポリマーを含むアクリルポリマー溶液を得ることができる。
Acrylic polymer can be formed by polymerizing the above monomer components. Examples of the polymerization method include solution polymerization, bulk polymerization, and emulsion polymerization, and solution polymerization is preferable. In solution polymerization, for example, a monomer component and a polymerization initiator are mixed with a solvent to prepare a reaction solution, and then the reaction solution is heated. Then, an acrylic polymer solution containing an acrylic polymer can be obtained by undergoing a polymerization reaction of the monomer components in the reaction solution.
重合開始剤としては、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、モノマー成分100質量部に対して、例えば、0.05質量部以上である。また、同使用量は、例えば、1質量部以下である。
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 with respect to 100 parts by mass of the monomer component. The amount used is, for example, 1 part by mass or less.
熱重合開始剤としては、例えば、アゾ系重合開始剤および過酸化物系重合開始剤が挙げられる。アゾ系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。過酸化物系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。
Examples of the thermal polymerization initiator include an azo-based polymerization initiator and a peroxide-based polymerization initiator. Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azobis (2-methylpropionic acid) dimethyl. 4,4'-Azobis-4-cyanovaleric acid, azobisisobutyvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2) -Imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, and 2,2'-azobis (N, N'-dimethyleneisobutyramidin) dihydrochloride Can be mentioned. Examples of the peroxide-based polymerization initiator include 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、粘着剤層10における凝集力の確保の観点からは、例えば、100000以上、好ましくは、300000以上、より好ましくは、500000以上である。同重量平均分子量は、例えば、5000000以下、好ましくは、3000000以下、より好ましくは、2000000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, for example, 100,000 or more, preferably 300,000 or more, and more preferably 500,000 or more, from the viewpoint of ensuring the cohesive force in the pressure-sensitive adhesive layer 10. The weight average molecular weight is, for example, 5,000,000 or less, preferably 3,000,000 or less, and more preferably 2000000 or less. The weight average molecular weight of the acrylic polymer is measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
ベースポリマーのガラス転移温度(Tg)は、例えば、0℃以下、好ましくは、-10℃以下、より好ましくは、-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 base polymer is, for example, 0 ° C. or lower, preferably −10 ° C. or lower, 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、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。以上は、後述のハードセグメントおよびソフトセグメントのガラス転移温度についても同様である。
For the glass transition temperature (Tg) of the polymer, the glass transition temperature (theoretical value) obtained based on the Fox formula below can be used. The Fox formula is a relational expression between the glass transition temperature Tg of the polymer and the glass transition temperature Tgi of the homopolymer of the monomer constituting the polymer. In the Fox equation 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 temperature of the homopolymer formed from the monomer i. (° C) is indicated. Literature values can be used for the glass transition temperature of homopolymers, for example, "Polymer Handbook" (4th edition, John Willey & Sons, Inc., 1999) and "New Polymer Bunko 7 Introduction to Synthetic Resins for Paints". (Kyozo Kitaoka, Polymer Publishing Association, 1995) lists the glass transition temperatures of various homopolymers. On the other hand, the glass transition temperature of the homopolymer of the monomer can also be obtained by the method specifically described in JP-A-2007-51271. The above is the same for the glass transition temperature of the hard segment and the soft segment described later.
Foxの式 1/(273+Tg)=Σ[Wi/(273+Tgi)]
Fox formula 1 / (273 + Tg) = Σ [Wi / (273 + Tgi)]
酸との反応により発色する化合物(発色性化合物)としては、例えば、ロイコ系色素、トリアリールメタン系色素、ジフェニルメタン系色素、フルオラン系色素、スピロピラン系色素、および、ローダミン系色素が挙げられる。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 compound (color-developing compound) that develops color by reaction with an acid include leuco-based dye, triarylmethane-based dye, diphenylmethane-based dye, fluorane-based dye, spiropyran-based dye, and rhodamine-based dye. The color-developing compound may be used alone or in combination of two or more.
ロイコ系色素としては、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。
Examples of leuco-based dyes include 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] and 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-xylidinofluorane, and 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methyl) Indol-3-yl) -4-azaphthalide can be mentioned.
トリアリールメタン系色素としては、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。ジフェニルメタン系色素としては、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。フルオラン系色素としては、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。スピロピラン系色素としては、例えば、3-メチルスピロジナフトピランが挙げられる。ローダミン系色素としては、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 the triarylmethane dye include p, p', p "-tris-dimethylaminotriphenylmethane. Examples of the diphenylmethane dye include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl. Examples of the fluorin-based dye include 3-diethylamino-6-methyl-7-chlorofluorane. Examples of the spiropyran-based dye include 3-methylspirodinaphthopyrane. Examples of the dye system include rhodamine-B-anilinolactum.
粘着剤層10において、良好な黒系着色性を確保する観点から、発色性化合物としては、好ましくは、ロイコ系色素、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 black coloration in the pressure-sensitive adhesive layer 10, the color-developing compound is preferably a leuco-based dye, more preferably 2'-anilino-6'-(N-ethyl-N-). Isopentylamino) -3'-methylspiro [phthalide-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、例えば、0.5質量部以上、好ましくは、1質量部以上である。同配合量は、例えば、10質量部以下、好ましくは、7質量部以下、より好ましくは、5質量部以下である。
The blending amount of the color-developing compound with respect to 100 parts by mass of the base polymer is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more. The blending amount is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.
酸発生剤としては、好ましくは、活性エネルギー線が照射されることによって酸を発生する光酸発生剤が用いられる。その場合、粘着剤層10は、外部刺激として活性エネルギー線の照射を受けた部分が変色可能である。具体的には、粘着剤層10において活性エネルギー線の照射を受けた部分では、光酸発生剤から酸が発生し、この酸によって発色性化合物が発色する。粘着剤層10において活性エネルギー線の照射を受けた部分は、発色性化合物の発色に応じて、例えば、黒系色に着色する。外部刺激としての活性エネルギー線の種類は、光酸発生剤の種類(具体的には、光酸発生剤が酸を発生する活性エネルギー線の波長)によって定まる。活性エネルギー線としては、例えば、紫外線、可視光、赤外線、X線、α線、β線、および、γ線が挙げられる。使用設備の多様性およびハンドリング容易性の観点からは、活性エネルギー線としては、好ましくは、紫外線が挙げられる。
As the acid generator, a photoacid generator that generates an acid by being irradiated with active energy rays is preferably used. In that case, the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy ray as an external stimulus can be discolored. Specifically, in the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays, an acid is generated from the photoacid generator, and the color-developing compound is developed by this acid. The portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays is colored, for example, into a blackish color according to the color development of the color-developing compound. The type of active energy ray as an external stimulus is determined by the type of photoacid generator (specifically, the wavelength of the active energy ray in which the photoacid generator generates acid). Examples of the active energy ray include ultraviolet rays, visible light, infrared rays, X-rays, α rays, β rays, and γ rays. From the viewpoint of variety of equipment used and ease of handling, the active energy ray preferably includes ultraviolet rays.
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、ヨードニウムおよびスルホ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
-とからなるオニウム塩(オニウム化合物)が挙げられる。
Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays. Onium compounds are provided, for example, in the form of onium salts of onium cations and anions. Examples of onium cations include iodonium and sulfonium. 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 generator may be used alone or in combination of two or more. The photoacid generator preferably includes an onium salt (onium compound) composed of sulfonium and C4 F 9 HSO 3- .
ベースポリマー100質量部に対する酸発生剤の配合量は、例えば、1質量部以上、好ましくは、2質量部以上、より好ましくは、5質量部以上、さらに好ましくは、6質量部以上である。同配合量は、例えば、20質量部以下、好ましくは、15質量部以下、より好ましくは、10質量部以下である。
The blending amount of the acid generator with respect to 100 parts by mass of the base polymer is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 6 parts by mass or more. The blending amount is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.
また、発色性化合物100質量部に対する酸発生剤の配合量は、例えば、100質量部以上、好ましくは、200質量部以上、より好ましくは、300質量部以上、さらに好ましくは、330質量部以上である。同配合量は、例えば、1000質量部以下、好ましくは、700質量部以下、より好ましくは、500質量部以下である。
The blending amount of the acid generator with respect to 100 parts by mass of the color-developing compound is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 300 parts by mass or more, and further preferably 330 parts by mass or more. be. The blending amount is, for example, 1000 parts by mass or less, preferably 700 parts by mass or less, and more preferably 500 parts by mass or less.
金属錯体は、第1変色幅W1、および、第2変色幅W2を、上記式(1)を満たすように調整するために、配合される。ロイコ系色素などの着色成分は、金属錯体との配位結合により、移動が抑制される。金属錯体は、金属イオンに配位子が配位されたものである。
金属イオンを構成する金属としては、周期律表(IUPAC Periodic Table of the Elements(version date 19 February 2010)に従う。以下同じ)第1族のアルカリ金属、第2族のアルカリ土類金属、第3族~第12族の遷移金属が挙げられる。金属としては、好ましくは、第2族のアルカリ土類金属、および、第3族~第12族の遷移金属、ロイコ系色素の発色体のカルボキシル基への強い配位性の観点からは、Mg(マグネシウム)、金属錯体によるロイコ系色素と形成される両性対イオンの寄与の観点からは、Zn(亜鉛)が挙げられる。 The metal complex is blended in order to adjust the first discoloration width W1 and the second discoloration width W2 so as to satisfy the above formula (1). The movement of coloring components such as leuco-based dyes is suppressed by the coordination bond with the metal complex. A metal complex is one in which a ligand is coordinated with a metal ion.
The metals that make up the metal ions are according to the IUPAC Periodic Table of the Elements (version date 19 February 2010). The same shall apply hereinafter.Group 1 alkali metals, Group 2 alkaline earth metals, Group 3 ~ Group 12 transition metals can be mentioned. The metal is preferably Mg from the viewpoint of the strong coordination of the group 2 alkaline earth metal, the group 3 to group 12 transition metal, and the leuco dye to the carboxyl group of the chromogen. From the viewpoint of the contribution of (magnesium) and the amphoteric counterion formed with the leuco-based dye by the metal complex, Zn (zinc) can be mentioned.
金属イオンを構成する金属としては、周期律表(IUPAC Periodic Table of the Elements(version date 19 February 2010)に従う。以下同じ)第1族のアルカリ金属、第2族のアルカリ土類金属、第3族~第12族の遷移金属が挙げられる。金属としては、好ましくは、第2族のアルカリ土類金属、および、第3族~第12族の遷移金属、ロイコ系色素の発色体のカルボキシル基への強い配位性の観点からは、Mg(マグネシウム)、金属錯体によるロイコ系色素と形成される両性対イオンの寄与の観点からは、Zn(亜鉛)が挙げられる。 The metal complex is blended in order to adjust the first discoloration width W1 and the second discoloration width W2 so as to satisfy the above formula (1). The movement of coloring components such as leuco-based dyes is suppressed by the coordination bond with the metal complex. A metal complex is one in which a ligand is coordinated with a metal ion.
The metals that make up the metal ions are according to the IUPAC Periodic Table of the Elements (version date 19 February 2010). The same shall apply hereinafter.
配位子としては、例えば、単座配位子、および、二座配位子が挙げられる。単座配位子としては、例えば、ヒドロキソ(OH-)、ハロゲン(例えば、クロロ(Cl-))、および、シアノ(CN-)が挙げられる。二座配位子としては、例えば、エチレンジアミン、ビピリジン、フェナントロリン、および、サリチル酸が挙げられる。このような金属錯体のうち、好ましくは、二座配位子、両性対イオンの寄与の観点からは、より好ましくは、サリチル酸亜鉛(具体的には、サリチル酸亜鉛三水和物)が挙げられる。金属錯体は、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 ligand include a monodentate ligand and a bidentate ligand. Examples of the monodentate ligand include hydroxo (OH − ), halogen (eg, chloro (Cl − )), and cyano (CN − ). Bidentate ligands include, for example, ethylenediamine, bipyridine, phenanthroline, and salicylic acid. Among such metal complexes, zinc salicylate (specifically, zinc salicylate trihydrate) is more preferable from the viewpoint of contribution of bidentate ligand and amphoteric counterion. The metal complex may be used alone or in combination of two or more.
ベースポリマー100質量部に対する金属錯体の配合量は、例えば、0.1質量部以上、好ましくは、0.2質量部以上、より好ましくは、0.5質量部以上、さらに好ましくは、0.8質量部以上である。同配合量は、例えば、5質量部以下、好ましくは、2質量部以下である。
The blending amount of the metal complex with respect to 100 parts by mass of the base polymer is, for example, 0.1 part by mass or more, preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8. It is more than a mass part. The blending amount is, for example, 5 parts by mass or less, preferably 2 parts by mass or less.
また、発色性化合物100質量部に対する金属錯体の配合量は、例えば、10質量部以上、好ましくは、20質量部以上、より好ましくは、40質量部以上である。同配合量は、例えば、100質量部以下、好ましくは、80質量部以下である。
The blending amount of the metal complex with respect to 100 parts by mass of the color-developing compound is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and more preferably 40 parts by mass or more. The blending amount is, for example, 100 parts by mass or less, preferably 80 parts by mass or less.
また、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。
Further, the adhesive composition may contain a cross-linking agent from the viewpoint of introducing a cross-linked structure into the base polymer. Examples of the cross-linking agent include an isocyanate cross-linking agent, an epoxy cross-linking agent, an oxazoline cross-linking agent, an aziridine cross-linking agent, a carbodiimide cross-linking agent, and a metal chelate cross-linking agent. The cross-linking agent may be used alone or in combination of two or more.
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。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,三井化学製)が挙げられる。
Examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalin diisocyanate, and triphenylmethane tri. Examples thereof include isocyanate and polymethylene polyphenyl isocyanate. Further, examples of the isocyanate cross-linking agent include derivatives of these isocyanates. Examples of isocyanate derivatives include isocyanurate-modified products and polyol-modified products. Examples of commercially available isocyanate cross-linking agents include coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh), coronate HL (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Tosoh), and coronate HX (hexa). Examples thereof include isocyanurate form of methylene diisocyanate (manufactured by Toso) and Takenate D110N (trimethylolpropane adduct form of xylylene diisocyanate, manufactured by Mitsui Kagaku).
エポキシ架橋剤としては、例えば、ビスフェノールA、エピクロルヒドリン型のエポキシ系樹脂、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 the epoxy cross-linking agent 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, and trimethylolpropane. Triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N', N'-tetraglycidyl-m-xylylenediamine, and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane Can be mentioned.
架橋剤としては、好ましくは、イソシアネート架橋剤、より好ましくは、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が挙げられる。
Examples of the cross-linking agent include an isocyanate cross-linking agent, and more preferably a trimethylolpropane adduct body of xylylene diisocyanate.
架橋剤の配合量は、粘着剤層10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、例えば、0.01質量部以上、好ましくは0.05質量部以上、より好ましくは、0.07質量部以上である。粘着剤層10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、例えば、10質量部以下であり、好ましくは、5質量部以下、より好ましくは、3質量部以下である。
From the viewpoint of ensuring the cohesive force of the pressure-sensitive adhesive layer 10, the blending amount of the cross-linking agent is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably, with respect to 100 parts by mass of the base polymer. Is 0.07 parts by mass or more. From the viewpoint of ensuring good tackiness in the pressure-sensitive adhesive layer 10, the blending amount of the cross-linking agent with respect to 100 parts by mass of the base polymer is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, and 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、金属系架橋触媒が挙げられる。金属系架橋触媒としては、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る。架橋触媒としては、好ましくは、ジラウリン酸ジブチルスズが挙げられる。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質量部以上である。また、同使用量は、例えば、1質量部以下である。
When a cross-linking 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 a metal-based cross-linking catalyst. Examples of the metal-based cross-linking catalyst include dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, and butyl tin oxide. The cross-linking catalyst is preferably dibutyltin dilaurate. The amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more with respect to 100 parts by mass of the base polymer. The amount used is, for example, 1 part by mass or less.
また、架橋剤として、イソシアネート架橋剤(具体的には、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)を配合し、また、架橋触媒として、金属系架橋触媒(具体的には、ジラウリン酸ジブチルスズ)を配合する場合には、好ましくは、粘着性組成物に、アセチルアセトンを配合する。
Further, an isocyanate cross-linking agent (specifically, a trimethylolpropane adduct of xylylene diisocyanate) is blended as a cross-linking agent, and a metal-based cross-linking catalyst (specifically, dibutyltin dilaurate) is used as a cross-linking catalyst. When blending, preferably, acetylacetone is blended in the adhesive composition.
アセチルアセトンを配合すると、アセチルアセトンがジラウリン酸ジブチルスズに配位する。これにより、粘着性組成物を、剥離フィルム(または基材20)上に塗布して塗膜を形成する前に、架橋反応の進行を抑制できる。また、詳しくは後述するが、塗膜形成時に加熱乾燥することで、アセチルアセトンを取り除き、架橋反応を進行させることができる。
When acetylacetone is added, acetylacetone coordinates with dibutyltin dilaurate. Thereby, the progress of the crosslinking reaction can be suppressed before the adhesive composition is applied onto the release film (or the base material 20) to form a coating film. Further, as will be described in detail later, acetylacetone can be removed and the crosslinking reaction can proceed by heating and drying at the time of forming the coating film.
アセチルアセトンの使用量は、架橋触媒100質量部に対して、例えば、100質量部以上、好ましくは、10000質量部以上である。また、同使用量は、例えば、50000質量部以下である。
The amount of acetylacetone used is, for example, 100 parts by mass or more, preferably 10,000 parts by mass or more, based on 100 parts by mass of the cross-linking catalyst. The amount used is, for example, 50,000 parts by mass or less.
また、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、重合性化合物およびその硬化物、光重合開始剤、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。
Further, the adhesive composition may contain other components, if necessary. Other components include, for example, polymerizable compounds and cured products thereof, photopolymerization initiators, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents. Can be mentioned.
重合性化合物としては、例えば、一つの重合性官能基(エチレン性不飽和二重結合)を有するモノマー(単官能モノマー)、および、複数の重合性官能基を有するモノマー(多官能モノマー)が挙げられる。単官能モノマーとしては、例えば、単官能(メタ)アクリレートが挙げられる。多官能モノマーとしては、例えば、多官能(メタ)アクリレートが挙げられる。
Examples of the polymerizable compound include a monomer having one polymerizable functional group (ethylenically unsaturated double bond) (monofunctional monomer) and a monomer having a plurality of polymerizable functional groups (polyfunctional monomer). Be done. Examples of the monofunctional monomer include monofunctional (meth) acrylate. Examples of the polyfunctional monomer include polyfunctional (meth) acrylate.
粘着性組成物が、重合性化合物を含む場合には、好ましくは、粘着性組成物は、さらに、光重合開始剤を含む。
When the adhesive composition contains a polymerizable compound, the adhesive composition preferably further contains a photopolymerization initiator.
粘着性組成物は、ベースポリマーと、酸との反応により発色する化合物と、酸発生剤と、金属錯体と、必要により配合される架橋剤と、必要により配合される架橋触媒と、必要により配合されるアセチルアセトンと、必要により配合される他の成分とを、上記した割合で配合することによって、得られる。
The tacky composition comprises a base polymer, a compound that develops color by reaction with an acid, an acid generator, a metal complex, a cross-linking agent to be blended if necessary, a cross-linking catalyst to be blended if necessary, and a cross-linking catalyst to be blended if necessary. It is obtained by blending the acetylacetone to be added and other components to be blended as necessary in the above-mentioned ratios.
粘着シートSは、例えば、上記の粘着性組成物を剥離フィルム(第1剥離フィルム)上に塗布して塗膜を形成した後、塗膜を乾燥させることによって、製造できる(図1では、仮想線で示す剥離フィルムL上に粘着シートSが配置されている)。
The pressure-sensitive adhesive sheet S can be produced, for example, by applying the above-mentioned adhesive composition on a release film (first release film) to form a coating film, and then drying the coating film (in FIG. 1, virtual). The adhesive sheet S is arranged on the release film L indicated by the line).
剥離フィルムとしては、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。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。剥離フィルムの厚みは、例えば、3μm以上である。また、同厚みは、例えば、200μm以下である。剥離フィルムの表面は、好ましくは、離型処理されている。
Examples of the release film include a flexible plastic film. Examples of the plastic film include polyethylene terephthalate film, polyethylene film, polypropylene film, and polyester film. The thickness of the release film is, for example, 3 μm or more. The same thickness is, for example, 200 μm or less. The surface of the release film is preferably mold-released.
粘着性組成物の塗布方法としては、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、および、ダイコートが挙げられる。塗膜の乾燥温度は、例えば、50℃以上である。また、同感想温度は、例えば、200℃以下である。乾燥時間は、例えば、5秒以上である。また、同乾燥時間は、例えば、20分以下である。
Examples of the method of applying the adhesive composition include roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, and lip coat. , And die coat. The drying temperature of the coating film is, for example, 50 ° C. or higher. The impression temperature is, for example, 200 ° C. or lower. The drying time is, for example, 5 seconds or more. The drying time is, for example, 20 minutes or less.
粘着性組成物が架橋剤を含む場合、上記の乾燥と同時に、または、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℃以上である。また、同エージング温度は、例えば、160℃以下である。エージング時間は、例えば、1分以上である。また、同エージング時間は、例えば、7日以下である。
When the adhesive composition contains a cross-linking agent, the cross-linking reaction proceeds at the same time as the above drying or by subsequent aging. The aging conditions are appropriately set depending on the type of the cross-linking agent. The aging temperature is, for example, 20 ° C. or higher. The aging temperature is, for example, 160 ° C. or lower. The aging time is, for example, 1 minute or more. The aging time is, for example, 7 days or less.
また、粘着性組成物がアセチルアセトンを含有する場合(換言すれば、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ている場合)には、乾燥時に、ジラウリン酸ジブチルスズに配位したアセチルアセトンが取り除かれる。これにより、架橋反応を進行させることができる。
Further, when the adhesive composition contains acetylacetone (in other words, when acetylacetone is coordinated to dibutyltin dilaurate), the acetylacetone coordinated to dibutyltin dilaurate is removed at the time of drying. This allows the cross-linking reaction to proceed.
また、エージングの前または後に、第1剥離フィルム上の粘着剤層10の上にさらに剥離フィルム(第2剥離フィルム)を積層してもよい。第2剥離フィルムは、例えば、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。第2剥離フィルムとしては、第1剥離フィルムに関して上記したのと同様のものを用いることができる。
Further, before or after aging, a release film (second release film) may be further laminated on the pressure-sensitive adhesive layer 10 on the first release film. The second release film is, for example, a flexible plastic film that has been subjected to a surface release treatment. As the second release film, the same film as described above for the first release film can be used.
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粘着シートSを製造できる。各剥離フィルムは、粘着シートSを使用する際に必要に応じて粘着シートSから剥がされる。
As described above, the pressure-sensitive adhesive sheet S whose adhesive surface is covered and protected by the release film can be manufactured. Each release film is peeled off from the pressure-sensitive adhesive sheet S as needed when using the pressure-sensitive adhesive sheet S.
粘着剤層10の厚みは、被着体に対する充分な粘着性を確保する観点から、例えば、10μm以上、好ましくは、15μm以上である。粘着シートSのハンドリング性の観点からは、粘着剤層10の厚みは、例えば、300μm以下、好ましくは、100μm以下、より好ましくは、50μm以下である。
The thickness of the pressure-sensitive adhesive layer 10 is, for example, 10 μm or more, preferably 15 μm or more, from the viewpoint of ensuring sufficient adhesiveness to the adherend. From the viewpoint of handleability of the pressure-sensitive adhesive sheet S, the thickness of the pressure-sensitive adhesive layer 10 is, for example, 300 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.
粘着剤層10のヘイズは、例えば、3%以下、好ましくは、2%以下、より好ましくは、1%以下である。このような構成は、粘着シートSを被着体に貼り合わせた後に粘着シートS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。粘着剤層10のヘイズは、JIS K7136(2000年)に準拠して、ヘイズメーターを使用して測定できる。ヘイズメーターとしては、例えば、日本電色工業社製の「NDH2000」、および、村上色彩技術研究所社製の「HM-150型」が挙げられる。
The haze of the pressure-sensitive adhesive layer 10 is, for example, 3% or less, preferably 2% or less, and more preferably 1% or less. Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend. The haze of the pressure-sensitive adhesive layer 10 can be measured using a haze meter in accordance with JIS K7136 (2000). Examples of the haze meter include "NDH2000" manufactured by Nippon Denshoku Kogyo Co., Ltd. and "HM-150 type" manufactured by Murakami Color Technology Research Institute.
粘着剤層10の波長400nm~700nmでの平均透過率(粘着剤層10に外部刺激を与える前の平均透過率)は、例えば、80%以上、好ましくは、85%以上、より好ましくは90%以上である。このような構成は、粘着シートSを被着体に貼り合わせた後に粘着シートS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。
The average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 nm to 700 nm (the average transmittance before applying an external stimulus to the pressure-sensitive adhesive layer 10) is, for example, 80% or more, preferably 85% or more, and more preferably 90%. That is all. Such a configuration is suitable for inspecting the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the pressure-sensitive adhesive sheet S is attached to the adherend.
また、粘着シートSにおいて、粘着剤層10を、ガラス板に対して貼着した後、23℃、剥離角度180°および剥離速度300mm/分の剥離条件での剥離試験において、ガラス板に対して示す粘着力は、例えば、1.0N/25mm以上、好ましくは、5.0N/25mm以上である。同粘着力は、好ましくは、50N/25mm以下、より好ましくは、40N/25mm以下、さらに好ましくは、20N/25mm以下である。
Further, in the pressure-sensitive adhesive sheet S, after the pressure-sensitive adhesive layer 10 is attached to the glass plate, in a peeling test under the peeling conditions of 23 ° C., a peeling angle of 180 ° and a peeling speed of 300 mm / min, the pressure-sensitive adhesive layer 10 is applied to the glass plate. The adhesive strength shown is, for example, 1.0 N / 25 mm or more, preferably 5.0 N / 25 mm or more. The adhesive strength is preferably 50 N / 25 mm or less, more preferably 40 N / 25 mm or less, and further preferably 20 N / 25 mm or less.
粘着剤層10が、周波数1Hzおよび昇温速度5℃/分の条件での動的粘弾性測定で示す、25℃でのせん断貯蔵弾性率は、好ましくは、0.1×105Pa以上、より好ましくは、0.5×105Pa以上、さらに好ましくは、1×105Pa以上である。せん断貯蔵弾性率は、好ましくは、10×105Pa以下、より好ましくは5×105Pa以下、さらに好ましくは、3×105Pa以下である。
The shear storage elastic modulus at 25 ° C., which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is preferably 0.1 × 105 Pa or more. More preferably, it is 0.5 × 10 5 Pa or more, and even more preferably 1 × 10 5 Pa or more. The shear storage elastic modulus is preferably 10 × 10 5 Pa or less, more preferably 5 × 10 5 Pa or less, and further preferably 3 × 10 5 Pa or less.
第2の実施形態では、粘着剤層10のポリマー成分(ベースポリマー)は、スフィア型のミクロ相分離構造を有する。スフィア型のミクロ相分離構造は、具体的には海島構造を有し、マトリクス(海部)中に球状の分散相(島部)が分散している。粘着剤層10において、分散相は発色性化合物と相溶性を有し、マトリクスは発色性化合物と相溶性を有さない。このような粘着シートSは、粘着剤層10に変色部分が形成された後(即ち、外部刺激によって発色性化合物が発色した後)に島部に発色性化合物が留まりやすいので、粘着剤層10内での発色性化合物の移動(拡散など)を抑制するのに適する。発色性化合物の移動の抑制により、変色部分の劣化(滲み、退色、色味の不均一化など)が抑制される。
In the second embodiment, the polymer component (base polymer) of the pressure-sensitive adhesive layer 10 has a sphere-type microphase-separated structure. The sphere-type microphase-separated structure specifically has a sea-island structure, in which spherical dispersed phases (islands) are dispersed in a matrix (sea). In the pressure-sensitive adhesive layer 10, the dispersed phase is compatible with the color-developing compound, and the matrix is not compatible with the color-developing compound. In such a pressure-sensitive adhesive sheet S, the color-developing compound tends to stay on the islands after the discolored portion is formed on the pressure-sensitive adhesive layer 10 (that is, after the color-developing compound is developed by an external stimulus). Suitable for suppressing the movement (diffusion, etc.) of color-developing compounds within. By suppressing the movement of the color-developing compound, deterioration of the discolored portion (bleeding, fading, non-uniformity of color, etc.) is suppressed.
ポリマー成分は、例えば、マトリクスを形成するソフトセグメントと、分散相を形成するハードセグメントとを分子内に有するポリマー(第1ポリマー)を含む。第1ポリマーとしては、例えば、ソフトセグメントとしての第1重合体ブロックと、ハードセグメントとしての第2重合体ブロックとを有するブロックポリマーが挙げられる。ブロックポリマーは、モノマー組成の異なる複数の第1重合体ブロックを有してもよいし、モノマー組成の異なる複数の第2重合体ブロックを有してもよい(この場合、ブロックポリマーは、モノマー組成に基づくブロック種類数が3以上であるマルチブロック共重合体である)。第1ポリマーとしては、ソフトセグメントとしてのポリマー主鎖と、ハードセグメントとしてのポリマー側鎖とを有するグラフトポリマーも挙げられる。グラフトポリマーは、モノマー組成の異なる複数のポリマー側鎖を有してもよいし、モノマー組成の異なる複数の重合体ブロックをポリマー主鎖内に有してもよい。ポリマー成分は、一種類の第1ポリマーを含んでもよいし、複数種類の第1ポリマーを含んでもよい。
The polymer component includes, for example, a polymer (first polymer) having a soft segment forming a matrix and a hard segment forming a dispersed phase in the molecule. Examples of the first polymer include a block polymer having a first polymer block as a soft segment and a second polymer block as a hard segment. The block polymer may have a plurality of first polymer blocks having different monomer compositions, or may have a plurality of second polymer blocks having different monomer compositions (in this case, the block polymer may have a plurality of second polymer blocks having different monomer compositions. It is a multi-block copolymer in which the number of block types based on the above is 3 or more). Examples of the first polymer include a graft polymer having a polymer main chain as a soft segment and a polymer side chain as a hard segment. The graft polymer may have a plurality of polymer side chains having different monomer compositions, or may have a plurality of polymer blocks having different monomer compositions in the polymer main chain. The polymer component may contain one kind of first polymer or may contain a plurality of kinds of first polymers.
ポリマー成分は、第1ポリマー以外のポリマー(第2ポリマー)を含んでもよい。例えば、ポリマー成分は、第1ポリマーのソフトセグメントと共にマトリクスを形成する第2ポリマーを含んでもよいし、第1ポリマーのハードセグメントと共に分散相を形成する第2ポリマーを含んでもよい。ポリマー成分は、一種類の第2ポリマーを含んでもよいし、複数種類の第2ポリマーを含んでもよい。
The polymer component may contain a polymer other than the first polymer (second polymer). For example, the polymer component may include a second polymer that forms a matrix with the soft segments of the first polymer, or may include a second polymer that forms a dispersed phase with the hard segments of the first polymer. The polymer component may contain one kind of second polymer or a plurality of kinds of second polymers.
本実施形態では、島部を形成するハードセグメントは、実施例に関して後述する相溶性判定試験によって着色剤が相溶性を有すると判定されるモノマー溶液(25℃でモノマー溶液を用意できない場合はポリマー溶液)と同一のモノマー組成を80質量%以上含有するセグメントである。このようなハードセグメントから形成される島部に対し、発色性化合物は相溶性を有する。このハードセグメントのガラス転移温度は、好ましくは0℃以上、より好ましくは30℃以上、更に好ましくは50℃以上である。
In the present embodiment, the hard segment forming the island portion is a monomer solution (when a monomer solution cannot be prepared at 25 ° C., a polymer solution) in which the colorant is determined to have compatibility by the compatibility determination test described later with respect to Examples. ), Which is a segment containing 80% by mass or more of the same monomer composition. The color-developing compound has compatibility with the islands formed from such hard segments. The glass transition temperature of this hard segment is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 50 ° C. or higher.
本実施形態では、海部を形成するソフトセグメントは、実施例に関して後述する相溶性判定試験によって着色剤が相溶性を有さないと判定されるモノマー溶液(25℃でモノマー溶液を用意できない場合はmポリマー溶液)と同一のモノマー組成を80質量%以上含有するセグメントである。このようなソフトセグメントから形成される第2相に対し、発色性化合物は相溶性を有さない。このソフトセグメントのガラス転移温度は、好ましくは0℃以下、より好ましくは0℃未満、更に好ましくは-30℃以下、特に好ましくは-50℃以下である。粘着剤層10の粘着力確保の観点から、ポリマー成分におけるソフトセグメントの質量割合は、好ましくはハードセグメントの質量割合より大きい。
In the present embodiment, the soft segment forming the sea portion is a monomer solution in which the colorant is determined to be incompatible by the compatibility determination test described later with respect to the examples (when the monomer solution cannot be prepared at 25 ° C., m). It is a segment containing 80% by mass or more of the same monomer composition as the polymer solution). The color-developing compound has no compatibility with the second phase formed from such soft segments. The glass transition temperature of this soft segment is preferably 0 ° C. or lower, more preferably less than 0 ° C., still more preferably −30 ° C. or lower, and particularly preferably −50 ° C. or lower. From the viewpoint of ensuring the adhesive strength of the pressure-sensitive adhesive layer 10, the mass ratio of the soft segment in the polymer component is preferably larger than the mass ratio of the hard segment.
本実施形態におけるベースポリマーに含まれるポリマーとしては、海島構造の形成のしやすさの観点から、好ましくは、ゴムポリマーおよび/またはアクリルポリマーが用いられる。
As the polymer contained in the base polymer in the present embodiment, a rubber polymer and / or an acrylic polymer is preferably used from the viewpoint of ease of forming a sea-island structure.
ゴムポリマーとしては、好ましくは、スチレン共重合体が用いられる。スチレン共重合体としては、例えば、スチレン-イソプレン-スチレン共重合体(SIS)、SISの水素添加物、スチレン-エチレン-ブチレン共重合体(SEB)、スチレン-ブタジエン-スチレン共重合体(SBS)、SBSの水素添加物、スチレン-イソブチレン-スチレン共重合体(SIBS)、および、スチレン-ブタジエン-スチレン-ブタジエン(SBSB)が挙げられる。これらスチレン共重合体において、スチレンはハードセグメントを形成し、スチレンと共重合している不飽和炭化水素はソフトセグメントを形成する。ゴムポリマーは、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。
As the rubber polymer, a styrene copolymer is preferably used. Examples of the styrene copolymer include styrene-isoprene-styrene copolymer (SIS), SIS hydrogenated additive, styrene-ethylene-butylene copolymer (SEB), and styrene-butadiene-styrene copolymer (SBS). , SBS hydrogenated additives, styrene-isobutylene-styrene copolymer (SIBS), and styrene-butadiene-styrene-butadiene (SBSB). In these styrene copolymers, styrene forms a hard segment and unsaturated hydrocarbons copolymerizing with styrene form a soft segment. The rubber polymer may be used alone or in combination of two or more.
スチレン共重合体におけるスチレン含有割合は、好ましくは5質量以上、より好ましくは7質量%以上、更に好ましくは10質量%以上である。スチレン共重合体におけるスチレン含有割合は、好ましくは40質量%以下、より好ましくは30質量%以下、更に好ましくは20質量%以下である。
The styrene content in the styrene copolymer is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more. The styrene content in the styrene copolymer is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
第2の実施形態におけるアクリルポリマーの(メタ)アクリル酸アルキルエステルおよび共重合性モノマーとしては、第1の実施形態における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および共重合性モノマーを用いることができる。ハードセグメントを形成する(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1~5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、アクリル酸メチル、メタクリル酸メチル、およびアクリル酸n-ブチル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。ソフトセグメントを形成する(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7~20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、アクリル酸ドデシル、およびアクリル酸オクタデシル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。ハードセグメントを形成する共重合性モノマーとしては、好ましくは芳香族ビニル化合物が用いられ、より好ましくはスチレンが用いられる。
As the (meth) acrylic acid alkyl ester and the copolymerizable monomer of the acrylic polymer in the second embodiment, the above-mentioned (meth) acrylic acid alkyl ester and the copolymerizable monomer for the acrylic polymer in the first embodiment are used. Can be done. As the (meth) acrylic acid alkyl ester forming a hard segment, an acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms is preferably used, and more preferably, methyl acrylate, methyl methacrylate, and acrylic. At least one selected from the group consisting of n-butyl acid acid is used. As the (meth) acrylic acid alkyl ester forming a soft segment, an acrylic acid alkyl ester having an alkyl group having 7 to 20 carbon atoms is preferably used, and more preferably 2-ethylhexyl acrylate, dodecyl acrylate, and the like. And at least one selected from the group consisting of octadecyl acrylate is used. As the copolymerizable monomer forming the hard segment, an aromatic vinyl compound is preferably used, and styrene is more preferably used.
ポリマー成分は、好ましくは、第1ポリマーとしてスチレン-イソプレン-スチレン共重合体を含み、第2ポリマーとしてスチレン・アクリル酸n-ブチル共重合体を含む。スチレン-イソプレン-スチレン共重合体100質量部に対するスチレン・アクリル酸n-ブチル共重合体の量は、好ましくは1質量部以上、より好ましくは3質量部以上、更に好ましくは5質量部以上であり、また、好ましくは50質量部以下、より好ましくは40質量部以下、更に好ましくは30質量部以下である。
The polymer component preferably contains a styrene-isoprene-styrene copolymer as the first polymer and a styrene-n-butyl acrylate copolymer as the second polymer. The amount of the styrene-n-butyl acrylate copolymer with respect to 100 parts by mass of the styrene-isoprene-styrene copolymer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less.
第2の実施形態の粘着シートSの粘着剤層10は、第1の実施形態に関して上述した金属錯体を含有してもよいし、含有しなくてもよい。
The pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S of the second embodiment may or may not contain the metal complex described above with respect to the first embodiment.
第1および第2の実施形態の各粘着シートSは、図2に示すように、粘着剤層10に加えて基材20を備える基材付き片面粘着シートであってもよい。この場合、粘着シートSは、具体的には、粘着剤層10と、その厚み方向Dの一方面側に配置される基材20とを備える。好ましくは、基材20は、粘着剤層10の厚み方向Dの一方面に接触する。
As shown in FIG. 2, each of the pressure-sensitive adhesive sheets S of the first and second embodiments may be a single-sided pressure-sensitive adhesive sheet with a base material provided with a base material 20 in addition to the pressure-sensitive adhesive layer 10. In this case, the pressure-sensitive adhesive sheet S specifically includes a pressure-sensitive adhesive layer 10 and a base material 20 arranged on one side in the thickness direction D thereof. Preferably, the base material 20 comes into contact with one surface of the pressure-sensitive adhesive layer 10 in the thickness direction D.
基材20は、透明な支持体として機能する要素である。基材20は、例えば、可撓性を有するプラスチックフィルムである。プラスチックフィルムの構成材料としては、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、ポリプロピレン、ポリ-1-ブテン、ポリ-4-メチル-1-ペンテン、エチレン・プロピレン共重合体、エチレン・1-ブテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・エチルアクリレート共重合体、および、エチレン・ビニルアルコール共重合体が挙げられる。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。基材20において、その透明性と機械的強度とを両立させる観点からは、基材20のプラスチック材料は、好ましくは、ポリエステル、より好ましくは、ポリエチレンテレフタレートである。
The base material 20 is an element that functions as a transparent support. The base material 20 is, for example, a flexible plastic film. Examples of the constituent material of the plastic film include polyolefin, polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, cellulose, polystyrene, and polycarbonate. Examples of the polyolefin include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, and the like. Examples thereof include an ethylene / ethyl acrylate copolymer and an ethylene / vinyl alcohol copolymer. Examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. Examples of the polyamide include polyamide 6, polyamide 6, 6 and partially aromatic polyamide. From the viewpoint of achieving both transparency and mechanical strength of the base material 20, the plastic material of the base material 20 is preferably polyester, more preferably polyethylene terephthalate.
基材20は、透明性を有する。基材20のヘイズは、例えば、3%以下、好ましくは、2%以下、より好ましくは1%以下である。基材20のヘイズは、JIS K7136(2000年)に準拠して、ヘイズメーターを使用して測定できる。
The base material 20 has transparency. The haze of the base material 20 is, for example, 3% or less, preferably 2% or less, and more preferably 1% or less. The haze of the base material 20 can be measured using a haze meter in accordance with JIS K7136 (2000).
基材20における粘着剤層10側の表面は、粘着剤層10との密着性を高めるための物理的処理、化学的処理、または、下塗り処理が施されていてもよい。物理的処理としては、例えば、コロナ処理およびプラズマ処理が挙げられる。化学的処理としては、例えば、酸処理およびアルカリ処理が挙げられる。
The surface of the base material 20 on the pressure-sensitive adhesive layer 10 side may be subjected to a physical treatment, a chemical treatment, or an undercoat treatment for enhancing the adhesion to the pressure-sensitive adhesive layer 10. Physical treatments include, for example, corona treatment and plasma treatment. Examples of the chemical treatment include acid treatment and alkali treatment.
基材20の厚みは、基材20が支持体として機能するための強度を確保する観点からは、例えば、5μm以上、好ましくは、10μm以上、より好ましくは、20μm以上である。また、粘着シートSにおいて適度な可撓性を実現する観点からは、基材20の厚みは、例えば、200μm以下、好ましくは、150μm以下、より好ましくは、100μm以下である。
The thickness of the base material 20 is, for example, 5 μm or more, preferably 10 μm or more, more preferably 20 μm or more, from the viewpoint of ensuring the strength for the base material 20 to function as a support. Further, from the viewpoint of realizing appropriate flexibility in the pressure-sensitive adhesive sheet S, the thickness of the base material 20 is, for example, 200 μm or less, preferably 150 μm or less, and more preferably 100 μm or less.
図2に示す粘着シートSは、例えば、第1剥離フィルムの代わりに基材20を用いること以外は上記の製造方法と同様にして、製造できる。
The pressure-sensitive adhesive sheet S shown in FIG. 2 can be manufactured in the same manner as the above-mentioned manufacturing method except that the base material 20 is used instead of the first release film, for example.
図3Aから図3Cは、第1および第2の実施形態の各粘着シートSの使用方法の一例を表す。本方法は、用意工程と、接合工程と、変色部分形成工程とを備える。
3A to 3C show an example of how to use each of the adhesive sheets S according to the first and second embodiments. This method includes a preparation step, a joining step, and a discolored portion forming step.
まず、用意工程では、図3Aに示すように、粘着シートSと、第1部材31と、第2部材32とを用意する。第1部材31は、例えば、ディスプレイパネルである。第1部材31は、他の電子デバイス、および、光学デバイスであってもよい。第2部材32は、例えば透明基材である。透明基材としては、透明プラスチック基材および透明ガラス基材が挙げられる。
First, in the preparation process, as shown in FIG. 3A, the adhesive sheet S, the first member 31, and the second member 32 are prepared. The first member 31 is, for example, a display panel. The first member 31 may be another electronic device or an optical device. The second member 32 is, for example, a transparent base material. Examples of the transparent base material include a transparent plastic base material and a transparent glass base material.
次に、接合工程では、図3Bに示すように、粘着シートSを介して第1部材31および第2部材32を接合する。これにより、積層体Wが得られる。積層体Wにおいて、粘着シートSは、第1部材31の厚み方向一方面に接触するように配置され、第2部材32は、その粘着シートSの厚み方向一方面に接触するように配置される。
Next, in the joining step, as shown in FIG. 3B, the first member 31 and the second member 32 are joined via the adhesive sheet S. As a result, the laminated body W is obtained. In the laminated body W, the adhesive sheet S is arranged so as to be in contact with one surface in the thickness direction of the first member 31, and the second member 32 is arranged so as to be in contact with one surface in the thickness direction of the adhesive sheet S. ..
接合工程の後、必要に応じて、部材31,32と粘着シートSとの間における異物および気泡の有無を検査する。
After the joining step, if necessary, inspect for foreign matter and air bubbles between the members 31, 32 and the pressure-sensitive adhesive sheet S.
次に、変色工程では、図3Cに示すように、積層体Wにおける粘着剤層10に外部刺激を与えて、粘着剤層10において変色部分11を形成する。具体的には、透明な第2部材32の側から、粘着剤層10における所定領域をマスクするためのマスクパターン(図示略)を介して、粘着剤層10に対して外部刺激としての活性エネルギー線を照射する。これにより、粘着剤層10におけるマスクパターンでマスクされていない部分を変色させる。
Next, in the discoloration step, as shown in FIG. 3C, an external stimulus is applied to the pressure-sensitive adhesive layer 10 in the laminated body W to form the discolored portion 11 in the pressure-sensitive adhesive layer 10. Specifically, the active energy as an external stimulus to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32 via a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10. Irradiate the line. As a result, the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored.
本工程では、粘着剤層10において、活性エネルギー線照射を受けた部分で、光酸発生剤から酸が発生し、この酸との反応によって発色性化合物が発色する。これによって、粘着剤層10に変色部分11が形成される。
In this step, an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays, and the color-developing compound is developed by the reaction with this acid. As a result, the discolored portion 11 is formed on the pressure-sensitive adhesive layer 10.
粘着シートSは、粘着剤層10が、上記のように、発色性化合物を含有する。そのため、粘着シートSを被着体(本実施形態では部材31,32)に貼り合わせた後、粘着剤層10における変色予定部分に対する外部刺激の付与により、粘着剤層10を局所的に変色させることができる。被着体に貼り合わせた後に粘着剤層10に変色部分11を形成できる粘着シートSでは、貼り合わせ後であって粘着剤層10の変色部分11形成前に、粘着シートSと被着体との間における異物および気泡の有無を検査できる。
In the pressure-sensitive adhesive sheet S, the pressure-sensitive adhesive layer 10 contains a color-developing compound as described above. Therefore, after the pressure-sensitive adhesive sheet S is attached to the adherend ( members 31, 32 in the present embodiment), the pressure-sensitive adhesive layer 10 is locally discolored by applying an external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer 10. be able to. In the pressure-sensitive adhesive sheet S capable of forming the discolored portion 11 on the pressure-sensitive adhesive layer 10 after being bonded to the adherend, the pressure-sensitive adhesive sheet S and the adherend are formed after the bonding and before the discolored portion 11 of the pressure-sensitive adhesive layer 10 is formed. The presence or absence of foreign matter and air bubbles can be inspected between.
また、粘着シートSでは、粘着剤層10の第1変色幅W1および第2変色幅W2が上記式(1)を満たす。このような粘着シートSは、外部刺激付与によって粘着剤層10に変色部分が形成された後に当該変色部分の劣化を抑制するに適し、従って、任意の箇所に、意匠性、遮蔽性、および、反射防止性を付与するのに適する。
Further, in the pressure-sensitive adhesive sheet S, the first color change width W1 and the second color change width W2 of the pressure-sensitive adhesive layer 10 satisfy the above formula (1). Such a pressure-sensitive adhesive sheet S is suitable for suppressing deterioration of the discolored portion after the discolored portion is formed on the pressure-sensitive adhesive layer 10 by applying an external stimulus. Suitable for imparting antireflection properties.
また、粘着シートSの使用方法の一例として、粘着シートSを、ディスプレイパネルにおける画素パネルの光出射側(画像表示側)に配置する場合がある。詳しくは、第1部材31がディスプレイパネルである場合、ディスプレイパネルが備える画素パネル上に形成された、金属配線としての導体層に対応する(即ち対面する)パターン形状で変色部分11を設ける。これにより、導体層での外光反射を抑制できる。
Further, as an example of how to use the adhesive sheet S, the adhesive sheet S may be arranged on the light emitting side (image display side) of the pixel panel in the display panel. Specifically, when the first member 31 is a display panel, the discolored portion 11 is provided with a pattern shape corresponding to (that is, facing) the conductor layer as the metal wiring formed on the pixel panel included in the display panel. Thereby, the reflection of external light in the conductor layer can be suppressed.
導体層の幅は、例えば10μm以上である。導体層の幅は、例えば300μm以下である。また、導体層は、好ましくは、ファインピッチで形成されている。各導体層同士の間隔は、例えば、10μm以上である。また、同間隔は、例えば、100000μm以下である。
The width of the conductor layer is, for example, 10 μm or more. The width of the conductor layer is, for example, 300 μm or less. Further, the conductor layer is preferably formed at a fine pitch. The distance between the conductor layers is, for example, 10 μm or more. The same interval is, for example, 100,000 μm or less.
変色部分11の線幅は、上記した導体層の幅と対応している。具体的には、変色部分11の線幅は、例えば10μm以上である。また、同線幅は、例えば300μm以下である。また、各変色部分11の間隔は、例えば10μm以上である。また、同間隔は、例えば100000μm以下である。
The line width of the discolored portion 11 corresponds to the width of the conductor layer described above. Specifically, the line width of the discolored portion 11 is, for example, 10 μm or more. The line width is, for example, 300 μm or less. Further, the interval between the discolored portions 11 is, for example, 10 μm or more. The same interval is, for example, 100,000 μm or less.
この粘着シートSでは、第1変色幅W1および第2変色幅W2が、上記式(1)を満たすため、遮蔽性、および、反射防止性を向上できる。その結果、金属配線での外光反射を抑制しつつ、金属配線が設けられたディスプレイパネルの視認性を向上できる。
In this adhesive sheet S, since the first discoloration width W1 and the second discoloration width W2 satisfy the above formula (1), the shielding property and the antireflection property can be improved. As a result, it is possible to improve the visibility of the display panel provided with the metal wiring while suppressing the reflection of external light on the metal wiring.
なお、本発明の特徴は、上記したW2/W1を調整し、好ましくは、W3/W1を調整することにある。すなわち、本発明の可変色フィルムの利用形態として、線状の着色部分(発色部分)を形成することに限定されず、各種形状の着色部分を形成することができる。より具体的には、形成可能な着色部分としては、線状、点状、矩形状、円形状、楕円形状、不定形状などを例示できる。
The feature of the present invention is to adjust W2 / W1 described above, preferably to adjust W3 / W1. That is, the mode of use of the variable color film of the present invention is not limited to forming a linear colored portion (color-developing portion), and various colored portions can be formed. More specifically, examples of the colored portion that can be formed include a linear shape, a point shape, a rectangular shape, a circular shape, an elliptical shape, and an indefinite shape.
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、上記の「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 blending amount (content), the physical property value, the parameter, etc. described below are the blending amounts corresponding to them described in the above-mentioned "form for carrying out the invention" (forms for carrying out the invention). It can be replaced with an upper limit (numerical value defined as "less than or equal to" or "less than") or a lower limit (numerical value defined as "greater than or equal to" or "greater than or equal to") such as content), physical property value, and parameter.
製造例1(ベースポリマーの調製)
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、アクリルポリマーを含有するポリマー溶液を得た。このポリマー溶液中のアクリルポリマーの重量平均分子量(Mw)は120万であった。 Production Example 1 (Preparation of base polymer)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2-acrylic acid. 13 parts by mass of hydroxyethyl (HEA), 15 parts by mass of N-vinyl-2-pyrrolidone (NVP), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator. The mixture containing 233 parts by mass of ethyl acetate as a solvent was stirred at 60 ° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). As a result, a polymer solution containing an acrylic polymer was obtained. The weight average molecular weight (Mw) of the acrylic polymer in this 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、アクリルポリマーを含有するポリマー溶液を得た。このポリマー溶液中のアクリルポリマーの重量平均分子量(Mw)は120万であった。 Production Example 1 (Preparation of base polymer)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, 63 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of methyl methacrylate (MMA), and 2-acrylic acid. 13 parts by mass of hydroxyethyl (HEA), 15 parts by mass of N-vinyl-2-pyrrolidone (NVP), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator. The mixture containing 233 parts by mass of ethyl acetate as a solvent was stirred at 60 ° C. for 7 hours under a nitrogen atmosphere (polymerization reaction). As a result, a polymer solution containing an acrylic polymer was obtained. The weight average molecular weight (Mw) of the acrylic polymer in this polymer solution was 1.2 million.
〔実施例1〕
〈粘着性組成物の調製〉
製造例1のアクリルポリマーを含有する上記のポリマー溶液に、アクリルポリマー(ベースポリマー)100質量部あたり、下記成分を均一に混合して粘着性組成物を調製した。 [Example 1]
<Preparation of adhesive composition>
The following components were uniformly mixed with the above polymer solution containing the acrylic polymer of Production Example 1 per 100 parts by mass of the acrylic polymer (base polymer) to prepare an adhesive composition.
〈粘着性組成物の調製〉
製造例1のアクリルポリマーを含有する上記のポリマー溶液に、アクリルポリマー(ベースポリマー)100質量部あたり、下記成分を均一に混合して粘着性組成物を調製した。 [Example 1]
<Preparation of adhesive composition>
The following components were uniformly mixed with the above polymer solution containing the acrylic polymer of Production Example 1 per 100 parts by mass of the acrylic polymer (base polymer) to prepare an adhesive composition.
酸との反応により発色する化合物:ロイコ系色素(商品名「S-205」,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],山田化学工業社製)2.00質量部
酸発生剤:光酸発生剤(商品名「CPI-310B」,スルホニウムと(C6F5)4B-とのオニウム塩,サンアプロ社製)7.00質量部
金属錯体:サリチル酸亜鉛三水和物(富士フイルム和光純薬社製)0.38質量部
架橋剤:「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の75%酢酸エチル溶液,三井化学製)0.25質量部(固形分換算量)架橋触媒:ジラウリン酸ジブチルスズ(1質量%酢酸エチル溶液)0.01質量部(固形分換算量)
アセチルアセトン:3.00質量部 Compound that develops color by reaction with acid: Leuco dye (trade name "S-205", 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3, 9'-[9H] xanthene], manufactured by Yamada Chemical Industry Co., Ltd.) 2.00 parts by mass Acid generator: Photoacid generator (trade name "CPI-310B", sulfonium and ( C6 F 5 ) 4 B- Onium salt, manufactured by San-Apro Co., Ltd.) 7.00 parts by mass Metal complex: Zinc salicylate trihydrate (manufactured by Fujifilm Wako Junyaku Co., Ltd.) 0.38 parts by mass Cross-linking agent: "Takenate D110N" (Trimethylol propane of xylylene diisocyanate) Adduct 75% ethyl acetate solution, manufactured by Mitsui Kagaku) 0.25 parts by mass (solid content equivalent) Cross-linking catalyst: dibutyltin dilaurate (1 mass% ethyl acetate solution) 0.01 parts by mass (solid content equivalent)
Acetylacetone: 3.00 parts by mass
酸発生剤:光酸発生剤(商品名「CPI-310B」,スルホニウムと(C6F5)4B-とのオニウム塩,サンアプロ社製)7.00質量部
金属錯体:サリチル酸亜鉛三水和物(富士フイルム和光純薬社製)0.38質量部
架橋剤:「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の75%酢酸エチル溶液,三井化学製)0.25質量部(固形分換算量)架橋触媒:ジラウリン酸ジブチルスズ(1質量%酢酸エチル溶液)0.01質量部(固形分換算量)
アセチルアセトン:3.00質量部 Compound that develops color by reaction with acid: Leuco dye (trade name "S-205", 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3, 9'-[9H] xanthene], manufactured by Yamada Chemical Industry Co., Ltd.) 2.00 parts by mass Acid generator: Photoacid generator (trade name "CPI-310B", sulfonium and ( C6 F 5 ) 4 B- Onium salt, manufactured by San-Apro Co., Ltd.) 7.00 parts by mass Metal complex: Zinc salicylate trihydrate (manufactured by Fujifilm Wako Junyaku Co., Ltd.) 0.38 parts by mass Cross-linking agent: "Takenate D110N" (Trimethylol propane of xylylene diisocyanate) Adduct 75% ethyl acetate solution, manufactured by Mitsui Kagaku) 0.25 parts by mass (solid content equivalent) Cross-linking catalyst: dibutyltin dilaurate (1 mass% ethyl acetate solution) 0.01 parts by mass (solid content equivalent)
Acetylacetone: 3.00 parts by mass
〈粘着剤層の形成〉
片面が剥離面となっている剥離フィルム(商品名「MRF#38」,ポリエステルフィルム,厚み38μm,三菱樹脂社製)に粘着性組成物を塗布して、塗膜を形成した。次に、この塗膜を、132℃で3分間乾燥させて、厚み25μmの粘着剤層を形成した。この粘着剤層に、片面が剥離面となっている剥離フィルム(商品名「MRF#38」,ポリエステルフィルム,厚み38μm,三菱樹脂社製)を貼り合わせた。その後、60℃で24時間、エージング処理し、粘着剤層において、架橋反応を進行させた。 <Formation of adhesive layer>
The adhesive composition was applied to a release film (trade name "MRF # 38", polyester film, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) having one side as a release surface to form a coating film. Next, this coating film was dried at 132 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 μm. A release film (trade name "MRF # 38", polyester film, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) having a release surface on one side was attached to this pressure-sensitive adhesive layer. Then, it was aged at 60 ° C. for 24 hours, and the crosslinking reaction was allowed to proceed in the pressure-sensitive adhesive layer.
片面が剥離面となっている剥離フィルム(商品名「MRF#38」,ポリエステルフィルム,厚み38μm,三菱樹脂社製)に粘着性組成物を塗布して、塗膜を形成した。次に、この塗膜を、132℃で3分間乾燥させて、厚み25μmの粘着剤層を形成した。この粘着剤層に、片面が剥離面となっている剥離フィルム(商品名「MRF#38」,ポリエステルフィルム,厚み38μm,三菱樹脂社製)を貼り合わせた。その後、60℃で24時間、エージング処理し、粘着剤層において、架橋反応を進行させた。 <Formation of adhesive layer>
The adhesive composition was applied to a release film (trade name "MRF # 38", polyester film, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) having one side as a release surface to form a coating film. Next, this coating film was dried at 132 ° C. for 3 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 μm. A release film (trade name "MRF # 38", polyester film, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) having a release surface on one side was attached to this pressure-sensitive adhesive layer. Then, it was aged at 60 ° C. for 24 hours, and the crosslinking reaction was allowed to proceed in the pressure-sensitive adhesive layer.
以上のようにして、実施例1の粘着シートを作製した。実施例1の粘着シートにおける粘着剤層の組成について、単位を質量部として表1に示す(後記の実施例1~3および比較例1についても同様である)。
As described above, the adhesive sheet of Example 1 was produced. The composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 1 is shown in Table 1 in units of mass (the same applies to Examples 1 to 3 and Comparative Example 1 described later).
〔実施例2,3および比較例1〕
実施例1の粘着シートと同様にして、実施例2,3および比較例1の各粘着シートを作製した。ただし、粘着性組成物の組成を表1に示す量に変更した。 [Examples 2 and 3 and Comparative Example 1]
Each of the pressure-sensitive adhesive sheets of Examples 2 and 3 and Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1. However, the composition of the adhesive composition was changed to the amount shown in Table 1.
実施例1の粘着シートと同様にして、実施例2,3および比較例1の各粘着シートを作製した。ただし、粘着性組成物の組成を表1に示す量に変更した。 [Examples 2 and 3 and Comparative Example 1]
Each of the pressure-sensitive adhesive sheets of Examples 2 and 3 and Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1. However, the composition of the adhesive composition was changed to the amount shown in Table 1.
〔実施例4〕
〈粘着性組成物の調製〉
第1ポリマー(ベースポリマー)としてのスチレン-イソプレン-スチレンブロック共重合体(商品名「Quintac 3520」,スチレン含有割合15質量%,日本ゼオン社製)100質量部あたり、下記成分を均一に混合して粘着性組成物を調製した。 [Example 4]
<Preparation of adhesive composition>
The following components are uniformly mixed per 100 parts by mass of a styrene-isoprene-styrene block copolymer (trade name "Quintac 3520", styrene content ratio 15% by mass, manufactured by Nippon Zeon Corporation) as the first polymer (base polymer). The adhesive composition was prepared.
〈粘着性組成物の調製〉
第1ポリマー(ベースポリマー)としてのスチレン-イソプレン-スチレンブロック共重合体(商品名「Quintac 3520」,スチレン含有割合15質量%,日本ゼオン社製)100質量部あたり、下記成分を均一に混合して粘着性組成物を調製した。 [Example 4]
<Preparation of adhesive composition>
The following components are uniformly mixed per 100 parts by mass of a styrene-isoprene-styrene block copolymer (trade name "Quintac 3520", styrene content ratio 15% by mass, manufactured by Nippon Zeon Corporation) as the first polymer (base polymer). The adhesive composition was prepared.
第2ポリマー:スチレン-アクリルブロック共重合体(商品名「FBP-001」,藤倉化成社製)5質量部
酸との反応により発色する化合物(発色性化合物):ロイコ系色素、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](商品名「S-205」,山田化学工業社製)2.00質量部
酸発生剤:光酸発生剤(商品名「CPI-310B」,スルホニウムと(C6F5)4B-とのオニウム塩,サンアプロ社製)7.00質量部
架橋剤: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(商品名「テトラッド-C」,三菱ガス化学社製)0.25質量部 Second polymer: styrene-acrylic block copolymer (trade name "FBP-001", manufactured by Fujikura Kasei Co., Ltd.) 5 parts by mass A compound that develops color by reaction with an acid (color-developing compound): Leuco-based dye, 2'-anilino -6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] (trade name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) 2. 00 parts by mass acid generator: Photoacid generator (trade name "CPI-310B", onium salt of sulfonium and (C 6 F 5 ) 4 B-, manufactured by San-Apro) 7.00 parts by mass cross-linking agent: 1, 3-Bis (N, N-diglycidylaminomethyl) cyclohexane (trade name "Tetrad-C", manufactured by Mitsubishi Gas Chemicals, Inc.) 0.25 parts by mass
酸との反応により発色する化合物(発色性化合物):ロイコ系色素、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](商品名「S-205」,山田化学工業社製)2.00質量部
酸発生剤:光酸発生剤(商品名「CPI-310B」,スルホニウムと(C6F5)4B-とのオニウム塩,サンアプロ社製)7.00質量部
架橋剤: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(商品名「テトラッド-C」,三菱ガス化学社製)0.25質量部 Second polymer: styrene-acrylic block copolymer (trade name "FBP-001", manufactured by Fujikura Kasei Co., Ltd.) 5 parts by mass A compound that develops color by reaction with an acid (color-developing compound): Leuco-based dye, 2'-anilino -6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene] (trade name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) 2. 00 parts by mass acid generator: Photoacid generator (trade name "CPI-310B", onium salt of sulfonium and (C 6 F 5 ) 4 B-, manufactured by San-Apro) 7.00 parts by mass cross-linking agent: 1, 3-Bis (N, N-diglycidylaminomethyl) cyclohexane (trade name "Tetrad-C", manufactured by Mitsubishi Gas Chemicals, Inc.) 0.25 parts by mass
〈粘着剤層の形成〉
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、実施例4の粘着シートを作製した。実施例4の粘着シートにおける粘着剤層の組成について、単位を質量部として表2に示す(後記の実施例5~7についても同様である)。 <Formation of adhesive layer>
A coating film is coated with an adhesive composition on the release-treated surface of a 38 μm-thick base film (trade name “MRF # 38”, polyester film, manufactured by Mitsubishi Plastics) whose one side is mold-released. Formed. The coating was then dried by heating at 132 ° C. for 3 minutes. As a result, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, on the pressure-sensitive adhesive layer on the base film, a release-treated surface of a 38 μm-thick release film (trade name “MRE # 38”, polyester film, manufactured by Mitsubishi Resin Co., Ltd.) whose one side is mold-released is applied. I pasted them together. Then, it was aged at 60 ° C. for 24 hours to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed. As described above, the pressure-sensitive adhesive sheet of Example 4 was produced. The composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 4 is shown in Table 2 in units of mass (the same applies to Examples 5 to 7 described later).
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、実施例4の粘着シートを作製した。実施例4の粘着シートにおける粘着剤層の組成について、単位を質量部として表2に示す(後記の実施例5~7についても同様である)。 <Formation of adhesive layer>
A coating film is coated with an adhesive composition on the release-treated surface of a 38 μm-thick base film (trade name “MRF # 38”, polyester film, manufactured by Mitsubishi Plastics) whose one side is mold-released. Formed. The coating was then dried by heating at 132 ° C. for 3 minutes. As a result, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the base film. Next, on the pressure-sensitive adhesive layer on the base film, a release-treated surface of a 38 μm-thick release film (trade name “MRE # 38”, polyester film, manufactured by Mitsubishi Resin Co., Ltd.) whose one side is mold-released is applied. I pasted them together. Then, it was aged at 60 ° C. for 24 hours to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed. As described above, the pressure-sensitive adhesive sheet of Example 4 was produced. The composition of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of Example 4 is shown in Table 2 in units of mass (the same applies to Examples 5 to 7 described later).
〔実施例5~7〕
実施例4の粘着シートと同様にして、実施例5~7の各粘着シートを作製した。ただし、第2ポリマーの配合量を表2に示す量に変更した。 [Examples 5 to 7]
Each of the pressure-sensitive adhesive sheets of Examples 5 to 7 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 4. However, the blending amount of the second polymer was changed to the amount shown in Table 2.
実施例4の粘着シートと同様にして、実施例5~7の各粘着シートを作製した。ただし、第2ポリマーの配合量を表2に示す量に変更した。 [Examples 5 to 7]
Each of the pressure-sensitive adhesive sheets of Examples 5 to 7 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 4. However, the blending amount of the second polymer was changed to the amount shown in Table 2.
<評価>
1.耐候性試験
(耐候性試験用試料の製造)
イーグルガラス(厚み0.55mm、松浪硝子社製)の厚み方向一方面に対して、各実施例および各比較例の粘着剤層25μm、UVA-TAC 32μm、UVA-OCA100μm、および、UVA-TAC 32μmの順になるように積層させた。各実施例および各比較例の積層体において、当該サンプルに対して紫外線を照射した。具体的には、サンプルにおける粘着シート(粘着剤層)に対し、23℃および相対湿度50%の環境下において、イーグルガラス側から同ガラス越しに、紫外線を照射した(当該UV照射により、粘着剤層中のロイコ系色素と光酸発生剤とを反応させた)。この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、照射積算光量を8000mJ/cm2(波長320nm~390nmの範囲での照射積算光量)とした。以上のようにして、耐候性試験用試料を作製した。 <Evaluation>
1. 1. Weather resistance test (manufacturing of sample for weather resistance test)
Adhesive layer 25 μm, UVA-TAC 32 μm, UVA-OCA 100 μm, and UVA-TAC 32 μm of each Example and each comparative example with respect to one side in the thickness direction of eagle glass (thickness 0.55 mm, manufactured by Matsunami Glass Co., Ltd.). They were laminated in the order of. In the laminated body of each Example and each Comparative Example, the sample was irradiated with ultraviolet rays. Specifically, the adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the glass in an environment of 23 ° C. and a relative humidity of 50% (adhesive by the UV irradiation). The leuco-based dye in the layer was reacted with the photoacid generator). In this UV irradiation, a UV-LED lamp having a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source, and the integrated irradiation amount is 8000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 320 nm to 390 nm). As described above, a sample for weather resistance test was prepared.
1.耐候性試験
(耐候性試験用試料の製造)
イーグルガラス(厚み0.55mm、松浪硝子社製)の厚み方向一方面に対して、各実施例および各比較例の粘着剤層25μm、UVA-TAC 32μm、UVA-OCA100μm、および、UVA-TAC 32μmの順になるように積層させた。各実施例および各比較例の積層体において、当該サンプルに対して紫外線を照射した。具体的には、サンプルにおける粘着シート(粘着剤層)に対し、23℃および相対湿度50%の環境下において、イーグルガラス側から同ガラス越しに、紫外線を照射した(当該UV照射により、粘着剤層中のロイコ系色素と光酸発生剤とを反応させた)。この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、照射積算光量を8000mJ/cm2(波長320nm~390nmの範囲での照射積算光量)とした。以上のようにして、耐候性試験用試料を作製した。 <Evaluation>
1. 1. Weather resistance test (manufacturing of sample for weather resistance test)
Adhesive layer 25 μm, UVA-
UVA-TAC:TACフィルム(KC2UA、コニカミノルタ社製)とハードコート層とを順に備えるフィルム(ハードコート処理により、KC2UA(厚み:25μm)の一方面にハードコート層(厚み:7μm)を形成することにより得られる(厚み:32μm)
UVA-OCA:紫外線吸収機能を有する粘着テープ、商品名「CS9934U」、厚み100μm、日東電工社製 UVA-TAC: A film having a TAC film (KC2UA, manufactured by Konica Minolta) and a hard coat layer in order (a hard coat layer (thickness: 7 μm) is formed on one surface of KC2UA (thickness: 25 μm) by a hard coat treatment). (Thickness: 32 μm)
UVA-OCA: Adhesive tape with UV absorption function, product name "CS9934U", thickness 100 μm, manufactured by Nitto Denko Corporation
UVA-OCA:紫外線吸収機能を有する粘着テープ、商品名「CS9934U」、厚み100μm、日東電工社製 UVA-TAC: A film having a TAC film (KC2UA, manufactured by Konica Minolta) and a hard coat layer in order (a hard coat layer (thickness: 7 μm) is formed on one surface of KC2UA (thickness: 25 μm) by a hard coat treatment). (Thickness: 32 μm)
UVA-OCA: Adhesive tape with UV absorption function, product name "CS9934U", thickness 100 μm, manufactured by Nitto Denko Corporation
(耐候性試験)
実施例1~3および比較例1の耐候性試験用試料において、平均透過率、L*、a*、および、b*の値を測定した。 (Weather resistance test)
The average transmittance, L * , a * , and b * values were measured in the weather resistance test samples of Examples 1 to 3 and Comparative Example 1.
実施例1~3および比較例1の耐候性試験用試料において、平均透過率、L*、a*、および、b*の値を測定した。 (Weather resistance test)
The average transmittance, L * , a * , and b * values were measured in the weather resistance test samples of Examples 1 to 3 and Comparative Example 1.
具体的には、耐候性試験用試料において、イーグルガラス側から光が当たるように、透過率測定装置(U4150形分光光度計、日立ハイテクサイエンス社製)に設置した。そして、波長400nm~700nmにおける平均透過率、L*、a*、および、b*の値をそれぞれ測定した。
Specifically, in the weather resistance test sample, it was installed in a transmittance measuring device (U4150 type spectrophotometer, manufactured by Hitachi High-Tech Science Co., Ltd.) so that light was applied from the eagle glass side. Then, the average transmittance and the values of L * , a * , and b * at wavelengths of 400 nm to 700 nm were measured.
詳しくは、耐候性試験用試料の波長400nm~700nmにおける平均透過率(T1)と、耐候性試験用試料に対するL*(L1
*)と、耐候性試験用試料に対するa*(a1
*)と、耐候性試験用試料に対するb*(b1
*)とをそれぞれ測定した。
Specifically, the average transmittance (T1) of the weathering test sample at a wavelength of 400 nm to 700 nm, L * (L 1 * ) for the weathering test sample, and a * (a 1 * ) for the weathering test sample. And b * (b 1 * ) for the weather resistance test sample were measured, respectively.
次いで、耐候性試験用試料に、スガ試験機社製スーパーキセノンウェザーメーターSX75用いて、波長300nm~400nmの範囲における照度が120Wであるスーパーキセノンランプを、24時間照射した。これにより、24時間照射後の耐候性試験用試料を得た。
Next, the weather resistance test sample was irradiated with a super xenon lamp having an illuminance of 120 W in the wavelength range of 300 nm to 400 nm for 24 hours using a super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd. As a result, a sample for weather resistance test after irradiation for 24 hours was obtained.
次いで、上記と同様の手順により、24時間照射後の耐候性試験用試料の平均透過率、L*、a*、および、b*の値を測定した。
Then, by the same procedure as above, the average transmittance, L * , a * , and b * values of the weather resistance test sample after irradiation for 24 hours were measured.
詳しくは、24時間照射後の耐候性試験用試料の波長400nm~700nmにおける平均透過率(T2)と、24時間照射後の耐候性試験用試料に対するL*(L2
*)と、24時間照射後の耐候性試験用試料に対するa*(a2
*)と、24時間照射後の耐候性試験用試料に対するb*(b2
*)とを、それぞれ測定した。
Specifically, the average transmittance (T2) of the weather resistance test sample after 24-hour irradiation at a wavelength of 400 nm to 700 nm, L * (L 2 * ) for the weather resistance test sample after 24-hour irradiation, and 24-hour irradiation. A * (a 2 *) for the later weather resistance test sample and b * (b 2 * ) for the weather resistance test sample after 24-hour irradiation were measured, respectively.
そして、下記式(7)に基づき、色差(ΔE)を算出した。
Then, the color difference (ΔE) was calculated based on the following formula (7).
ΔE=((L2
*-L1
*)2+(a2
*-a1
*)2+(b2
*-b1
*)2)1/2
(7) ΔE = ((L 2 * -L 1 * ) 2 + (a 2 * -a 1 * ) 2 + (b 2 * -b 1 * ) 2 ) 1/2
(7)
(7) ΔE = ((L 2 * -L 1 * ) 2 + (a 2 * -a 1 * ) 2 + (b 2 * -b 1 * ) 2 ) 1/2
(7)
T1、T2、および、色差(ΔE)の結果を表1に示す。
Table 1 shows the results of T1, T2, and the color difference (ΔE).
2.耐久性試験
粘着シートの粘着剤層に対する、線状の開口部を有するフォトマスクを介した紫外線照射により、粘着剤層に線状の変色部分を形成した。フォトマスクは、粘着シートにおける基材フィルム側表面に配置されたドライフィルムフォトレジストから形成され、フォトマスクの開口部の線幅は200μmであった。紫外線照射では、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、フォトマスクおよび基材フィルム越しに粘着剤層に紫外線を照射し、照射積算光量を2000mJ/cm2(波長320nm~390nmの範囲での照射積算光量)とした。 2. 2. Durability test A linear discolored portion was formed on the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with ultraviolet rays through a photomask having a linear opening. The photomask was formed from a dry film photoresist placed on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask was 200 μm. For ultraviolet irradiation, a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source through a photo mask and a base film. The pressure-sensitive adhesive layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (the integrated irradiation light amount in the wavelength range of 320 nm to 390 nm).
粘着シートの粘着剤層に対する、線状の開口部を有するフォトマスクを介した紫外線照射により、粘着剤層に線状の変色部分を形成した。フォトマスクは、粘着シートにおける基材フィルム側表面に配置されたドライフィルムフォトレジストから形成され、フォトマスクの開口部の線幅は200μmであった。紫外線照射では、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、フォトマスクおよび基材フィルム越しに粘着剤層に紫外線を照射し、照射積算光量を2000mJ/cm2(波長320nm~390nmの範囲での照射積算光量)とした。 2. 2. Durability test A linear discolored portion was formed on the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with ultraviolet rays through a photomask having a linear opening. The photomask was formed from a dry film photoresist placed on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask was 200 μm. For ultraviolet irradiation, a UV-LED lamp with a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source through a photo mask and a base film. The pressure-sensitive adhesive layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (the integrated irradiation light amount in the wavelength range of 320 nm to 390 nm).
次に、粘着剤層に形成された線状変色部分の線幅を測定した(第1変色幅W1の測定)。具体的には、まず、粘着剤層に形成された線状変色部分をデジタルマイクロスコープ(商品名「VHX-900」、KEYENCE社製)によって観察し、変色部分の一部とその近傍とを包含する領域を50倍の倍率で撮影した。次に、撮影された画像を画像解析ソフトによって二値化処理した。次に、二値化処理後の画像において、線状変色部分の線幅(第1変色幅W1)を測定した。
Next, the line width of the linear discolored portion formed on the pressure-sensitive adhesive layer was measured (measurement of the first discolored width W1). Specifically, first, the linear discolored portion formed on the adhesive layer is observed with a digital microscope (trade name "VHX-900", manufactured by KEYENCE), and a part of the discolored portion and its vicinity are included. The area to be used was photographed at a magnification of 50 times. Next, the captured image was binarized by image analysis software. Next, in the image after the binarization process, the line width (first color change width W1) of the linear color change portion was measured.
次に、粘着剤層に線状変色部分が形成されている粘着シートを、85℃で120時間、加熱処理した(第1耐久性試験)。
Next, the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 85 ° C. for 120 hours (first durability test).
次に、粘着シートの粘着剤層における線状変色部分の線幅を測定した(第2変色幅W2の測定)。具体的な測定方法は、第1変色幅W1の測定に関して上記した測定方法と同じである。第1耐久性試験前の線状変色部分の第1変色幅W1、第1耐久性試験後の線状変色部分の第2変色幅W2、および、第1変色幅W1に対する第2変色幅W2の変化率(W2/W1)を、表1および表2に示す。
Next, the line width of the linear discolored portion in the adhesive layer of the adhesive sheet was measured (measurement of the second discolored width W2). The specific measurement method is the same as the measurement method described above for the measurement of the first color change width W1. The first discoloration width W1 of the linear discoloration portion before the first durability test, the second discoloration width W2 of the linear discoloration portion after the first durability test, and the second discoloration width W2 with respect to the first discoloration width W1. The rate of change (W2 / W1) is shown in Tables 1 and 2.
また、実施例1~7および比較例1の各粘着シートの粘着剤層について、第1耐久性試験に代えて第2耐久性試験を実施したこと以外は上記の方法と同様にして、形成される線状変色部分の線幅調べた。第2耐久性試験では、粘着剤層に線状変色部分が形成されている粘着シートを、85℃で240時間、加熱処理した。第2耐久性試験前の線状変色部分の第1変色幅W1、第2耐久性試験後の線状変色部分の第3変色幅W3、および、第1変色幅W1に対する第3変色幅W3の変化率(第3変色幅W3/第1変色幅W1)を、表1および表2に示す。
Further, the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 7 and Comparative Example 1 were formed in the same manner as in the above method except that the second durability test was performed instead of the first durability test. The line width of the linear discolored part was examined. In the second durability test, the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 85 ° C. for 240 hours. The first discoloration width W1 of the linear discoloration portion before the second durability test, the third discoloration width W3 of the linear discoloration portion after the second durability test, and the third discoloration width W3 with respect to the first discoloration width W1. The rate of change (third color change width W3 / first color change width W1) is shown in Tables 1 and 2.
3.剥離試験
各実施例および各比較例の粘着剤層を、ガラス板に対して貼着した。その後、下記条件に基づき、ガラス板に対する粘着力を測定した。その結果を表1に示す。 3. 3. Peeling test The pressure-sensitive adhesive layers of each example and each comparative example were attached to a glass plate. Then, the adhesive strength to the glass plate was measured based on the following conditions. The results are shown in Table 1.
各実施例および各比較例の粘着剤層を、ガラス板に対して貼着した。その後、下記条件に基づき、ガラス板に対する粘着力を測定した。その結果を表1に示す。 3. 3. Peeling test The pressure-sensitive adhesive layers of each example and each comparative example were attached to a glass plate. Then, the adhesive strength to the glass plate was measured based on the following conditions. The results are shown in Table 1.
(測定条件)
温度:23℃
剥離角度:180°
剥離速度:300mm/分 (Measurement condition)
Temperature: 23 ° C
Peeling angle: 180 °
Peeling speed: 300 mm / min
温度:23℃
剥離角度:180°
剥離速度:300mm/分 (Measurement condition)
Temperature: 23 ° C
Peeling angle: 180 °
Peeling speed: 300 mm / min
4.ミクロ相分離構造の確認
実施例4~7の各粘着シートの粘着剤層について、次のようにして、ミクロ相分離構造を確認した。まず、透過電子顕微鏡(TEM)による観察用のサンプルを作製した。具体的には、粘着剤層を染色した後に急速凍結し、当該粘着剤層からウルトラミクロトーム(Leica製)を使用して薄片を切り出した。そして、当該薄片について、透過型電子顕微鏡(商品名「HT7820」,日立ハイテクノロジーズ社製)を使用して観察および撮影を実施した。次に、得られたTEM画像を、画像解析ソフトによって解析して二値化した。実施例7における粘着剤層のミクロ相分離を代表的に図4に示す。 4. Confirmation of Micro-Phase Separation Structure The micro-phase separation structure was confirmed for the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7 as follows. First, a sample for observation with a transmission electron microscope (TEM) was prepared. Specifically, the pressure-sensitive adhesive layer was stained and then rapidly frozen, and flakes were cut out from the pressure-sensitive adhesive layer using an ultramicrotome (manufactured by Leica). Then, the flakes were observed and photographed using a transmission electron microscope (trade name "HT7820", manufactured by Hitachi High-Technologies Corporation). Next, the obtained TEM image was analyzed by image analysis software and binarized. The microphase separation of the pressure-sensitive adhesive layer in Example 7 is typically shown in FIG.
実施例4~7の各粘着シートの粘着剤層について、次のようにして、ミクロ相分離構造を確認した。まず、透過電子顕微鏡(TEM)による観察用のサンプルを作製した。具体的には、粘着剤層を染色した後に急速凍結し、当該粘着剤層からウルトラミクロトーム(Leica製)を使用して薄片を切り出した。そして、当該薄片について、透過型電子顕微鏡(商品名「HT7820」,日立ハイテクノロジーズ社製)を使用して観察および撮影を実施した。次に、得られたTEM画像を、画像解析ソフトによって解析して二値化した。実施例7における粘着剤層のミクロ相分離を代表的に図4に示す。 4. Confirmation of Micro-Phase Separation Structure The micro-phase separation structure was confirmed for the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7 as follows. First, a sample for observation with a transmission electron microscope (TEM) was prepared. Specifically, the pressure-sensitive adhesive layer was stained and then rapidly frozen, and flakes were cut out from the pressure-sensitive adhesive layer using an ultramicrotome (manufactured by Leica). Then, the flakes were observed and photographed using a transmission electron microscope (trade name "HT7820", manufactured by Hitachi High-Technologies Corporation). Next, the obtained TEM image was analyzed by image analysis software and binarized. The microphase separation of the pressure-sensitive adhesive layer in Example 7 is typically shown in FIG.
実施例4~7の各粘着シートの粘着剤層では、スフィア型のミクロ相分離構造を確認できた。各粘着剤層では、第1ポリマーのイソプレンブロック(ソフトセグメント)が形成するマトリクス(海部)に、第1ポリマーのスチレン(ハードセグメント)と第2ポリマー(スチレン・アクリル酸n-ブチル共重合体)とが形成する球状の分散相(島部)が、分散していた。
In the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7, a sphere-type microphase-separated structure could be confirmed. In each pressure-sensitive adhesive layer, the matrix (sea part) formed by the isoprene block (soft segment) of the first polymer is filled with the styrene (hard segment) of the first polymer and the second polymer (styrene-n-butyl acrylate copolymer). The spherical dispersed phase (island) formed by and was dispersed.
5.相溶性判定試験
実施例4~7で用いた発色性化合物および酸発生剤のそれぞれについて、各種モノマーまたはポリマー溶液との相溶性を調べた。 5. Compatibility determination test The compatibility of each of the color-developing compound and the acid generator used in Examples 4 to 7 with various monomer or polymer solutions was examined.
実施例4~7で用いた発色性化合物および酸発生剤のそれぞれについて、各種モノマーまたはポリマー溶液との相溶性を調べた。 5. Compatibility determination test The compatibility of each of the color-developing compound and the acid generator used in Examples 4 to 7 with various monomer or polymer solutions was examined.
具体的には、まず、モノマー溶液として、スチレン、アクリル酸n-ブチル、メタクリル酸メチル(MMA)、アクリル酸、N-ビニル-2-ピロリドン(NVP)、アクリル酸2-メトキシエチル(2MEA)、アクリル酸メチル、アクリル酸2-エチルヘキシル(2EHA)、アクリル酸ラウリル(アクリル酸ドデシル)、およびアクリル酸ステアリル(アクリル酸オクタデシル)の各溶液を用意した。
Specifically, first, as a monomer solution, styrene, n-butyl acrylate, methyl methacrylate (MMA), acrylic acid, N-vinyl-2-pyrrolidone (NVP), 2-methoxyethyl acrylate (2MEA), Solutions of methyl acrylate, 2-ethylhexyl acrylate (2EHA), lauryl acrylate (dodecyl acrylate), and stearyl acrylate (octadecyl acrylate) were prepared.
次に、50mLのスクリュー管内で、モノマー溶液7.8gと、化合物C(発色性化合物または光酸発生剤)0.2gとを含む混合物(化合物Cの割合は2.5質量%)を撹拌した(第1の撹拌)。撹拌には、マグネティックスターラーを使用した。撹拌において、温度は25℃とし、スターラーの回転数は500rpmとし、撹拌時間は5分間とした。撹拌の後、このような撹拌によって化合物Cが濁り又は沈殿を生じずにモノマー溶液に溶解するかどうかを、目視で確認した。発色性化合物および光酸発生剤は、それぞれ、スチレン、アクリル酸n-ブチル、MMA、アクリル酸、NVP、2MEA、およびアクリル酸メチルの各溶液に対し、濁り又は沈殿を生じずに溶解した(化合物Cは相溶性を示した)。一方、発色性化合物および光酸発生剤は、それぞれ、2EHA、アクリル酸ラウリル、およびアクリル酸ステアリルの各溶液に対し、濁り又は沈殿を生じた(化合物Cは相溶性を示さなかった)。
Next, a mixture containing 7.8 g of the monomer solution and 0.2 g of compound C (color-developing compound or photoacid generator) was stirred in a 50 mL screw tube (the ratio of compound C was 2.5% by mass). (First stirring). A magnetic stirrer was used for stirring. In stirring, the temperature was 25 ° C., the rotation speed of the stirrer was 500 rpm, and the stirring time was 5 minutes. After stirring, it was visually confirmed whether the compound C was dissolved in the monomer solution without causing turbidity or precipitation by such stirring. The color-developing compound and the photoacid generator were dissolved in each solution of styrene, n-butyl acrylate, MMA, acrylic acid, NVP, 2MEA, and methyl acrylate without causing turbidity or precipitation (compound). C showed compatibility). On the other hand, the color-developing compound and the photoacid generator caused turbidity or precipitation with respect to each solution of 2EHA, lauryl acrylate, and stearyl acrylate, respectively (Compound C did not show compatibility).
一方、ポリマー溶液として、ポリイソプレン溶液を用意した(イソプレンの揮発性が高すぎするため、イソプレンのモノマー溶液を用意できなかった)。次に、50mLのスクリュー管内で、ポリマー溶液7.8gと、化合物C(発色性化合物または光酸発生剤)0.2gとを含む混合物(化合物Cの割合は2.5質量%)を撹拌した(第2の撹拌)。第2の撹拌の条件は、上述の第1の撹拌の条件と同じである。発色性化合物および光酸発生剤は、それぞれ、ポリマー溶液に対し、濁り又は沈殿を生じたこと(化合物Cは相溶性を示さなかった)ことを、第2の撹拌後の観察によって確認した。
On the other hand, a polyisoprene solution was prepared as the polymer solution (the isoprene monomer solution could not be prepared because the isoprene is too volatile). Next, a mixture containing 7.8 g of the polymer solution and 0.2 g of compound C (color-developing compound or photoacid generator) was stirred in a 50 mL screw tube (the ratio of compound C was 2.5% by mass). (Second stirring). The conditions for the second stirring are the same as the conditions for the first stirring described above. It was confirmed by observation after the second stirring that the color-developing compound and the photoacid generator each produced turbidity or precipitation with respect to the polymer solution (Compound C did not show compatibility).
そして、化合物Cが上述の相溶性を示すモノマー溶液と同一のモノマー組成を80質量%以上含有するセグメントが、当該セグメントを有するポリマー成分によるミクロ相分離構造内に形成する相に対し、化合物Cが相溶性を有すると判定した。また、化合物Cが上述の相溶性を示さないモノマー溶液と同一のモノマー組成を80質量%以上含有するセグメントが、当該セグメントを有するポリマー成分によるミクロ相分離構造内に形成する相に対し、化合物Cが相溶性を有さないと判定した。すなわち、実施例4~7で用いた発色性化合物および光酸発生剤は、それぞれ、スチレンとアクリル酸n-ブチルとを含むハードセグメント(HS)がミクロ相分離構造内で形成する島部に対して相溶性を有する(実施例4~7におけるHSでは、化合物Cが相溶性を示すモノマー(スチレン,アクリル酸n-ブチル)の割合は80質量%以上である)。実施例4~7で用いた発色性化合物および光酸発生剤は、それぞれ、イソプレンを含むソフトセグメント(SS)がミクロ相分離構造内で形成する海部に対して相溶性を有さない(実施例4~7におけるSSでは、化合物Cが相溶性を示さないイソプレンの割合は80質量%以上である)。
Then, with respect to the phase in which the segment containing 80% by mass or more of the same monomer composition as the monomer solution in which the compound C exhibits the above-mentioned compatibility is formed in the microphase separation structure by the polymer component having the segment, the compound C is added. It was determined to have compatibility. Further, with respect to a phase in which a segment containing 80% by mass or more of the same monomer composition as the above-mentioned monomer solution in which compound C does not exhibit compatibility is formed in a microphase separation structure by a polymer component having the segment, compound C is used. Was determined to be incompatible. That is, the color-developing compound and the photoacid generator used in Examples 4 to 7 each have an island portion formed by a hard segment (HS) containing styrene and n-butyl acrylate in a microphase-separated structure. (In HS in Examples 4 to 7, the proportion of the monomer (styrene, n-butyl acrylate) in which compound C is compatible is 80% by mass or more). The color-developing compound and the photoacid generator used in Examples 4 to 7 are not compatible with the sea portion formed by the soft segment (SS) containing isoprene in the microphase-separated structure, respectively (Example). In SS in 4 to 7, the proportion of isoprene in which compound C is incompatible is 80% by mass or more).
6.光透過率
実施例4~7の各粘着シートの粘着剤層について、次のようにして、波長400nm~700nmでの平均透過率を調べた。 6. Light Transmittance For the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7, the average transmittance at a wavelength of 400 nm to 700 nm was examined as follows.
実施例4~7の各粘着シートの粘着剤層について、次のようにして、波長400nm~700nmでの平均透過率を調べた。 6. Light Transmittance For the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 4 to 7, the average transmittance at a wavelength of 400 nm to 700 nm was examined as follows.
まず、粘着シートをイーグルガラス(厚さ0.55mm,松浪硝子社製)に貼り合せて、測定用サンプル(第1の測定用サンプル)を作製した。次に、測定用サンプルについて、日立ハイテクノロジーズ社製の分光光度計U4150を使用して、波長400nm~700nmでの平均透過率を測定した(第1の透過率測定)。本測定では、測定用サンプルに対してそのイーグルガラス側から光が当たるように測定用サンプルを装置内に設置した状態で、測定用サンプルの波長400nm~700nmにおける全光線透過率を1nmピッチで測定した。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。実施例1~3および比較例1における上述の平均透過率の測定も、具体的には本測定と同様に実施した。測定された粘着剤層の平均透過率T1(UV照射前の波長400nm~700nmでの平均透過率)を、表2に示す。
First, the adhesive sheet was attached to eagle glass (thickness 0.55 mm, manufactured by Matsunami Glass Co., Ltd.) to prepare a measurement sample (first measurement sample). Next, with respect to the measurement sample, the average transmittance at a wavelength of 400 nm to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (first transmittance measurement). In this measurement, the total light transmittance of the measurement sample at a wavelength of 400 nm to 700 nm is measured at a pitch of 1 nm with the measurement sample installed in the device so that the measurement sample is exposed to light from the eagle glass side. did. In this measurement, the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as the baseline. The above-mentioned average transmittance measurements in Examples 1 to 3 and Comparative Example 1 were also specifically carried out in the same manner as in this measurement. Table 2 shows the measured average transmittance T1 (average transmittance at a wavelength of 400 nm to 700 nm before UV irradiation) of the pressure-sensitive adhesive layer.
一方、実施例4~7の各粘着シートについて、次のようにして、UV照射後における波長400nm~700nmでの平均透過率を調べた。
On the other hand, for each of the pressure-sensitive adhesive sheets of Examples 4 to 7, the average transmittance at a wavelength of 400 nm to 700 nm after UV irradiation was examined as follows.
まず、上述の第1の測定用サンプルと同様のサンプルを作製した。次に、当該サンプルに対して紫外線を照射した。具体的には、サンプルにおける粘着シート(粘着剤層)に対し、23℃および相対湿度50%の環境下において、イーグルガラス側から同ガラス越しに、紫外線を照射した(当該UV照射により、粘着剤層中のロイコ系色素と光酸発生剤とを反応させた)。この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、照射積算光量を8000mJ/cm2(波長320nm~390nmの範囲での照射積算光量)とした。以上のようにして、測定用サンプル(第2の測定用サンプル)を作製した。
First, a sample similar to the above-mentioned first measurement sample was prepared. Next, the sample was irradiated with ultraviolet rays. Specifically, the adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the glass in an environment of 23 ° C. and a relative humidity of 50% (adhesive by the UV irradiation). The leuco-based dye in the layer was reacted with the photoacid generator). In this UV irradiation, a UV-LED lamp having a wavelength of 365 nm in a UV-LED irradiation device (model number "QEL-350-RU6W-CW-MY") manufactured by Quark Technology Co., Ltd. is used as a light source, and the integrated irradiation amount is 8000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 320 nm to 390 nm). As described above, a measurement sample (second measurement sample) was prepared.
次に、第2の測定用サンプルについて、日立ハイテクノロジーズ社製の分光光度計U4150を使用して、波長400nm~700nmでの平均透過率を測定した(第2の透過率測定)。具体的な測定の方法および条件について、第2の透過率測定は、上述の第1の透過率測定と同じである。測定された粘着剤層の平均透過率T2(UV照射後の波長400nm~700nmでの平均透過率)を、表2に示す。また、上述の平均透過率T1に対する平均透過率T2の比率も、表2に示す。
Next, for the second measurement sample, the average transmittance at a wavelength of 400 nm to 700 nm was measured using a spectrophotometer U4150 manufactured by Hitachi High-Technologies Corporation (second transmittance measurement). Regarding the specific measurement method and conditions, the second transmittance measurement is the same as the first transmittance measurement described above. Table 2 shows the measured average transmittance T2 (average transmittance at a wavelength of 400 nm to 700 nm after UV irradiation) of the pressure-sensitive adhesive layer. Table 2 also shows the ratio of the average transmittance T2 to the above-mentioned average transmittance T1.
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 embodiment is an example of the present invention, and the present invention should not be construed in a limited manner by the embodiment. Modifications of the invention that are apparent to those skilled in the art are included in the claims below.
本発明の可変色粘着シートは、例えば、ディスプレイパネルの製造過程において、ディスプレイパネルの積層構造に含まれる要素どうしの貼り合わせのために、用いられる。
The variable color adhesive sheet of the present invention is used, for example, in the process of manufacturing a display panel for bonding elements included in a laminated structure of a display panel.
S 粘着シート(可変色粘着シート)
10 粘着剤層
11 変色部分
20 基材
31 第1部材
32 第2部材 S Adhesive sheet (variable color adhesive sheet)
10Adhesive layer 11 Discolored part 20 Base material 31 First member 32 Second member
10 粘着剤層
11 変色部分
20 基材
31 第1部材
32 第2部材 S Adhesive sheet (variable color adhesive sheet)
10
Claims (5)
- 外部刺激によって変色可能な粘着剤層を備え、
下記試験1により求められる第1変色幅W1、および、下記試験2により求められる第2変色幅W2が、下記式(1)を満たす、可変色粘着シート。
0.5<W2/W1<2 (1)
<試験1>
ステップA:粘着剤層に対して外部刺激を線状に付与する。
ステップB:ステップAの後に、粘着剤層内に形成された変色領域の幅を測定する。
<試験2>
ステップC:前記試験1のステップA、ステップBの後に、85℃で120時間加熱処理する。
ステップD:ステップCの後に、粘着剤層内に形成された変色領域の幅を測定する。 Equipped with an adhesive layer that can be discolored by external stimuli
A variable color adhesive sheet in which the first discoloration width W1 determined by the following test 1 and the second discoloration width W2 determined by the following test 2 satisfy the following formula (1).
0.5 <W2 / W1 <2 (1)
<Test 1>
Step A: External stimulus is linearly applied to the pressure-sensitive adhesive layer.
Step B: After step A, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured.
<Test 2>
Step C: After step A and step B of the test 1, heat treatment is performed at 85 ° C. for 120 hours.
Step D: After step C, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured. - 前記第1変色幅W1、および、下記試験3により求められる第3変色幅W3が、下記式(2)を満たす、請求項1に記載の可変色粘着シート。
0.5<W3/W1<2 (2)
<試験3>
ステップE:上記の<試験1>のステップA、ステップBの後に、85℃で240時間加熱処理する。
ステップF:ステップEの後に、粘着剤層内に形成された変色領域の幅を測定する。 The variable color adhesive sheet according to claim 1, wherein the first color change width W1 and the third color change width W3 obtained by the following test 3 satisfy the following formula (2).
0.5 <W3 / W1 <2 (2)
<Test 3>
Step E: After step A and step B of <Test 1> above, heat treatment is performed at 85 ° C. for 240 hours.
Step F: After step E, the width of the discolored area formed in the pressure-sensitive adhesive layer is measured. - 前記粘着剤層が、10μm以上300μm以下の厚みを有する、請求項1に記載の可変色粘着シート。 The variable color pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 10 μm or more and 300 μm or less.
- 前記粘着剤層の厚み方向一方側に配置された基材をさらに備える、請求項1に記載の可変色粘着シート。 The variable color pressure-sensitive adhesive sheet according to claim 1, further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer.
- 前記粘着剤層を、ガラス板に対して貼着した後、23℃、剥離角度180°および剥離速度300mm/分の剥離条件での剥離試験において、前記ガラス板に対して示す粘着力が、1.0N/25mm以上50N/25mm以下である、請求項1に記載の可変色粘着シート。 After the pressure-sensitive adhesive layer is attached to the glass plate, in a peeling test under the peeling conditions of 23 ° C., a peeling angle of 180 ° and a peeling speed of 300 mm / min, the adhesive strength shown to the glass plate is 1. The variable color adhesive sheet according to claim 1, which is 0.0N / 25 mm or more and 50N / 25 mm or less.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62153377A (en) * | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
JPH11140388A (en) * | 1997-09-08 | 1999-05-25 | Sekisui Chem Co Ltd | Hardenable pressure-sensitive adhesive sheet |
JP2003160767A (en) * | 2001-11-27 | 2003-06-06 | Nitto Denko Corp | Thermochromic heat-exfoliative-type pressure-sensitive adhesive sheet |
JP2004175978A (en) * | 2002-11-28 | 2004-06-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, method for forming the same and pressure-sensitive adhesive sheet |
JP2016196541A (en) * | 2015-04-02 | 2016-11-24 | 山本化成株式会社 | Liquid resin composition for active ray-curable adhesive |
WO2019035411A1 (en) * | 2017-08-18 | 2019-02-21 | 積水化学工業株式会社 | Moisture curable resin composition, adhesive for electronic components, and adhesive for display elements |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017203810A (en) | 2016-05-09 | 2017-11-16 | 日本化薬株式会社 | Light absorption layer contained in color filter for organic electroluminescence display and sheet using the same |
-
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62153377A (en) * | 1985-12-27 | 1987-07-08 | F S K Kk | Pressure-sensitive adhesive sheet |
JPH11140388A (en) * | 1997-09-08 | 1999-05-25 | Sekisui Chem Co Ltd | Hardenable pressure-sensitive adhesive sheet |
JP2003160767A (en) * | 2001-11-27 | 2003-06-06 | Nitto Denko Corp | Thermochromic heat-exfoliative-type pressure-sensitive adhesive sheet |
JP2004175978A (en) * | 2002-11-28 | 2004-06-24 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, method for forming the same and pressure-sensitive adhesive sheet |
JP2016196541A (en) * | 2015-04-02 | 2016-11-24 | 山本化成株式会社 | Liquid resin composition for active ray-curable adhesive |
WO2019035411A1 (en) * | 2017-08-18 | 2019-02-21 | 積水化学工業株式会社 | Moisture curable resin composition, adhesive for electronic components, and adhesive for display elements |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023243510A1 (en) * | 2022-06-15 | 2023-12-21 | 日東電工株式会社 | Variable color pressure-sensitive adhesive sheet |
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