WO2022054635A1 - Variable color adhesive sheet - Google Patents
Variable color adhesive sheet Download PDFInfo
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- WO2022054635A1 WO2022054635A1 PCT/JP2021/031867 JP2021031867W WO2022054635A1 WO 2022054635 A1 WO2022054635 A1 WO 2022054635A1 JP 2021031867 W JP2021031867 W JP 2021031867W WO 2022054635 A1 WO2022054635 A1 WO 2022054635A1
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- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive layer
- meth
- adhesive sheet
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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
- 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]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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.
- the present invention provides a variable color pressure-sensitive adhesive sheet capable of discoloring at least a part of the pressure-sensitive adhesive layer after being attached to an adherend and suitable for suppressing deterioration of the discolored portion of the pressure-sensitive adhesive layer. ..
- the present invention is a variable color pressure-sensitive adhesive sheet provided with a color-changing pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains a colorant capable of developing a color by a first external stimulus.
- the pressure-sensitive adhesive layer which can be cured by a different second external stimulus, has a first shear storage at 25 ° C., as shown by dynamic viscoelastic measurements at a frequency of 1 Hz and a heating rate of 5 ° C./min.
- the elastic modulus is 0.1 ⁇ 10 5 Pa or more and 10 ⁇ 10 5 Pa or less, and the second shear storage elastic modulus at 25 ° C., which is shown by the dynamic viscoelastic measurement under the above conditions, for the adhesive layer after curing.
- the ratio of the first shear storage elastic modulus to the first shear storage elastic modulus is 2 or more and 300 or less, and includes a variable color pressure-sensitive adhesive sheet.
- the third color change width W3 of the color change region after further heat-treating the pressure-sensitive adhesive layer at 65 ° C. and 90% relative humidity for 120 hours satisfies 0.5 ⁇ W3 / W1 ⁇ 2.4.
- the variable color adhesive sheet according to [2] is included.
- the present invention [4] is any one of the above [1] to [3], wherein the colorant is a compound that develops a color by reacting with an acid, and the pressure-sensitive adhesive layer further contains a photoacid generator. Includes the variable color adhesive sheets described in 1.
- the present invention [5] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the pressure-sensitive adhesive layer has a thickness of 10 to 300 ⁇ m.
- the present invention [6] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [5], further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer contains a colorant capable of developing a color by a first external stimulus as described above. 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 a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. According to such a variable color pressure-sensitive adhesive sheet, it is possible to inspect the presence or absence of foreign matter and air bubbles between the sheet and the adherend after bonding and before forming a discolored portion of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer can be cured by a second external stimulus different from the first external stimulus, and in the pressure-sensitive adhesive layer, the first shear storage before the curing is performed.
- the elastic modulus is 0.1 ⁇ 10 5 Pa or more and 10 ⁇ 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less.
- Such a variable color adhesive sheet secures adhesive properties suitable for bonding to an adherend at the time of bonding in the pressure-sensitive adhesive layer (before curing), and a colorant in the pressure-sensitive adhesive layer (after curing) after bonding. Suitable for suppressing the diffusion of.
- the diffusion of the colorant is suppressed, so that deterioration of the discolored portion over time (bleeding, fading, non-uniformity of color, etc.) is suppressed.
- FIG. 3A shows a process of preparing a variable color adhesive sheet and a member (adhesive body)
- FIG. 3B shows a process of joining members to each other via a variable color adhesive sheet
- FIG. 3C shows a variable color adhesive sheet.
- 3D represents a step of forming a discolored portion in the pressure-sensitive adhesive layer of a variable-color pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet S as an embodiment of the variable-color pressure-sensitive adhesive sheet of the present invention includes the 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 adhesive sheet S is used, for example, as a transparent adhesive sheet arranged on the image display side of the pixel panel in a display panel such as an organic EL panel (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 pressure-sensitive adhesive layer 10 contains a colorant that can be colored by the first external stimulus described later, and the portion that has been subjected to the first external stimulus can be discolored. Specifically, the pressure-sensitive adhesive layer 10 can reduce the transparency of the portion that has been subjected to the first external stimulus. Further, the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus described later, which is different from the first external stimulus.
- the shear storage elastic modulus (first shear storage elastic modulus) at 25 ° C. shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 before curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min is 0. .1 ⁇ 10 5 Pa or more and 10 ⁇ 10 5 Pa or less.
- the ratio of the shear storage elastic modulus (second shear storage elastic modulus) at 25 ° C. shown by the dynamic viscoelasticity measurement under the above conditions to the first shear storage elastic modulus of the cured pressure-sensitive adhesive layer 10 is 2 or more and 300 or less.
- the pressure-sensitive adhesive layer 10 contains a colorant that can be colored by a first external stimulus, as described above. Therefore, after the pressure-sensitive adhesive sheet S is attached to the adherend, the pressure-sensitive adhesive layer 10 is discolored by applying a first external stimulus to the portion to be discolored (at least a part of the pressure-sensitive adhesive layer) in the pressure-sensitive adhesive layer 10. Can be made to. According to the pressure-sensitive adhesive sheet S capable of forming a discolored portion 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 bonding and before the discolored portion of the pressure-sensitive adhesive layer 10 is formed. The presence of foreign matter and air bubbles in between can be inspected.
- the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus different from the first external stimulus, and the pressure-sensitive adhesive layer 10 has the first shear before its curing.
- the storage elastic modulus is 0.1 ⁇ 10 5 Pa or more and 10 ⁇ 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less.
- Such an adhesive sheet S is colored in the adhesive layer 10 (after curing) after bonding while ensuring the adhesive properties suitable for bonding to the adherend at the time of bonding in the adhesive layer 10 (before curing). Suitable for suppressing the diffusion of the agent.
- the diffusion of the colorant is suppressed, so that deterioration of the discolored portion over time (bleeding, fading, non-uniformity of color, etc.) is suppressed.
- the pressure-sensitive adhesive sheet S can discolor at least a part of the pressure-sensitive adhesive layer 10 after being attached to the adherend, and is suitable for suppressing deterioration of the discolored portion of the pressure-sensitive adhesive layer 10. Suppressing the deterioration of the discolored portion in the pressure-sensitive adhesive layer 10 is useful for maintaining the functional characteristics of the discolored portion such as designability, shielding property, and antireflection property.
- the above-mentioned first shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is preferably 0.2 ⁇ 10 5 Pa or more, and more preferably 0.3 ⁇ 10 5 Pa or more.
- the first shear storage elastic modulus is preferably 5 ⁇ 10 5 Pa or less, more preferably 3 ⁇ 10 5 Pa or less.
- the ratio of the second shear storage elastic modulus to the first shear storage elastic modulus is preferably 5 or more, more preferably 10 or more.
- the ratio is preferably 250 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less.
- the adjustment of the first shear storage elasticity of the pressure-sensitive adhesive layer 10 is, for example, adjustment of the constituent monomer composition in the polymer component such as the base polymer contained in the pressure-sensitive adhesive layer 10, and adjustment of the molecular weight (for example, weight average molecular weight) of the polymer component. This can be achieved by using a cross-linking agent for cross-linking the polymer component and adjusting the content ratio of the polymer component in the pressure-sensitive adhesive layer 10.
- the adjustment of the first shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is, for example, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10 and adjustment of the content ratio of the monomer component in the pressure-sensitive adhesive layer 10. May be realized by.
- the adjustment of the second shear storage elasticity of the pressure-sensitive adhesive layer 10 includes, for example, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10, adjustment of the content ratio of the monomer component in the pressure-sensitive adhesive layer 10. It can also be realized by using a cross-linking agent that cross-links a polymer component such as a base polymer contained in the pressure-sensitive adhesive layer 10.
- the adjustment of the second shear storage elastic modulus is realized by, for example, adjusting the composition of the constituent monomers of the polymer component in the pressure-sensitive adhesive layer 10, adjusting the molecular weight of the polymer component, and adjusting the content ratio of the polymer component in the pressure-sensitive adhesive layer 10. You may.
- the adjustment of the ratio of the second shear storage elasticity to the first shear storage elasticity is, for example, adjustment of the constituent monomer composition in the polymer component such as the base polymer contained in the pressure-sensitive adhesive layer 10, adjustment of the molecular weight of the polymer component, and adhesion. Adjustment of the content ratio of the polymer component in the agent layer 10, use of a cross-linking agent for cross-linking the polymer component, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10, and the monomer component in the pressure-sensitive adhesive layer 10. It can be realized by adjusting the content ratio of.
- the second color change width W2 of the color change region after the agent layer 10 is further heat-treated at 85 ° C. for 120 hours satisfies the following formula (1).
- Such a configuration is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion formed on the pressure-sensitive adhesive layer 10, and therefore is useful for maintaining the functional characteristics of the discolored portion. ..
- the first color change width W1 of the color change region formed in the pressure-sensitive adhesive layer 10 and the pressure-sensitive adhesive layer 10 are further added.
- the third color change width W3 of the color change region after heat treatment at 65 ° C. and 90% relative humidity for 120 hours satisfies the following formula (2).
- Such a configuration is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion formed on the pressure-sensitive adhesive layer 10, and therefore is useful for maintaining the functional characteristics of the discolored portion. ..
- the above-mentioned second shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is preferably 0.2 ⁇ 10 5 Pa or more, more preferably 2 ⁇ 10 5 Pa or more, and further preferably 5 ⁇ 10 5 Pa or more. Such a configuration is suitable for suppressing the diffusion of the colorant in the discolored portion in the pressure-sensitive adhesive layer 10 in which the discolored portion is formed by the first external stimulus, and is therefore suitable for suppressing the deterioration of the discolored portion.
- the second shear storage elastic modulus is preferably 100 ⁇ 10 5 Pa or less, more preferably 50 ⁇ 10 5 Pa or less, and further preferably 25 ⁇ 10 5 Pa or less. Such a configuration is suitable for ensuring the adhesive force with respect to the adherend in the adhesive layer 10 after curing.
- these configurations regarding the second shear storage elastic modulus are preferable for adjusting the pressure-sensitive adhesive layer 10 so as to satisfy the above formula (1), and the pressure-sensitive adhesive layer 10 so as to satisfy the above formula (1). It is preferable to adjust.
- the pressure-sensitive adhesive layer 10 can be adjusted so as to satisfy the above formulas (1) and / or formula (2).
- a first shear storage elastic modulus and a second shear storage elastic modulus with respect to the first shear storage elastic modulus are used. It is also possible to apply, for example, the following method while maintaining the ratio of the rate within the above range.
- a method of blending a metal complex in a pressure-sensitive adhesive layer (tacky composition) (first method), and a method of using a component bonded to another component as a coloring component in the pressure-sensitive adhesive layer (second method).
- the metal complex in the first method will be described later.
- a method in which a polymer in which a component capable of developing a color in a predetermined color is bonded is used as a component having both a polymer component and a coloring component such as a base polymer in an adhesive layer, initially separated from each other.
- a coloring component and a polymer component in a state of being bonded are bonded through a reaction in a pressure-sensitive adhesive layer, and a method in which these are combined.
- a first polymer component having a high compatibility with the coloring component and a second polymer component having a low compatibility with the coloring component are used as the polymer component in the pressure-sensitive adhesive layer, and the present invention is used.
- a method of providing the coloring component on the island portion by forming a sea-island structure in which the first polymer component forms an island portion in the pressure-sensitive adhesive layer can be mentioned.
- the pressure-sensitive adhesive layer 10 contains, for example, a base polymer, a polymerizable compound, and a photopolymerization initiator in addition to a colorant that can be colored by a first external stimulus.
- 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 preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass, from the viewpoint of appropriately expressing the function of the base polymer in the pressure-sensitive adhesive layer 10. % 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.
- 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 preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 60% by mass or more, 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.
- 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 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 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.
- 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 ( Examples include 4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
- the ratio of the hydroxyl group-containing monomer in the monomer component is preferably 1% by mass or more, 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 preferable 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). Is 30% by mass or less, more 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 ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 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 more preferably 3% by mass or more, still more preferably 5% by mass or more. The same ratio is preferably 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, more 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. It is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The same ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and 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. , 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 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.
- Examples of the amide group-containing monomer include N-vinylcarboxylic acid amides such as (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkyl (meth) acrylamide, and N-vinylacetamide, and N-hydroxyalkyl.
- Examples include (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N- (meth) acryloylmorpholin.
- 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).
- N- (3-hydroxypropyl) (meth) acrylamide N- (2-hydroxybutyl) (meth) acrylamide, N- (3-hydroxybutyl) (meth) acrylamide, and N- (4-hydroxybutyl) Examples include (meth) acrylamide.
- N-alkoxyalkyl (meth) acrylamide 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. Be done.
- 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 can be mentioned.
- alkoxy group-containing monomer examples 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. , Butoxyethyl (meth) acrylate, and ethoxypropyl (meth) 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-mentioned 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 and, for example, 1 part by mass or less with respect to 100 parts by mass of the monomer component.
- thermal polymerization initiator examples include an azo polymerization initiator and a peroxide polymerization initiator.
- examples of the azo 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 polymerization initiator include dibenzoyl peroxide, t-butyl permaleate, and lauroyl peroxide.
- the weight average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 300,000 or more, still 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 preferably 5,000,000 or less, more preferably 3,000,000 or less, still 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 preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, still 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 of the homopolymer formed from the monomer i. Indicates the temperature (° C).
- Literature values can be used for the glass transition temperature of homopolymers, for example, "Polymer Handbook” (4th edition, John Wiley & Sons, Inc., 1999) and “New Polymer Bunko 7 Introduction to Synthetic Resins for Paints”. (Kyozo Kitaoka, Polymer Publications, 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 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 isocyanates and polymethylene polyphenyl isocyanates. Further, examples of the isocyanate cross-linking agent include derivatives of these isocyanates.
- isocyanate derivative examples 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.
- 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, based on 100 parts by mass of the base polymer. It is preferably 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 3 parts by mass. It is as follows.
- a cross-linking catalyst may be used to effectively promote the cross-linking reaction.
- the cross-linking catalyst include dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, and butyltin oxide, and dibutyltin dilaurate is preferably used.
- the amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the base polymer.
- a cross-linking inhibitor that can be removed ex post facto from the sticky composition may be added to the sticky composition.
- dibutyltin dilaurate is used as the cross-linking catalyst
- acetylacetone is preferably used as the cross-linking inhibitor. In this case, in the adhesive composition, acetylacetone coordinates with dibutyltin dilaurate, and the cross-linking reaction of the cross-linking agent with the veil polymer is suppressed.
- acetylacetone can be volatilized and removed from the coating film by heating at a desired timing. This makes it possible to proceed with the cross-linking reaction of the cross-linking agent.
- the blending amount of the cross-linking inhibitor is, for example, 100 parts by mass or more, preferably 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking catalyst.
- the blending amount is, for example, 5000 parts by mass or less.
- the polymerizable compound is a compound having a polymerizable functional group.
- the polymerizable functional group has an ethylenically unsaturated double bond.
- Examples of the polymerizable functional group include a vinyl group, a propenyl group, and a (meth) acryloyl group.
- the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group. From the viewpoint of reactivity, a compound having a (meth) acryloyl group as a polymerizable functional group is preferably used as the polymerizable compound.
- the polymerizable compound may be used alone or in combination of two or more.
- examples of the polymerizable compound include a monomer having one polymerizable functional group (monofunctional monomer) and a monomer having a plurality of polymerizable functional groups (polyfunctional monomer).
- Examples of the monofunctional monomer include ethyl (meth) acrylate, n-butyl (meth) acrylate, ter-butyl (meth) acrylate, isobutyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and butoxydiethylene glycol (.
- Meta acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) Meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Meta) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol
- polyfunctional monomer examples include a bifunctional monomer, a trifunctional monomer, and a tetrafunctional or higher polyfunctional monomer.
- bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethierlenglucol dimethacrylate, 1,6-hexanediol di (meth).
- trifunctional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate.
- tetrafunctional or higher polyfunctional monomer examples include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. Examples thereof include pentaerythritol hexa (meth) acrylate.
- the polymerizable compound is preferably a polyfunctional monomer, more preferably a trifunctional monomer or a tetrafunctional or higher polyfunctional monomer.
- the trifunctional monomer for the polymerizable compound trimethylolpropane tri (meth) acrylate is preferably used, and trimethylolpropane triacrylate is more preferably used.
- the tetrafunctional or higher functional monomer for the polymerizable compound dipentaerythritol hexa (meth) acrylate is preferably used, and more preferably dipentaerythritol hexaacrylate is used.
- the amount of the polymerizable compound is preferably 5 parts by mass or more, more preferably 7 parts by mass or more with respect to 100 parts by mass of the base polymer. It is more preferably 9 parts by mass or more, and particularly preferably 10 parts by mass or more. From the viewpoint of ensuring sufficient adhesive strength in the cured pressure-sensitive adhesive layer 10, the blending amount of the polymerizable compound with respect to 100 parts by mass of the base polymer is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably. Is 43 parts by mass or less.
- the photopolymerization initiator is irradiated with active energy rays as a second external stimulus to initiate the polymerization reaction of the polymerizable compound.
- the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an ⁇ -ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, a photoactive oxime photopolymerization initiator, and a benzoin photopolymerization initiator.
- Examples thereof include an initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
- the colorant is preferably a compound (color-developing compound) that develops color by reaction with an acid. If the colorant is a color-developing compound, the tacky composition further contains an acid generator.
- color-developing compound examples include leuco dye, triarylmethane dye, diphenylmethane dye, fluorane dye, spiropyran dye, and rhodamine dye.
- the color-developing compound may be used alone or in combination of two or more.
- leuco dyes examples include 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene], 3-dibutylamino-.
- Examples of the triarylmethane dye include p, p', p "-tris-dimethylaminotriphenylmethane.
- Examples of the diphenylmethane dye include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether.
- Examples of the fluorane dye include 3-diethylamino-6-methyl-7-chlorofluorane.
- Examples of the spiropyran dye include 3-methylspirodinaphthopyrane.
- Examples of the rhodamine dye include 3-methylspirodinaphthopyrane.
- Rhodamine-B-anilinolactum can be mentioned.
- the color-developing compound is preferably a leuco 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 preferably 0.5 parts by mass or more, more preferably 1 part by mass or more.
- the blending amount is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
- 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 the first external stimulus can be discolored.
- an acid is generated from the photoacid generator, and the color-developing compound is colored by the acid. That is, the color-developing compound as a colorant can develop color by the first external stimulus.
- the portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays is colored, for example, in a dark color according to the color development of the color-developing compound.
- the type of the active energy ray as the first external stimulus is determined by the type of the photoacid generator (specifically, the wavelength of the active energy ray in which the photoacid generator generates an acid).
- Examples of 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 (first external stimulus).
- 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 tacky composition preferably contains an onium salt (onium compound) composed of sulfonium and C 4 F 9 HSO 3- as a photoacid generator.
- the pressure-sensitive adhesive layer 10 preferably has a ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator. It has a wavelength region of 2 or more in a wavelength range of 300 nm or more and 500 nm or less. The ratio is preferably 3 or more, more preferably 10 or more, still more preferably 50 or more, and particularly preferably 100 or more. The same ratio is, for example, 1 million or less.
- the blending amount of the acid generator with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more.
- the blending amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 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.
- the blending amount is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and further preferably 500 parts by mass or less.
- the adhesive composition may contain other components as needed.
- Other components include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
- the adhesive composition may contain a metal complex that can be coordinated and bonded to a coloring component such as a leuco dye.
- a metal complex can be used as a means for adjusting the pressure-sensitive adhesive layer 10 so as to satisfy the above formulas (1) and / or the formula (2).
- the metals constituting the metal ions of the metal complex are group 1 alkali metals and group 2 alkaline earth metals in the periodic table (IUPAC Periodic Table of the Elements (version date 19 February 2010); the same applies hereinafter).
- Group 3 to Group 12 transition metals preferably Group 2 alkaline earth metals and Group 3 to Group 12 transition metals are used.
- magnesium (Mg) is preferable as the metal from the viewpoint of the strong coordination bond between the carboxyl group and the metal that the leuco dye has in the form of a color-developing body.
- zinc (Zn) is preferable as the metal from the viewpoint of stabilizing the amphoteric counterion formed by the leuco dye and the metal complex.
- Examples of the ligand of the metal complex 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.
- a metal complex having a bidentate ligand is preferably used, and from the viewpoint of stabilizing the amphoteric counterion described above, zinc salicylate (specifically, zinc salicylate trihydration) is more preferable. Thing) is used.
- 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 parts by mass or more. be.
- 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 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).
- the adhesive sheet S is arranged on the release film L indicated by the virtual 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, and 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 to 200 ° C.
- the drying time is, for example, 5 seconds to 20 minutes.
- the cross-linking reaction proceeds at the same time as the above-mentioned drying or by aging thereafter.
- the aging conditions are appropriately set depending on the type of the cross-linking agent.
- the aging temperature is, for example, 20 ° C to 160 ° C.
- the aging time is, for example, 1 minute to 7 days.
- 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 a flexible plastic film that has been subjected to a surface release treatment, and the same film as described above can be used for the first release film.
- 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 preferably 10 ⁇ m or more, 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 preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the adhesive force exhibited by the adhesive sheet S on the stainless steel 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 after being bonded to the glass plate is, for example, 1 N / 25 mm or more. It is, for example, 50 N / 25 mm or less.
- the haze of the pressure-sensitive adhesive layer 10 is preferably 3% or less, more 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 T1 (average transmittance before UV irradiation) of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
- the average transmittance T1 is, for example, 100% 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 average transmittance T1 is determined by the method described later with respect to Examples.
- the average transmittance T2 of the pressure-sensitive adhesive layer 10 subjected to UV irradiation (specifically, UV irradiation under the conditions described later with respect to the second transmittance measurement in the second embodiment described later) at a wavelength of 400 to 700 nm is preferable. It is 50% or less, more preferably 40% or less, still more preferably 30% or less, and particularly preferably 25% or less.
- the average transmittance T2 is, for example, 0% or more. Such a configuration is preferable from the viewpoint of ensuring the function of the discolored portion in the pressure-sensitive adhesive layer 10 on which the discolored portion is formed.
- the average transmittance T2 is determined by the method described later with respect to Examples.
- the ratio of the average transmittance T2 to the average transmittance T1 (T2 / T1) is preferably 0.4 or less, more preferably 0.3 or less, and further preferably 0.2 or less.
- the ratio (T2 / T1) is, for example, 0.001 or more.
- the pressure-sensitive adhesive sheet S may be a single-sided pressure-sensitive adhesive sheet with a base material, which comprises 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 thereof.
- the substrate 20 contacts one side of the pressure-sensitive adhesive layer 10 in the thickness direction.
- 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 preferably 3% or less, more preferably 2% or less, still 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 preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and 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 preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less.
- the pressure-sensitive adhesive sheet S shown in FIG. 2 can be manufactured by the same method as the above-mentioned pressure-sensitive adhesive sheet manufacturing method except that the base material 20 is used instead of the first release film, for example.
- FIGS. 3A to 3D show an example of how to use the adhesive sheet S.
- the method includes a preparation step, a joining step, a curing 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 such as an organic EL 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 Z 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. Will be done.
- a second external stimulus is applied to the pressure-sensitive adhesive layer 10 in the laminate Z (in the case where the above inspection is performed, the laminate Z that has passed the inspection) to provide a pressure-sensitive adhesive.
- the layer 10 is cured.
- the second external stimulus is irradiation with active energy rays.
- This active energy ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32.
- the light source for irradiating the active energy ray in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp.
- a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
- the wavelength range of the active energy ray as the second external stimulus is different from that of the active energy ray as the first external stimulus.
- the active energy ray as the second external stimulus has a wavelength that does not substantially generate an acid in the acid generator.
- the lower limit of the wavelength range of the active energy ray is preferably 365 nm, more preferably 370 nm, still more preferably 375 nm, still more preferably 380 nm, still more preferably 385 nm, still more preferably 390 nm, and particularly preferably 395 nm.
- a photopolymerization initiator that initiates the polymerization reaction of the polymerizable compound by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
- the polymerization reaction of the polymerizable compound is started by the photopolymerization initiator, and the polymerization reaction proceeds.
- the elastic modulus of the pressure-sensitive adhesive layer 10 increases.
- the pressure-sensitive adhesive layer 10 has a wavelength region (wavelength region R) in which the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is 2 or more within the range of a wavelength of 300 nm or more and 500 nm or less. It is preferable to have it in.
- the ratio (Y / X) in the wavelength region R is preferably 3 or more, more preferably 10 or more, and further preferably 100 or more.
- at least a part of the wavelength of the active energy ray irradiated as the second external stimulus is in the wavelength region R. More preferably, all the wavelengths of the active energy rays irradiated as the second external stimulus are in the wavelength region R.
- Such a configuration in which an active energy ray having a wavelength within the wavelength region is given to the pressure-sensitive adhesive layer 10 as a second external stimulus cures the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step.
- the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is larger. preferable.
- the pressure-sensitive adhesive layer 10 in the laminated body Z is given a first external stimulus to form the discoloration portion 11 in the pressure-sensitive adhesive layer 10.
- a first 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 active energy ray (first active energy ray).
- the shape of the discolored portion 11 thus formed include a linear shape, a dot shape, a rectangular shape, a circular shape, an elliptical shape, and an indefinite shape.
- Examples of the light source for irradiating the active energy beam in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the activation energy ray irradiation in this step, a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
- the wavelength range of the first active energy ray is different from that of the above-mentioned active energy ray (second active energy ray) as the second external stimulus.
- the wavelength range of the first active energy ray preferably includes at least a range smaller than the wavelength range of the second active energy ray (wavelength range on the short wavelength side) (the wavelength range of the first active energy ray is the second active energy). It may include a range that overlaps with the wavelength range of the line).
- the first active energy ray has a lower limit in the wavelength range, or when the lower limit is set in the wavelength range of the first active energy ray by using, for example, a wavelength cut filter, the lower limit of the wavelength range of the first active energy ray is set.
- the first active energy ray may contain light having a wavelength of less than 300 nm.
- Light sources of such light include, for example, high pressure mercury lamps and metal halide lamps.
- the upper limit of the wavelength range of the first active energy ray is It is preferably 400 nm, more preferably 395 nm, more preferably 390 nm, even more preferably 385 nm, still more preferably 380 nm, still more preferably 375 nm, and particularly preferably 370 nm.
- a photoacid generator that generates an acid by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
- the adhesive sheet S can be used for joining between members.
- the metal is provided by providing the discolored portion 11 in a pattern shape corresponding to (that is, facing) the metal wiring formed on the pixel panel included in the panel. External light reflection in wiring can be suppressed.
- the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S contains a colorant capable of developing a color by a first external stimulus
- the pressure-sensitive adhesive sheet S is attached to an adherend (members 31, 32 in this embodiment).
- the pressure-sensitive adhesive layer 10 can be locally discolored by applying a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer 10.
- 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 pressure-sensitive adhesive layer 10 can be cured by a second external stimulus different from the first external stimulus, and in the pressure-sensitive adhesive layer 10, the first shear storage elastic modulus before curing is the same. It is 0.1 ⁇ 10 5 Pa or more and 10 ⁇ 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less.
- Such an adhesive sheet S is colored in the adhesive layer 10 (after curing) after bonding while ensuring the adhesive properties suitable for bonding to the adherend at the time of bonding in the adhesive layer 10 (before curing). Suitable for suppressing the diffusion of the agent.
- the diffusion of the colorant is suppressed, so that deterioration of the discolored portion 11 over time (bleeding, fading, non-uniformity of color, etc.) is suppressed.
- Suppressing the deterioration of the discolored portion 11 in the pressure-sensitive adhesive layer 10 is useful for maintaining the functional characteristics of the discolored portion 11 such as designability, shielding property, and antireflection property.
- 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 compounding amount (content), the physical property value, the parameter, etc. described below are the compounding 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.
- DPHA dipentaerythritol hexaacrylate
- Polymerization initiator (trade name "Omnirad 819", bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by IGM Resins BV) 0.1 part by mass and leuco dye as a color-developing compound (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 .2 parts by mass, photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured by ADEKA), 7.8 parts by mass, and isocyanate cross-linking as a cross-linking agent.
- photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured
- 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 and Comparative Examples described later).
- each component was blended in the blending amount shown in Table 1 in the preparation of the tacky composition.
- TMPTA trimethylolpropane triacrylate
- each component was blended in the blending amounts shown in Table 1 (the polymerizable compound and the photopolymerization initiator were not blended).
- 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 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 to 700 nm was measured at a pitch of 1 nm.
- the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as the baseline.
- the measured average transmittance T1 (average transmittance at a wavelength of 400 to 700 nm before UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1.
- the sample was irradiated with ultraviolet rays.
- the pressure-sensitive adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the same glass in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive by the UV irradiation).
- the leuco 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 to 390 nm). As described above, a measurement sample (second measurement sample) was prepared.
- the average transmittance at a wavelength of 400 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.
- the measured average transmittance T2 (average transmittance at a wavelength of 400 to 700 nm after UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1. Table 1 also shows the ratio of the average transmittance T2 to the above-mentioned average transmittance T1.
- Shear storage elastic modulus of adhesive layer (before hardening treatment)> The shear storage elastic modulus of the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 was examined by dynamic viscoelasticity measurement (first measurement).
- the sample for the first measurement was prepared as follows. First, 60 pressure-sensitive adhesive layers (thickness 25 ⁇ m) were laminated for each pressure-sensitive adhesive layer to be measured to obtain a laminated pressure-sensitive adhesive layer (thickness 1.5 mm). Next, a columnar pellet (thickness 1.5 mm, diameter 7.9 mm) as a first measurement sample was obtained by punching the laminated pressure-sensitive adhesive layer.
- a dynamic viscoelasticity measuring device (trade name "ARES", manufactured by Leometric Co., Ltd.) was used for the dynamic viscoelasticity measurement. Specifically, after fixing the measurement sample to the jig of the parallel plate having a diameter of 7.9 mm, the dynamic viscoelasticity measurement was carried out by the above-mentioned apparatus. In this measurement, the measurement mode was the shear mode, the measurement temperature range was ⁇ 70 ° C. to 250 ° C., the temperature rise rate was 5 ° C./min, and the frequency was 1 Hz. Table 1 shows the shear storage elastic modulus E1 of the pressure-sensitive adhesive layer (before the curing treatment) at 25 ° C.
- the sample for the second measurement (cylindrical pellet obtained by punching the laminated pressure-sensitive adhesive layer with a thickness of 1.5 mm) was irradiated with ultraviolet rays (curing treatment) on each of the 60 pressure-sensitive adhesive layers before stacking. Except for the above, it was prepared in the same manner as the first measurement sample. In the curing treatment, specifically, each pressure-sensitive adhesive layer before laminating was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50%.
- a UV-LED lamp having a wavelength of 405 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 2000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm).
- Table 1 shows the shear storage modulus E2 of the pressure-sensitive adhesive layer (after the curing treatment) at 25 ° C., 65 ° C., and 85 ° C.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 was cured by the UV irradiation).
- a UV-LED lamp having a wavelength of 405 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 an adhesive is applied through the base film.
- the layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm). Same as UV irradiation conditions).
- 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 is formed from a dry film photoresist arranged on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask is about 250 to 280 ⁇ m (the line width of the opening is the photomask). Different for each).
- 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.
- 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 to 390 nm).
- the line width of the linear discolored portion formed on the adhesive layer was measured (measurement of the initial line width). 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 observed. The area to be included 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 (W1) of the linear discolored 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 line width of the linear discolored portion in the adhesive layer of the adhesive sheet was measured.
- the specific measurement method is the same as the measurement method described above for the measurement of the initial line width.
- the line width W1 of the linear discolored portion before the first durability test, the line width W2 of the linear discolored portion after the first durability test, and the rate of increase of the line width W2 with respect to the line width W1 (W2 / W1). Is shown in Table 1. Further, the relationship between the shear storage elastic modulus of the pressure-sensitive adhesive layer at 85 ° C. (the shear storage elastic modulus of the cured pressure-sensitive adhesive layer in Examples 1 to 5) and the increase rate of the line width (W2 / W1) is shown. The graph is shown in FIG.
- the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 were formed in the same manner as described above except that the second durability test was performed instead of the first durability test. The degree of suppression of bleeding in the linear discolored part was investigated.
- the pressure-sensitive adhesive sheet having the linear discolored portion formed on the pressure-sensitive adhesive layer was heat-treated at 65 ° C. and 90% relative humidity for 120 hours.
- the line width W1 of the linear discolored portion before the second durability test, the line width W3 of the linear discolored portion after the second durability test, and the rate of increase of the line width W3 with respect to the line width W1 (W3 / W1). Is shown in Table 1.
- the rate of increase in line width (W2 / W1) of the linearly discolored portion after the first durability test is the shear storage at 25 ° C. with respect to the shear storage elastic modulus E1 of each of the adhesive sheets of Examples 1 to 5.
- the ratio of elastic modulus E2 (E2 / E1) was 2 or more and 300 or less), which was smaller than that of the pressure-sensitive adhesive sheet of Comparative Example 1.
- the rate of increase in the line width (W3 / W1) of the linearly discolored portion after the second durability test was also smaller in each of the pressure-sensitive adhesive sheets of Examples 1 to 5 than that of the pressure-sensitive adhesive sheet of Comparative Example 1. That is, in each of the pressure-sensitive adhesive sheets of Examples 1 to 5, bleeding of the discolored portion of the pressure-sensitive adhesive layer was suppressed as compared with the pressure-sensitive adhesive sheet of Comparative Example 1.
- 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
An adhesive sheet (S) according to the present invention is a variable color adhesive sheet which is provided with a variable color adhesive agent layer (20). The adhesive agent layer (20) contains an adhesive agent which can develop color as a result of a first outside stimulus, and can be cured by a second outside stimulus different from the first outside stimulus. A first shear storage modulus of elasticity at 25°C exhibited by the adhesive agent layer (20) prior to curing when subjected to dynamic viscoelasticity measurement under conditions of a frequency of 1 Hz and a heating speed of 5°C/min is 0.1 × 105 Pa or more and 10 × 105 Pa or less. A ratio, with respect to the first shear storage modulus of elasticity, of a second shear storage modulus of elasticity at 25°C displayed by the adhesive agent layer (20) after curing when subjected to dynamic viscoelasticity measurement under the aforementioned conditions is 2 or more and 300 or less.
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、被着体に対する当該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、当該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, a foreign substance between the adherend and the colored portion of the adhesive sheet is used after the adhesive sheet is attached to the adherend. And 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 the bonding.
一方、ディスプレイパネル用の透明粘着シートに設けられる着色部分の機能確保の観点からは、着色部分の劣化が抑制されることが求められる。
On the other hand, from the viewpoint of ensuring the function of the colored portion provided on the transparent adhesive sheet for the display panel, it is required to suppress the deterioration of the colored portion.
本発明は、被着体への貼合わせ後に粘着剤層の少なくとも一部を変色可能であって、当該粘着剤層の変色部分の劣化を抑制するのに適した、可変色粘着シートを提供する。
The present invention provides a variable color pressure-sensitive adhesive sheet capable of discoloring at least a part of the pressure-sensitive adhesive layer after being attached to an adherend and suitable for suppressing deterioration of the discolored portion of the pressure-sensitive adhesive layer. ..
本発明[1]は、変色可能な粘着剤層を備える可変色粘着シートであって、前記粘着剤層は、第1外部刺激によって発色可能な着色剤を含有し、前記第1外部刺激とは異なる第2外部刺激によって硬化可能であり、硬化前の前記粘着剤層が、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℃での第1せん断貯蔵弾性率は、0.1×105Pa以上10×105Pa以下であり、硬化後の前記粘着剤層が前記条件での動的粘弾性測定で示す25℃での第2せん断貯蔵弾性率の、前記第1せん断貯蔵弾性率に対する比率は、2以上300以下である、可変色粘着シートを含む。
The present invention [1] is a variable color pressure-sensitive adhesive sheet provided with a color-changing pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer contains a colorant capable of developing a color by a first external stimulus. The pressure-sensitive adhesive layer, which can be cured by a different second external stimulus, has a first shear storage at 25 ° C., as shown by dynamic viscoelastic measurements at a frequency of 1 Hz and a heating rate of 5 ° C./min. The elastic modulus is 0.1 × 10 5 Pa or more and 10 × 10 5 Pa or less, and the second shear storage elastic modulus at 25 ° C., which is shown by the dynamic viscoelastic measurement under the above conditions, for the adhesive layer after curing. The ratio of the first shear storage elastic modulus to the first shear storage elastic modulus is 2 or more and 300 or less, and includes a variable color pressure-sensitive adhesive sheet.
本発明[2]は、硬化後の前記粘着剤層に対して前記第1外部刺激を線状に付与することによって当該粘着剤層内に形成された変色領域の第1変色幅W1、および、当該粘着剤層を更に85℃で120時間加熱処理した後の前記変色領域の第2変色幅W2が、0.5≦W2/W1≦2を満たす、上記[1]に記載の可変色粘着シートを含む。
In the present invention [2], the first discoloration width W1 of the discoloration region formed in the pressure-sensitive adhesive layer by linearly applying the first external stimulus to the pressure-sensitive adhesive layer after curing, and The variable color pressure-sensitive adhesive sheet according to the above [1], wherein the second color change width W2 of the color change region after further heat-treating the pressure-sensitive adhesive layer at 85 ° C. for 120 hours satisfies 0.5 ≦ W2 / W1 ≦ 2. including.
本発明[3]は、硬化後の前記粘着剤層に対して前記第1外部刺激を線状に付与することによって当該粘着剤層内に形成された変色領域の第1変色幅W1、および、当該粘着剤層を更に65℃および相対湿度90%で120時間加熱処理した後の前記変色領域の第3変色幅W3が、0.5≦W3/W1≦2.4を満たす、上記[1]または[2]に記載の可変色粘着シートを含む。
In the present invention [3], the first discoloration width W1 of the discoloration region formed in the pressure-sensitive adhesive layer by linearly applying the first external stimulus to the pressure-sensitive adhesive layer after curing, and The third color change width W3 of the color change region after further heat-treating the pressure-sensitive adhesive layer at 65 ° C. and 90% relative humidity for 120 hours satisfies 0.5 ≦ W3 / W1 ≦ 2.4. Alternatively, the variable color adhesive sheet according to [2] is included.
本発明[4]は、前記着色剤が、酸との反応により発色する化合物であり、前記粘着剤層が、光酸発生剤を更に含有する、上記[1]から[3]のいずれか一つに記載の可変色粘着シートを含む。
The present invention [4] is any one of the above [1] to [3], wherein the colorant is a compound that develops a color by reacting with an acid, and the pressure-sensitive adhesive layer further contains a photoacid generator. Includes the variable color adhesive sheets described in 1.
本発明[5]は、前記粘着剤層が、10~300μmの厚さを有する、上記[1]から[4]のいずれか一つに記載の可変色粘着シートを含む。
The present invention [5] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the pressure-sensitive adhesive layer has a thickness of 10 to 300 μm.
本発明[6]は、前記粘着剤層の厚さ方向一方側に配置された基材を更に備える、上記[1]から[5]のいずれか一つに記載の可変色粘着シートを含む。
The present invention [6] includes the variable color pressure-sensitive adhesive sheet according to any one of the above [1] to [5], further comprising a base material arranged on one side in the thickness direction of the pressure-sensitive adhesive layer.
本発明の可変色粘着シートにおいては、粘着剤層が、上記のように、第1外部刺激によって発色可能な着色剤を含有する。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する第1外部刺激の付与により、当該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によると、貼り合わせ後であって粘着剤層の変色部分形成前に、同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。
In the variable color pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive layer contains a colorant capable of developing a color by a first external stimulus as described above. 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 a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer. According to such a variable color pressure-sensitive adhesive sheet, it is possible to inspect the presence or absence of foreign matter and air bubbles between the sheet and the adherend after bonding and before forming a discolored portion of the pressure-sensitive adhesive layer.
また、可変色粘着シートは、上記のように、粘着剤層が、第1外部刺激とは異なる第2外部刺激によって硬化可能であり、当該粘着剤層において、その硬化前の上記第1せん断貯蔵弾性率が0.1×105Pa以上10×105Pa以下であり、且つ当該第1せん断貯蔵弾性率に対する硬化後の上記第2せん断貯蔵弾性率の比率が2以上300以下である。このような可変色粘着シートは、被着体に対する貼り合わせに適した粘着特性を粘着剤層(硬化前)において貼り合わせ時に確保しつつ、貼り合わせ後の粘着剤層(硬化後)において着色剤の拡散を抑制するのに適する。変色部分が形成された粘着剤層においては、着色剤の拡散が抑制されることにより、変色部分の経時的な劣化(滲み、退色、色味の不均一化など)が抑制される。
Further, in the variable color pressure-sensitive adhesive sheet, as described above, the pressure-sensitive adhesive layer can be cured by a second external stimulus different from the first external stimulus, and in the pressure-sensitive adhesive layer, the first shear storage before the curing is performed. The elastic modulus is 0.1 × 10 5 Pa or more and 10 × 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less. Such a variable color adhesive sheet secures adhesive properties suitable for bonding to an adherend at the time of bonding in the pressure-sensitive adhesive layer (before curing), and a colorant in the pressure-sensitive adhesive layer (after curing) after bonding. Suitable for suppressing the diffusion of. In the pressure-sensitive adhesive layer on which the discolored portion is formed, the diffusion of the colorant is suppressed, so that deterioration of the discolored portion over time (bleeding, fading, non-uniformity of color, etc.) is suppressed.
本発明の可変色粘着シートの一実施形態としての粘着シート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、所定の厚さのシート形状を有し、厚さ方向と直交する方向(面方向)に延びる。粘着シートSは、例えば、有機ELパネルなどのディスプレイパネル(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)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 as an embodiment of the variable-color pressure-sensitive adhesive sheet of the present invention includes the 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 adhesive sheet S is used, for example, as a transparent adhesive sheet arranged on the image display side of the pixel panel in a display panel such as an organic EL panel (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。粘着剤層10は、後述の第1外部刺激によって発色可能な着色剤を含有し、第1外部刺激を受けた部分が変色可能である。具体的には、粘着剤層10は、第1外部刺激を受けた部分の透明性が低下可能である。また、粘着剤層10は、第1外部刺激とは異なる後述の第2外部刺激によって硬化可能である。
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 pressure-sensitive adhesive layer 10 contains a colorant that can be colored by the first external stimulus described later, and the portion that has been subjected to the first external stimulus can be discolored. Specifically, the pressure-sensitive adhesive layer 10 can reduce the transparency of the portion that has been subjected to the first external stimulus. Further, the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus described later, which is different from the first external stimulus.
硬化前の粘着剤層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(第1せん断貯蔵弾性率)は、0.1×105Pa以上10×105Pa以下である。これとともに、硬化後の粘着剤層10が、上記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(第2せん断貯蔵弾性率)の、第1せん断貯蔵弾性率に対する比率は、2以上300以下である。
The shear storage elastic modulus (first shear storage elastic modulus) at 25 ° C. shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 before curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min is 0. .1 × 10 5 Pa or more and 10 × 10 5 Pa or less. At the same time, the ratio of the shear storage elastic modulus (second shear storage elastic modulus) at 25 ° C. shown by the dynamic viscoelasticity measurement under the above conditions to the first shear storage elastic modulus of the cured pressure-sensitive adhesive layer 10 is 2 or more and 300 or less.
粘着シートSにおいては、粘着剤層10が、上述のように、第1外部刺激によって発色可能な着色剤を含有する。そのため、粘着シートSを被着体に貼り合わせた後、粘着剤層10における変色予定部分(粘着剤層の少なくとも一部)において、当該部分に対する第1外部刺激の付与によって粘着剤層10を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に変色部分を形成できる粘着シートSによると、貼り合わせ後であって粘着剤層10の変色部分形成前に、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 colorant that can be colored by a first external stimulus, as described above. Therefore, after the pressure-sensitive adhesive sheet S is attached to the adherend, the pressure-sensitive adhesive layer 10 is discolored by applying a first external stimulus to the portion to be discolored (at least a part of the pressure-sensitive adhesive layer) in the pressure-sensitive adhesive layer 10. Can be made to. According to the pressure-sensitive adhesive sheet S capable of forming a discolored portion 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 bonding and before the discolored portion of the pressure-sensitive adhesive layer 10 is formed. The presence of foreign matter and air bubbles in between can be inspected.
また、粘着シートSは、上述のように、粘着剤層10が、第1外部刺激とは異なる第2外部刺激によって硬化可能であり、当該粘着剤層10において、その硬化前の上記第1せん断貯蔵弾性率が0.1×105Pa以上10×105Pa以下であり、且つ当該第1せん断貯蔵弾性率に対する硬化後の上記第2せん断貯蔵弾性率の比率が2以上300以下である。このような粘着シートSは、被着体に対する貼り合わせに適した粘着特性を粘着剤層10(硬化前)において貼り合わせ時に確保しつつ、貼り合わせ後の粘着剤層10(硬化後)において着色剤の拡散を抑制するのに適する。変色部分が形成された粘着剤層10においては、着色剤の拡散が抑制されることにより、変色部分の経時的な劣化(滲み、退色、色味の不均一化など)が抑制される。
Further, as described above, in the pressure-sensitive adhesive sheet S, the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus different from the first external stimulus, and the pressure-sensitive adhesive layer 10 has the first shear before its curing. The storage elastic modulus is 0.1 × 10 5 Pa or more and 10 × 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less. Such an adhesive sheet S is colored in the adhesive layer 10 (after curing) after bonding while ensuring the adhesive properties suitable for bonding to the adherend at the time of bonding in the adhesive layer 10 (before curing). Suitable for suppressing the diffusion of the agent. In the pressure-sensitive adhesive layer 10 on which the discolored portion is formed, the diffusion of the colorant is suppressed, so that deterioration of the discolored portion over time (bleeding, fading, non-uniformity of color, etc.) is suppressed.
以上のように、粘着シートSは、被着体への貼合わせ後に粘着剤層10の少なくとも一部を変色可能であって、当該粘着剤層10の変色部分の劣化を抑制するのに適する。粘着剤層10における変色部分の劣化の抑制は、意匠性、遮蔽性、反射防止性など、変色部分が担う機能特性の維持に役立つ。
As described above, the pressure-sensitive adhesive sheet S can discolor at least a part of the pressure-sensitive adhesive layer 10 after being attached to the adherend, and is suitable for suppressing deterioration of the discolored portion of the pressure-sensitive adhesive layer 10. Suppressing the deterioration of the discolored portion in the pressure-sensitive adhesive layer 10 is useful for maintaining the functional characteristics of the discolored portion such as designability, shielding property, and antireflection property.
粘着剤層10の上述の第1せん断貯蔵弾性率は、好ましくは0.2×105Pa以上、より好ましくは0.3×105Pa以上である。第1せん断貯蔵弾性率は、好ましくは5×105Pa以下、より好ましくは3×105Pa以下である。これら構成は、被着体に対する貼り合わせに適した粘着特性(粘着力およびタック性など)を粘着剤層10(硬化前)において確保するのに適する。
The above-mentioned first shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is preferably 0.2 × 10 5 Pa or more, and more preferably 0.3 × 10 5 Pa or more. The first shear storage elastic modulus is preferably 5 × 10 5 Pa or less, more preferably 3 × 10 5 Pa or less. These configurations are suitable for ensuring the adhesive properties (adhesive strength, tackiness, etc.) suitable for bonding to the adherend in the pressure-sensitive adhesive layer 10 (before curing).
粘着剤層10において、第1せん断貯蔵弾性率に対する第2せん断貯蔵弾性率の上記比率は、好ましくは5以上、より好ましくは10以上である。同比率は、好ましくは250以下、より好ましくは100以下、更に好ましくは50以下、特に好ましくは30以下である。これら構成は、硬化前の粘着剤層10における上述の粘着特性と、硬化後の粘着剤層10における上述の着色剤拡散抑制との、両立を図るのに適する。
In the pressure-sensitive adhesive layer 10, the ratio of the second shear storage elastic modulus to the first shear storage elastic modulus is preferably 5 or more, more preferably 10 or more. The ratio is preferably 250 or less, more preferably 100 or less, still more preferably 50 or less, and particularly preferably 30 or less. These configurations are suitable for achieving both the above-mentioned adhesive properties in the pressure-sensitive adhesive layer 10 before curing and the above-mentioned suppression of diffusion of the colorant in the pressure-sensitive adhesive layer 10 after curing.
粘着剤層10の上記第1せん断貯蔵弾性率の調整は、例えば、粘着剤層10に含有されるベースポリマーなどポリマー成分における構成モノマー組成の調整、ポリマー成分の分子量(例えば重量平均分子量)の調整、ポリマー成分を架橋する架橋剤の利用、および、粘着剤層10におけるポリマー成分の含有割合の調整によって、実現できる。粘着剤層10の第1せん断貯蔵弾性率の調整は、例えば、粘着剤層10に硬化用成分として含有されるモノマー成分の種類の選択、および、粘着剤層10におけるモノマー成分の含有割合の調整によって、実現してもよい。
The adjustment of the first shear storage elasticity of the pressure-sensitive adhesive layer 10 is, for example, adjustment of the constituent monomer composition in the polymer component such as the base polymer contained in the pressure-sensitive adhesive layer 10, and adjustment of the molecular weight (for example, weight average molecular weight) of the polymer component. This can be achieved by using a cross-linking agent for cross-linking the polymer component and adjusting the content ratio of the polymer component in the pressure-sensitive adhesive layer 10. The adjustment of the first shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is, for example, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10 and adjustment of the content ratio of the monomer component in the pressure-sensitive adhesive layer 10. May be realized by.
粘着剤層10の上記第2せん断貯蔵弾性率の調整は、例えば、粘着剤層10に硬化用成分として含有されるモノマー成分の種類の選択、粘着剤層10におけるモノマー成分の含有割合の調整、および、粘着剤層10に含有されるベースポリマーなどポリマー成分を架橋する架橋剤の利用によって、実現できる。第2せん断貯蔵弾性率の調整は、例えば、粘着剤層10におけるポリマー成分の構成モノマー組成の調整、ポリマー成分の分子量の調整、および、粘着剤層10におけるポリマー成分の含有割合の調整によって、実現してもよい。
The adjustment of the second shear storage elasticity of the pressure-sensitive adhesive layer 10 includes, for example, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10, adjustment of the content ratio of the monomer component in the pressure-sensitive adhesive layer 10. It can also be realized by using a cross-linking agent that cross-links a polymer component such as a base polymer contained in the pressure-sensitive adhesive layer 10. The adjustment of the second shear storage elastic modulus is realized by, for example, adjusting the composition of the constituent monomers of the polymer component in the pressure-sensitive adhesive layer 10, adjusting the molecular weight of the polymer component, and adjusting the content ratio of the polymer component in the pressure-sensitive adhesive layer 10. You may.
第1せん断貯蔵弾性率に対する第2せん断貯蔵弾性率の上記比率の調整は、例えば、粘着剤層10に含有されるベースポリマーなどポリマー成分における構成モノマー組成の調整、ポリマー成分の分子量の調整、粘着剤層10におけるポリマー成分の含有割合の調整、ポリマー成分を架橋する架橋剤の利用、粘着剤層10に硬化用成分として含有されるモノマー成分の種類の選択、および、粘着剤層10におけるモノマー成分の含有割合の調整によって、実現できる。
The adjustment of the ratio of the second shear storage elasticity to the first shear storage elasticity is, for example, adjustment of the constituent monomer composition in the polymer component such as the base polymer contained in the pressure-sensitive adhesive layer 10, adjustment of the molecular weight of the polymer component, and adhesion. Adjustment of the content ratio of the polymer component in the agent layer 10, use of a cross-linking agent for cross-linking the polymer component, selection of the type of monomer component contained as a curing component in the pressure-sensitive adhesive layer 10, and the monomer component in the pressure-sensitive adhesive layer 10. It can be realized by adjusting the content ratio of.
粘着シートSにおいて、硬化後の粘着剤層10に対して第1外部刺激を線状に付与することによって当該粘着剤層10内に形成された変色領域の第1変色幅W1、および、当該粘着剤層10を更に85℃で120時間加熱処理した後の変色領域の第2変色幅W2は、下記の式(1)を満たす。
In the pressure-sensitive adhesive sheet S, the first discoloration width W1 of the discoloration region formed in the pressure-sensitive adhesive layer 10 by linearly applying the first external stimulus to the pressure-sensitive adhesive layer 10 after curing, and the pressure-sensitive adhesive. The second color change width W2 of the color change region after the agent layer 10 is further heat-treated at 85 ° C. for 120 hours satisfies the following formula (1).
0.5≦W2/W1≦2 ・・・(1)
0.5 ≤ W2 / W1 ≤ 2 ... (1)
このような構成は、粘着剤層10に形成される変色部分の劣化(滲み、退色、色味の不均一化など)を抑制するのに適し、従って、変色部分が担う機能特性の維持に役立つ。
Such a configuration is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion formed on the pressure-sensitive adhesive layer 10, and therefore is useful for maintaining the functional characteristics of the discolored portion. ..
硬化後の粘着剤層10に対して第1外部刺激を線状に付与することによって当該粘着剤層10内に形成された変色領域の第1変色幅W1、および、当該粘着剤層10を更に65℃および相対湿度90%で120時間加熱処理した後の変色領域の第3変色幅W3は、下記の式(2)を満たす。
By linearly applying the first external stimulus to the cured pressure-sensitive adhesive layer 10, the first color change width W1 of the color change region formed in the pressure-sensitive adhesive layer 10 and the pressure-sensitive adhesive layer 10 are further added. The third color change width W3 of the color change region after heat treatment at 65 ° C. and 90% relative humidity for 120 hours satisfies the following formula (2).
0.5≦W3/W1≦2.4 ・・・(2)
0.5 ≤ W3 / W1 ≤ 2.4 ... (2)
このような構成は、粘着剤層10に形成される変色部分の劣化(滲み、退色、色味の不均一化など)を抑制するのに適し、従って、変色部分が担う機能特性の維持に役立つ。
Such a configuration is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion formed on the pressure-sensitive adhesive layer 10, and therefore is useful for maintaining the functional characteristics of the discolored portion. ..
粘着剤層10の上述の第2せん断貯蔵弾性率は、好ましくは0.2×105Pa以上、より好ましくは2×105Pa以上、更に好ましくは5×105Pa以上である。このような構成は、第1外部刺激によって変色部分が形成された粘着剤層10において、変色部分の着色剤の拡散を抑制するのに適し、従って、変色部分の劣化を抑制するのに適する。
また、第2せん断貯蔵弾性率は、好ましくは100×105Pa以下、より好ましくは50×105Pa以下、更に好ましくは25×105Pa以下である。このような構成は、硬化後の粘着剤層10において、被着体に対する粘着力を確保するのに適する。また、第2せん断貯蔵弾性率に関するこれら構成は、上記の式(1)を満たすように粘着剤層10を調整するうえで好ましく、また、上記の式(1)を満たすように粘着剤層10を調整するうえで好ましい。粘着剤層10の第2せん断貯蔵弾性率の調整により、上記の式(1)および/または式(2)を満たすように粘着剤層10を調整できる。 The above-mentioned second shear storage elastic modulus of the pressure-sensitive adhesive layer 10 is preferably 0.2 × 10 5 Pa or more, more preferably 2 × 10 5 Pa or more, and further preferably 5 × 10 5 Pa or more. Such a configuration is suitable for suppressing the diffusion of the colorant in the discolored portion in the pressure-sensitive adhesive layer 10 in which the discolored portion is formed by the first external stimulus, and is therefore suitable for suppressing the deterioration of the discolored portion.
The second shear storage elastic modulus is preferably 100 × 10 5 Pa or less, more preferably 50 × 10 5 Pa or less, and further preferably 25 × 10 5 Pa or less. Such a configuration is suitable for ensuring the adhesive force with respect to the adherend in theadhesive layer 10 after curing. Further, these configurations regarding the second shear storage elastic modulus are preferable for adjusting the pressure-sensitive adhesive layer 10 so as to satisfy the above formula (1), and the pressure-sensitive adhesive layer 10 so as to satisfy the above formula (1). It is preferable to adjust. By adjusting the second shear storage elastic modulus of the pressure-sensitive adhesive layer 10, the pressure-sensitive adhesive layer 10 can be adjusted so as to satisfy the above formulas (1) and / or formula (2).
また、第2せん断貯蔵弾性率は、好ましくは100×105Pa以下、より好ましくは50×105Pa以下、更に好ましくは25×105Pa以下である。このような構成は、硬化後の粘着剤層10において、被着体に対する粘着力を確保するのに適する。また、第2せん断貯蔵弾性率に関するこれら構成は、上記の式(1)を満たすように粘着剤層10を調整するうえで好ましく、また、上記の式(1)を満たすように粘着剤層10を調整するうえで好ましい。粘着剤層10の第2せん断貯蔵弾性率の調整により、上記の式(1)および/または式(2)を満たすように粘着剤層10を調整できる。 The above-mentioned second shear storage elastic modulus of the pressure-
The second shear storage elastic modulus is preferably 100 × 10 5 Pa or less, more preferably 50 × 10 5 Pa or less, and further preferably 25 × 10 5 Pa or less. Such a configuration is suitable for ensuring the adhesive force with respect to the adherend in the
また、上記の式(1)および/または式(2)を満たすように粘着剤層10を調整する手法としては、第1せん断貯蔵弾性率と、第1せん断貯蔵弾性率に対する第2せん断貯蔵弾性率の比率とを、上記範囲内に維持した状態で、例えば次のような方法を適用することも挙げられる。粘着剤層(粘着性組成物)に金属錯体を配合する方法(第1の方法)、粘着剤層中の着色用成分として、他の成分に結合された成分を用いる方法(第2の方法)、および、互いに非相溶または低相溶の少なくとも2成分によって形成される海島構造における島部に着色成分を設ける方法(第3の方法)などである。
Further, as a method for adjusting the pressure-sensitive adhesive layer 10 so as to satisfy the above formulas (1) and / or the formula (2), a first shear storage elastic modulus and a second shear storage elastic modulus with respect to the first shear storage elastic modulus are used. It is also possible to apply, for example, the following method while maintaining the ratio of the rate within the above range. A method of blending a metal complex in a pressure-sensitive adhesive layer (tacky composition) (first method), and a method of using a component bonded to another component as a coloring component in the pressure-sensitive adhesive layer (second method). , And a method (third method) of providing a colored component on an island portion in a sea-island structure formed by at least two components that are incompatible with each other or have low phase compatibility with each other.
第1の方法における金属錯体については、後述する。
The metal complex in the first method will be described later.
第2の方法としては、例えば、所定の色に発色可能な成分が結合されたポリマーを、粘着剤層中のベースポリマーなどポリマー成分と着色成分とを兼用する成分として用いる方法、当初は互いに分離した状態をとる着色成分とポリマー成分とを粘着剤層中での反応を経て結合させる方法、および、これらを組み合わせた方法が、挙げられる。
As a second method, for example, a method in which a polymer in which a component capable of developing a color in a predetermined color is bonded is used as a component having both a polymer component and a coloring component such as a base polymer in an adhesive layer, initially separated from each other. Examples thereof include a method in which a coloring component and a polymer component in a state of being bonded are bonded through a reaction in a pressure-sensitive adhesive layer, and a method in which these are combined.
第3の方法としては、例えば、着色成分との相溶性が高い第1ポリマー成分と、着色成分との相溶性が低い第2ポリマー成分とを、粘着剤層中のポリマー成分として用い、且つ当該粘着剤層において第1ポリマー成分が島部をなす海島構造を形成することによって、着色成分を島部に設ける方法が挙げられる。
As a third method, for example, a first polymer component having a high compatibility with the coloring component and a second polymer component having a low compatibility with the coloring component are used as the polymer component in the pressure-sensitive adhesive layer, and the present invention is used. A method of providing the coloring component on the island portion by forming a sea-island structure in which the first polymer component forms an island portion in the pressure-sensitive adhesive layer can be mentioned.
粘着剤層10は、第1外部刺激によって発色可能な着色剤に加えて、例えば、ベースポリマーと、重合性化合物と、光重合開始剤とを含有する。
The pressure-sensitive adhesive layer 10 contains, for example, a base polymer, a polymerizable compound, and a photopolymerization initiator in addition to a colorant that can be colored by a first external stimulus.
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、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上である。
The content ratio of the base polymer in the pressure-sensitive adhesive layer 10 is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass, from the viewpoint of appropriately expressing the function of the base polymer in the pressure-sensitive adhesive layer 10. % 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、更に好ましくは、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 eicocil (meth) acrylate. 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、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上である。同割合は、例えば99質量%以下である。
The ratio of the (meth) acrylic acid alkyl ester in the monomer component is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 60% by mass or more, 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が挙げられる。極性基含有モノマーとしては、例えば、水酸基含有モノマー、窒素原子含有環を有するモノマー、および、カルボキシ基含有モノマーが挙げられる。極性基含有モノマーは、アクリルポリマーへの架橋点の導入、アクリルポリマーの凝集力の確保など、アクリルポリマーの改質に役立つ。
The 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. 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 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.
共重合性モノマーは、好ましくは、水酸基含有モノマー、窒素原子含有環を有するモノマー、および、カルボキシ基含有モノマーからなる群から選択される少なくとも一種を含む。より好ましくは、共重合性モノマーは、水酸基含有モノマーおよび/または窒素原子含有環を有するモノマーを含む。
The copolymerizable monomer preferably contains at least one selected from the group consisting of 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 ( Examples include 4-hydroxymethylcyclohexyl) methyl (meth) acrylate. As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate is preferably used, and 2-hydroxyethyl acrylate is more preferably used.
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、好ましくは1質量%以上、より好ましくは3質量%以上、更に好ましくは5質量%以上である。同割合は、アクリルポリマー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、好ましくは30質量%以下、より好ましくは20質量%以下である。
The ratio of the hydroxyl group-containing monomer in the monomer component is preferably 1% by mass or more, 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 preferable 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). Is 30% by mass or less, more 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 are 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、好ましくは1質量%以上、より好ましくは3質量%以上、更に好ましくは5質量%以上である。同割合は、アクリルポリマーのガラス転移温度の調整、および、アクリルポリマーの極性(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、好ましくは30質量%以下、より好ましくは20質量%以下である。
The ratio of the monomer having a nitrogen atom-containing ring in the monomer component is preferably 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 more preferably 3% by mass or more, still more preferably 5% by mass or more. The same ratio is preferably 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, more 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、好ましくは1質量%以上、より好ましくは3質量%以上、更に好ましくは5質量%以上である。同割合は、アクリルポリマーのガラス転移温度の調整、および、酸による被着体の腐食リスクの回避の観点からは、好ましくは30質量%以下、より好ましくは20質量%以下である。
The ratio of the 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. It is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The same ratio is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of adjusting the glass transition temperature of the acrylic polymer and 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. , 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 acrylates 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、(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、N-ビニルアセトアミドなどの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。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。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。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 the amide group-containing monomer include N-vinylcarboxylic acid amides such as (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N-alkyl (meth) acrylamide, and N-vinylacetamide, and N-hydroxyalkyl. Examples include (meth) acrylamide, N-alkoxyalkyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N- (meth) acryloylmorpholin. 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. Examples of N-alkyl (meth) acrylamide include N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. 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. Be done.
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 can be mentioned.
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. , Butoxyethyl (meth) acrylate, and ethoxypropyl (meth) 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、上述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。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質量部以上であり、また、例えば1質量部以下である。
Acrylic polymer can be formed by polymerizing the above-mentioned 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. As the polymerization initiator, for example, a thermal polymerization initiator is used. The amount of the polymerization initiator used is, for example, 0.05 parts by mass or more and, for example, 1 part by mass or less with respect to 100 parts by mass of the monomer component.
熱重合開始剤としては、例えば、アゾ重合開始剤および過酸化物重合開始剤が挙げられる。アゾ重合開始剤としては、例えば、2,2'-アゾビスイソブチロニトリル、2,2'-アゾビス-2-メチルブチロニトリル、2,2'-アゾビス(2-メチルプロピオン酸)ジメチル、4,4'-アゾビス-4-シアノバレリアン酸、アゾビスイソバレロニトリル、2,2'-アゾビス(2-アミジノプロパン)ジヒドロクロライド、2,2'-アゾビス[2-(5-メチル-2-イミダゾリン-2-イル)プロパン]ジヒドロクロライド、2,2'-アゾビス(2-メチルプロピオンアミジン)二硫酸塩、および、2,2'-アゾビス(N,N'-ジメチレンイソブチルアミジン)ジヒドロクロライドが挙げられる。過酸化物重合開始剤としては、例えば、ジベンゾイルペルオキシド、t-ブチルペルマレエ-ト、および過酸化ラウロイルが挙げられる。
Examples of the thermal polymerization initiator include an azo polymerization initiator and a peroxide polymerization initiator. Examples of the azo 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 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、好ましくは100000以上、より好ましくは300000以上、更に好ましくは500000以上である。同重量平均分子量は、好ましくは5000000以下、より好ましくは3000000以下、更に好ましくは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 preferably 100,000 or more, more preferably 300,000 or more, still 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 preferably 5,000,000 or less, more preferably 3,000,000 or less, still 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、好ましくは0℃以下、より好ましくは-10℃以下、更に好ましくは-20℃以下である。同ガラス転移温度は、例えば-80℃以上である。
The glass transition temperature (Tg) of the base polymer is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, still more preferably −20 ° C. or lower. The glass transition temperature is, for example, −80 ° C. or higher.
ポリマーのガラス転移温度(Tg)については、下記のFoxの式に基づき求められるガラス転移温度(理論値)を用いることができる。Foxの式は、ポリマーのガラス転移温度Tgと、当該ポリマーを構成するモノマーのホモポリマーのガラス転移温度Tgiとの関係式である。下記のFoxの式において、Tgはポリマーのガラス転移温度(℃)を表し、Wiは当該ポリマーを構成するモノマーiの重量分率を表し、Tgiは、モノマーiから形成されるホモポリマーのガラス転移温度(℃)を示す。ホモポリマーのガラス転移温度については文献値を用いることができ、例えば、「Polymer Handbook」(第4版,John Wiley & Sons, Inc., 1999年)および「新高分子文庫7 塗料用合成樹脂入門」(北岡協三著,高分子刊行会,1995年)には、各種のホモポリマーのガラス転移温度が挙げられている。一方、モノマーのホモポリマーのガラス転移温度については、特開2007-51271号公報に具体的に記載されている方法によって求めることも可能である。
For the glass transition temperature (Tg) of the polymer, the glass transition temperature (theoretical value) obtained based on the 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 formula below, Tg represents the glass transition temperature (° C.) of the polymer, Wi represents the weight fraction of the monomer i constituting the polymer, and Tgi represents the glass transition of the homopolymer formed from the monomer i. Indicates the temperature (° C). Literature values can be used for the glass transition temperature of homopolymers, for example, "Polymer Handbook" (4th edition, John Wiley & Sons, Inc., 1999) and "New Polymer Bunko 7 Introduction to Synthetic Resins for Paints". (Kyozo Kitaoka, Polymer Publications, 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.
Foxの式 1/(273+Tg)=Σ[Wi/(273+Tgi)]
Fox formula 1 / (273 + Tg) = Σ [Wi / (273 + Tgi)]
粘着性組成物は、ベースポリマーへの架橋構造の導入の観点から、架橋剤を含有してもよい。架橋剤としては、例えば、イソシアネート架橋剤、エポキシ架橋剤、オキサゾリン架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、および金属キレート架橋剤が挙げられる。架橋剤は、単独で用いられてもよいし、二種類以上が併用されてもよい。
The 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。当該イソシアネート誘導体としては、例えば、イソシアヌレート変性体およびポリオール変性体が挙げられる。イソシアネート架橋剤の市販品としては、例えば、コロネートL(トリレンジイソシアネートのトリメチロールプロパンアダクト体,東ソー製)、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 isocyanates and polymethylene polyphenyl isocyanates. Further, examples of the isocyanate cross-linking agent include derivatives of these isocyanates. Examples of the isocyanate derivative 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、ビスフェノールA、エピクロルヒドリン型のエポキシ樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、1,6-ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、N,N,N',N'-テトラグリシジル-m-キシリレンジアミン、および1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサンが挙げられる。
Examples of 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.
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質量部以上であり、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, based on 100 parts by mass of the base polymer. It is preferably 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 3 parts by mass. It is as follows.
ベースポリマーに架橋構造が導入される場合、架橋反応を効果的に進行させるために架橋触媒が用いられてもよい。架橋触媒としては、例えば、ジラウリン酸ジブチルスズ、テトラ-n-ブチルチタネート、テトライソプロピルチタネート、ナーセム第二鉄、およびブチルスズオキシドが挙げられ、好ましくはジラウリン酸ジブチルスズが用いられる。架橋触媒の使用量は、ベースポリマー100質量部に対して例えば0.0001質量部以上であり、また、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 dibutyltin dilaurate, tetra-n-butyl titanate, tetraisopropyl titanate, ferric nasem, and butyltin oxide, and dibutyltin dilaurate is preferably used. The amount of the cross-linking catalyst used is, for example, 0.0001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the base polymer.
架橋触媒が用いられる場合、粘着性組成物から事後的に除去可能な架橋抑制剤が粘着性組成物に配合されてもよい。架橋触媒としてジラウリン酸ジブチルスズが用いられる場合、架橋抑制剤としては、好ましくはアセチルアセトンが用いられる。この場合、粘着性組成物においては、アセチルアセトンがジラウリン酸ジブチルスズに配位し、ベールポリマーに対する架橋剤の架橋反応は抑制される。粘着シートSの後述の製造過程において、剥離フィルム上に粘着性組成物が塗布されて塗膜が形成された後、所望のタイミングでの加熱により、アセチルアセトンを揮発させて塗膜から除去できる。これにより、架橋剤の架橋反応を進行させることができる。
When a cross-linking catalyst is used, a cross-linking inhibitor that can be removed ex post facto from the sticky composition may be added to the sticky composition. When dibutyltin dilaurate is used as the cross-linking catalyst, acetylacetone is preferably used as the cross-linking inhibitor. In this case, in the adhesive composition, acetylacetone coordinates with dibutyltin dilaurate, and the cross-linking reaction of the cross-linking agent with the veil polymer is suppressed. In the manufacturing process described later for the pressure-sensitive adhesive sheet S, after the pressure-sensitive adhesive composition is applied onto the release film to form a coating film, acetylacetone can be volatilized and removed from the coating film by heating at a desired timing. This makes it possible to proceed with the cross-linking reaction of the cross-linking agent.
架橋抑制剤の配合量は、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1000質量部以上である。同配合量は、例えば5000質量部以下である。
The blending amount of the cross-linking inhibitor is, for example, 100 parts by mass or more, preferably 1000 parts by mass or more with respect to 100 parts by mass of the cross-linking catalyst. The blending amount is, for example, 5000 parts by mass or less.
重合性化合物は、重合性官能基を有する化合物である。当該重合性官能基は、エチレン性不飽和二重結合を有する。重合性官能基としては、例えば、ビニル基、プロペニル基、および、(メタ)アクリロイル基が挙げられる。(メタ)アクリロイル基は、アクリロイル基および/またはメタクリロイル基を意味する。反応性の観点からは、重合性官能基として(メタ)アクリロイル基を有する化合物が、重合性化合物として用いられるのが好ましい。
重合性化合物は、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。 The polymerizable compound is a compound having a polymerizable functional group. The polymerizable functional group has an ethylenically unsaturated double bond. Examples of the polymerizable functional group include a vinyl group, a propenyl group, and a (meth) acryloyl group. The (meth) acryloyl group means an acryloyl group and / or a methacryloyl group. From the viewpoint of reactivity, a compound having a (meth) acryloyl group as a polymerizable functional group is preferably used as the polymerizable compound.
The polymerizable compound may be used alone or in combination of two or more.
重合性化合物は、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。 The polymerizable compound is a compound having a polymerizable functional group. The polymerizable functional group has an ethylenically unsaturated double bond. Examples of the polymerizable functional group include a vinyl group, a propenyl group, and a (meth) acryloyl group. The (meth) acryloyl group means an acryloyl group and / or a methacryloyl group. From the viewpoint of reactivity, a compound having a (meth) acryloyl group as a polymerizable functional group is preferably used as the polymerizable compound.
The polymerizable compound may be used alone or in combination of two or more.
また、重合性化合物としては、例えば、一つの重合性官能基を有するモノマー(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。
Further, examples of the polymerizable compound include a monomer having one polymerizable functional group (monofunctional monomer) and a monomer having a plurality of polymerizable functional groups (polyfunctional monomer).
単官能モノマーとしては、例えば、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、ter-ブチル(メタ)アクリレート、イソブチルメタクリレート、2-エチルヘキシル(メタ)アクリレート、イソデシル(メタ)アクリレート、ブトキシジエチレングリコール(メタ)アクリレート、メトキシポリエチレングリコール(メタ)アクリレート、グリシジル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、カプロラクトン変性テトラヒドロフルフリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシ(メタ)アクリレート、イソボルニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、フェノキシジエチレングリコール(メタ)アクリレート、フェノキシテトラエチレングリコール(メタ)アクリレート、ノニルフェノキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、グリセロール(メタ)アクリレート、トリフロロエチル(メタ)アクリレート、メタクリロキシオキシエチルアシッドフォスフェート、2-ヒドロキシエチルメタクリル酸フォスフェート、γ-メタクリロキシプロピルトリメトキシシラン、γ-アクリロキシプロピルトリメトキシシラン、アクリロイルモルホリン、モルホリノエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、およびN,N-ジメチルアミノエチル(メタ)アクリレートが挙げられる。
Examples of the monofunctional monomer include ethyl (meth) acrylate, n-butyl (meth) acrylate, ter-butyl (meth) acrylate, isobutyl methacrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and butoxydiethylene glycol (. Meta) acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) Meta) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Meta) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, trifluoroethyl (meth) acrylate, methacryloxyoxyethyl acid phosphate, 2-hydroxyethyl methacrylate phosphate, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, acryloylmorpholin, morpholinoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and N, N-dimethylamino Ethyl (meth) acrylate can be mentioned.
多官能モノマーとしては、二官能モノマー、三官能モノマー、および、四官能以上の多官能モノマーが挙げられる。
Examples of the polyfunctional monomer include a bifunctional monomer, a trifunctional monomer, and a tetrafunctional or higher polyfunctional monomer.
二官能モノマーとしては、例えば、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチエレングルコールジメタクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ステアリン酸変性ペンタエリスリトールジ(メタ)アクリレート、ジシクロペンテニルジアクリレート、ジ(メタ)アクリロイルイソシアヌレート、およびアルキレンオキサイド変性ビスフェノールジ(メタ)アクリレートが挙げられる。
Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethierlenglucol dimethacrylate, 1,6-hexanediol di (meth). Acrylate, 1,9-nonandiol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dicyclopentenyl diacrylate, di (meth) ) Acryloyl isocyanurate, and alkylene oxide-modified bisphenol di (meth) acrylates.
三官能モノマーとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、およびトリス(アクリロイルオキシエチル)イソシアヌレートが挙げられる。
Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (acryloyloxyethyl) isocyanurate.
四官能以上の多官能モノマーとしては、例えば、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールモノヒドロキシペンタ(メタ)アクリレート、アルキル変性ジペンタエリスリトールペンタアクリレート、およびジペンタエリスリトールヘキサ(メタ)アクリレートが挙げられる。
Examples of the tetrafunctional or higher polyfunctional monomer include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate. Examples thereof include pentaerythritol hexa (meth) acrylate.
粘着剤層10の速硬化性の観点から、重合性化合物としては、好ましくは多官能モノマー、より好ましくは、三官能モノマーまたは四官能以上の多官能モノマーが用いられる。重合性化合物用の三官能モノマーとしては、好ましくはトリメチロールプロパントリ(メタ)アクリレート、より好ましくはトリメチロールプロパントリアクリレートが用いられる。重合性化合物用の四官能以上の多官能モノマーとしては、好ましくはジペンタエリスリトールヘキサ(メタ)アクリレート、より好ましくはジペンタエリスリトールヘキサアクリレートが用いられる。
From the viewpoint of the quick-curing property of the pressure-sensitive adhesive layer 10, the polymerizable compound is preferably a polyfunctional monomer, more preferably a trifunctional monomer or a tetrafunctional or higher polyfunctional monomer. As the trifunctional monomer for the polymerizable compound, trimethylolpropane tri (meth) acrylate is preferably used, and trimethylolpropane triacrylate is more preferably used. As the tetrafunctional or higher functional monomer for the polymerizable compound, dipentaerythritol hexa (meth) acrylate is preferably used, and more preferably dipentaerythritol hexaacrylate is used.
重合性化合物の配合量は、硬化後の粘着剤層10において充分な硬さを確保する観点からは、ベースポリマー100質量部に対して、好ましくは5質量部以上、より好ましくは7質量部以上、更に好ましくは9質量部以上、特に好ましくは10質量部以上である。硬化後の粘着剤層10において充分な粘着力を確保する観点からは、ベースポリマー100質量部に対する重合性化合物の配合量は、好ましくは50質量部以下、より好ましくは45質量部以下、更に好ましくは43質量部以下である。
From the viewpoint of ensuring sufficient hardness in the pressure-sensitive adhesive layer 10 after curing, the amount of the polymerizable compound is preferably 5 parts by mass or more, more preferably 7 parts by mass or more with respect to 100 parts by mass of the base polymer. It is more preferably 9 parts by mass or more, and particularly preferably 10 parts by mass or more. From the viewpoint of ensuring sufficient adhesive strength in the cured pressure-sensitive adhesive layer 10, the blending amount of the polymerizable compound with respect to 100 parts by mass of the base polymer is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably. Is 43 parts by mass or less.
光重合開始剤は、第2外部刺激として活性エネルギー線の照射を受けて、重合性化合物の重合反応を開始させる。光重合開始剤としては、例えば、ベンゾインエーテル光重合開始剤、アセトフェノン光重合開始剤、α-ケトール光重合開始剤、芳香族スルホニルクロリド光重合開始剤、光活性オキシム光重合開始剤、ベンゾイン光重合開始剤、ベンジル光重合開始剤、ベンゾフェノン光重合開始剤、ケタール光重合開始剤、チオキサントン光重合開始剤、および、アシルフォスフィンオキサイド光重合開始剤が挙げられる。
The photopolymerization initiator is irradiated with active energy rays as a second external stimulus to initiate the polymerization reaction of the polymerizable compound. Examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, a photoactive oxime photopolymerization initiator, and a benzoin photopolymerization initiator. Examples thereof include an initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.
着色剤は、好ましくは、酸との反応により発色する化合物(発色性化合物)である。着色剤が発色性化合物である場合、粘着性組成物は、酸発生剤を更に含有する。
The colorant is preferably a compound (color-developing compound) that develops color by reaction with an acid. If the colorant is a color-developing compound, the tacky composition further contains an acid generator.
発色性化合物としては、例えば、ロイコ色素、トリアリールメタン色素、ジフェニルメタン色素、フルオラン色素、スピロピラン色素、およびローダミン色素が挙げられる。発色性化合物は、単独で用いられてもよいし、二種類以上が併用されてもよい。
Examples of the color-developing compound include leuco dye, triarylmethane dye, diphenylmethane dye, fluorane dye, spiropyran dye, and rhodamine dye. The color-developing compound may be used alone or in combination of two or more.
ロイコ色素としては、例えば、2'-アニリノ-6'-(N-エチル-N-イソペンチルアミノ)-3'-メチルスピロ[フタリド-3,9'-[9H]キサンテン]、3-ジブチルアミノ-6-メチル-7-アニリノフルオラン、3-ジプロピルアミノ-6-メチル-7-アニリノフルオラン、3-ジエチルアミノ-6-メチル-7-アニリノフルオラン、3-ジメチルアミノ-6-メチル-7-アニリノフルオラン、3-ジエチルアミノ-6-メチル-7-キシリジノフルオラン、および、3-(4-ジエチルアミノ-2-エトキシフェニル)-3-(1-エチル-2-メチルインドール-3-イル)-4-アザフタリドが挙げられる。
Examples of leuco dyes include 2'-anilino-6'-(N-ethyl-N-isopentylamino) -3'-methylspiro [phthalide-3,9'-[9H] xanthene], 3-dibutylamino-. 6-Methyl-7-anilinofluorane, 3-dipropylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-dimethylamino-6- Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, and 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole) -3-yl) -4-azaphthalide can be mentioned.
トリアリールメタン色素としては、例えば、p,p',p”-トリス-ジメチルアミノトリフェニルメタンが挙げられる。ジフェニルメタン色素としては、例えば、4,4-ビス-ジメチルアミノフェニルベンズヒドリルベンジルエーテルが挙げられる。フルオラン色素としては、例えば、3-ジエチルアミノ-6-メチル-7-クロロフルオランが挙げられる。スピロピラン色素としては、例えば、3-メチルスピロジナフトピランが挙げられる。ローダミン色素としては、例えば、ローダミン-B-アニリノラクタムが挙げられる。
Examples of the triarylmethane dye include p, p', p "-tris-dimethylaminotriphenylmethane. Examples of the diphenylmethane dye include 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether. Examples of the fluorane dye include 3-diethylamino-6-methyl-7-chlorofluorane. Examples of the spiropyran dye include 3-methylspirodinaphthopyrane. Examples of the rhodamine dye include 3-methylspirodinaphthopyrane. For example, Rhodamine-B-anilinolactum can be mentioned.
粘着剤層10において良好な着色性を確保する観点からは、発色性化合物としては、好ましくはロイコ色素、より好ましくは2'-アニリノ-6'-(N-エチル-N-イソペンチルアミノ)-3'-メチルスピロ[フタリド-3,9'-[9H]キサンテン]が用いられる。
From the viewpoint of ensuring good colorability in the pressure-sensitive adhesive layer 10, the color-developing compound is preferably a leuco 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、好ましくは0.5質量部以上、より好ましくは1質量部以上である。同配合量は、好ましくは10質量部以下、より好ましくは7質量部以下である。
The blending amount of the color-developing compound with respect to 100 parts by mass of the base polymer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. The blending amount is preferably 10 parts by mass or less, more preferably 7 parts by mass or less.
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、第1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、当該酸によって発色性化合物が発色する。すなわち、着色剤としての発色性化合物は、第1外部刺激に因って発色可能である。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、例えば暗色に着色する。第1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 the first external stimulus can be discolored. Specifically, in the portion of the pressure-sensitive adhesive layer 10 irradiated with the active energy rays, an acid is generated from the photoacid generator, and the color-developing compound is colored by the acid. That is, the color-developing compound as a colorant can develop color by the first external stimulus. The portion of the pressure-sensitive adhesive layer 10 that has been irradiated with the active energy rays is colored, for example, in a dark color according to the color development of the color-developing compound. The type of the active energy ray as the first external stimulus is determined by the type of the photoacid generator (specifically, the wavelength of the active energy ray in which the photoacid generator generates an 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(第1外部刺激)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。粘着性組成物は、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)を光酸発生剤として含む。
Examples of the photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays (first external stimulus). 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 tacky composition preferably contains an onium salt (onium compound) composed of sulfonium and C 4 F 9 HSO 3- as a photoacid generator.
粘着剤層10が上述の光酸発生剤および光重合開始剤を共に含有する場合、当該粘着剤層10は、好ましくは、光酸発生剤の吸光度Xに対する光重合開始剤の吸光度Yの比率が2以上である波長領域を、波長300nm以上500nm以下の範囲内に有する。同比率は、好ましくは3以上、より好ましくは10以上、更に好ましくは50以上、特に好ましくは100以上である。同比率は、例えば100万以下である。
When the pressure-sensitive adhesive layer 10 contains both the photoacid generator and the photopolymerization initiator described above, the pressure-sensitive adhesive layer 10 preferably has a ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator. It has a wavelength region of 2 or more in a wavelength range of 300 nm or more and 500 nm or less. The ratio is preferably 3 or more, more preferably 10 or more, still more preferably 50 or more, and particularly preferably 100 or more. The same ratio is, for example, 1 million or less.
ベースポリマー100質量部に対する酸発生剤の配合量は、好ましくは1質量部以上、より好ましくは2質量部以上、更に好ましくは5質量部以上、特に好ましくは7質量部以上である。同配合量は、好ましくは20質量部以下、より好ましくは15質量部以下、更に好ましくは12質量部以下である。
The blending amount of the acid generator with respect to 100 parts by mass of the base polymer is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more. The blending amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 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、更に好ましくは330質量部以上である。同配合量は、好ましくは1000質量部以下、より好ましくは700質量部以下、更に好ましくは500質量部以下である。
The 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. The blending amount is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and further preferably 500 parts by mass or less.
粘着性組成物は、必要に応じて他の成分を含有してもよい。他の成分としては、例えば、シランカップリング剤、粘着性付与剤、可塑剤、軟化剤、酸化防止剤、界面活性剤、および帯電防止剤が挙げられる。
The adhesive composition may contain other components as needed. Other components include, for example, silane coupling agents, tackifiers, plasticizers, softeners, antioxidants, surfactants, and antistatic agents.
粘着性組成物は、ロイコ色素など着色成分と配位結合可能な金属錯体を含有してもよい。上記の式(1)および/または式(2)を満たすように粘着剤層10を調整する手段として、このような金属錯体を用いることができる。
The adhesive composition may contain a metal complex that can be coordinated and bonded to a coloring component such as a leuco dye. Such a metal complex can be used as a means for adjusting the pressure-sensitive adhesive layer 10 so as to satisfy the above formulas (1) and / or the formula (2).
金属錯体の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)における第1族のアルカリ金属、第2族のアルカリ土類金属、および、第3族~第12族の遷移金属が挙げられ、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族の遷移金属が用いられる。着色成分としてロイコ色素が用いられる場合の当該ロイコ色素が発色体の形態において有するカルボキシル基と金属との間の強い配位結合性の観点からは、前記金属としてはマグネシウム(Mg)が好ましい。着色成分としてロイコ色素が用いられる場合の当該ロイコ色素と金属錯体とにより形成される両性対イオンの安定化の観点からは、前記金属としては亜鉛(Zn)が好ましい。
The metals constituting the metal ions of the metal complex are group 1 alkali metals and group 2 alkaline earth metals in the periodic table (IUPAC Periodic Table of the Elements (version date 19 February 2010); the same applies hereinafter). , And Group 3 to Group 12 transition metals, preferably Group 2 alkaline earth metals and Group 3 to Group 12 transition metals are used. When a leuco dye is used as a coloring component, magnesium (Mg) is preferable as the metal from the viewpoint of the strong coordination bond between the carboxyl group and the metal that the leuco dye has in the form of a color-developing body. When a leuco dye is used as the coloring component, zinc (Zn) is preferable as the metal from the viewpoint of stabilizing the amphoteric counterion formed by the leuco dye and the metal complex.
金属錯体の配位子としては、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。
Examples of the ligand of the metal complex 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.
金属錯体としては、好ましくは、二座配位子を有する金属錯体が用いられ、上述の両性対イオンの安定化の観点からは、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)が用いられる。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。
As the metal complex, a metal complex having a bidentate ligand is preferably used, and from the viewpoint of stabilizing the amphoteric counterion described above, zinc salicylate (specifically, zinc salicylate trihydration) is more preferable. Thing) is used. 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、更に好ましくは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 parts by mass or more. be. 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.
粘着シートSは、例えば、上述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、当該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). The adhesive sheet S is arranged on the release film L indicated by the virtual 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。当該プラスチックフィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、およびポリエステルフィルムが挙げられる。剥離フィルムの厚さは、例えば3μm以上であり、また、例えば200μm以下である。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, and 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℃~200℃である。乾燥時間は、例えば5秒~20分である。
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 to 200 ° C. The drying time is, for example, 5 seconds to 20 minutes.
粘着性組成物が架橋剤を含む場合、上述の乾燥と同時に又はその後のエージングによって、架橋反応が進行する。エージング条件は、架橋剤の種類によって適宜設定される。エージング温度は、例えば20℃~160℃である。エージング時間は、例えば、1分から7日である。
When the adhesive composition contains a cross-linking agent, the cross-linking reaction proceeds at the same time as the above-mentioned drying or by aging thereafter. The aging conditions are appropriately set depending on the type of the cross-linking agent. The aging temperature is, for example, 20 ° C to 160 ° C. The aging time is, for example, 1 minute to 7 days.
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の上に更に剥離フィルム(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、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り、第1剥離フィルムに関して上述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 a flexible plastic film that has been subjected to a surface release treatment, and the same film as described above can be used for the first release film.
以上のようにして、剥離フィルムによって粘着面が被覆保護された粘着シート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の厚さは、被着体に対する充分な粘着性を確保する観点から、好ましくは10μm以上、より好ましくは15μm以上である。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の厚さは、好ましくは300μm以下、より好ましくは200μm以下、更に好ましくは100μm以下、特に好ましくは50μm以下である。
The thickness of the pressure-sensitive adhesive layer 10 is preferably 10 μm or more, 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 preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less.
粘着シートSが、ガラス板に対する貼り合せを経た後に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当該ステンレス板に対して示す粘着力は、例えば1N/25mm以上であり、また、例えば50N/25mm以下である。
The adhesive force exhibited by the adhesive sheet S on the stainless steel 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 after being bonded to the glass plate is, for example, 1 N / 25 mm or more. It is, for example, 50 N / 25 mm or less.
粘着剤層10のヘイズは、好ましくは3%以下、より好ましくは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 preferably 3% or less, more 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400~700nmでの平均透過率T1(UV照射前の平均透過率)は、好ましくは80%以上、より好ましくは85%以上、更に好ましくは90%以上である。平均透過率T1は、例えば100%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。平均透過率T1は、実施例に関して後述する方法で求められる。
The average transmittance T1 (average transmittance before UV irradiation) of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more. The average transmittance T1 is, for example, 100% 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 average transmittance T1 is determined by the method described later with respect to Examples.
UV照射(具体的には、後記の実施例における第2の透過率測定に関して後述する条件でのUV照射)を受けた粘着剤層10の波長400~700nmでの平均透過率T2は、好ましくは50%以下、より好ましくは40%以下、更に好ましくは30%以下、特に好ましくは25%以下である。平均透過率T2は、例えば0%以上である。このような構成は、変色部分が形成された粘着剤層10における当該変色部分の機能確保の観点から好ましい。平均透過率T2は、実施例に関して後述する方法で求められる。
The average transmittance T2 of the pressure-sensitive adhesive layer 10 subjected to UV irradiation (specifically, UV irradiation under the conditions described later with respect to the second transmittance measurement in the second embodiment described later) at a wavelength of 400 to 700 nm is preferable. It is 50% or less, more preferably 40% or less, still more preferably 30% or less, and particularly preferably 25% or less. The average transmittance T2 is, for example, 0% or more. Such a configuration is preferable from the viewpoint of ensuring the function of the discolored portion in the pressure-sensitive adhesive layer 10 on which the discolored portion is formed. The average transmittance T2 is determined by the method described later with respect to Examples.
平均透過率T1に対する平均透過率T2の比率(T2/T1)は、好ましくは0.4以下、より好ましくは0.3以下、更に好ましくは0.2以下である。また、比率(T2/T1)は、例えば0.001以上である。これら構成は、変色部分が形成された粘着剤層10における当該変色部分の機能確保の観点から好ましい。
The ratio of the average transmittance T2 to the average transmittance T1 (T2 / T1) is preferably 0.4 or less, more preferably 0.3 or less, and further preferably 0.2 or less. The ratio (T2 / T1) is, for example, 0.001 or more. These configurations are preferable from the viewpoint of ensuring the function of the discolored portion in the pressure-sensitive adhesive layer 10 on which the discolored portion is formed.
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、その厚さ方向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の厚さ方向の一方面に接触する。
As shown in FIG. 2, the pressure-sensitive adhesive sheet S may be a single-sided pressure-sensitive adhesive sheet with a base material, which comprises 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 thereof. Preferably, the substrate 20 contacts one side of the pressure-sensitive adhesive layer 10 in the thickness direction.
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であり、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、好ましくは3%以下、より好ましくは2%以下、更に好ましくは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 preferably 3% or less, more preferably 2% or less, still 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の厚さは、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、好ましくは5μm以上、より好ましくは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の厚さは、好ましくは200μm以下、より好ましくは150μm以下、更に好ましくは100μm以下である。
The thickness of the base material 20 is preferably 5 μm or more, more preferably 10 μm or more, and 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 preferably 200 μm or less, more preferably 150 μm or less, still 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述の粘着シート製造方法と同様の方法により、製造できる。
The pressure-sensitive adhesive sheet S shown in FIG. 2 can be manufactured by the same method as the above-mentioned pressure-sensitive adhesive sheet manufacturing method except that the base material 20 is used instead of the first release film, for example.
図3Aから図3Dは、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、硬化工程と、変色部分形成工程とを含む。
FIGS. 3A to 3D show an example of how to use the adhesive sheet S. The method includes a preparation step, a joining step, a curing 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、有機ELパネルなどのディスプレイパネルである。第1部材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 such as an organic EL 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Zが得られる。積層体Zにおいて、粘着シートSは、第1部材31の厚さ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の厚さ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 Z is obtained. In the laminated body Z, 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. Will be done.
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、硬化工程では、図3Cに示すように、積層体Z(上記検査を実施した場合には、検査を通過した積層体Z)における粘着剤層10に第2外部刺激を与えて粘着剤層10を硬化させる。本実施形態では、第2外部刺激は、活性エネルギー線照射である。この活性エネルギー線は、透明な第2部材32の側から粘着剤層10に対して照射される。本工程での活性エネルギー線照射用の光源としては、例えば、紫外線LEDライト、高圧水銀ランプ、およびメタルハライドランプが挙げられる。また、本工程の活性エネルギー線照射においては、光源から出射される活性エネルギー線における一部の波長領域をカットするための波長カットフィルターを、必要に応じて用いてもよい。
Next, in the curing step, as shown in FIG. 3C, a second external stimulus is applied to the pressure-sensitive adhesive layer 10 in the laminate Z (in the case where the above inspection is performed, the laminate Z that has passed the inspection) to provide a pressure-sensitive adhesive. The layer 10 is cured. In this embodiment, the second external stimulus is irradiation with active energy rays. This active energy ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member 32. Examples of the light source for irradiating the active energy ray in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the activation energy ray irradiation in this step, a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
第2外部刺激としての活性エネルギー線は、第1外部刺激としての活性エネルギー線とは波長範囲が異なる。第2外部刺激としての活性エネルギー線は、本実施形態では、酸発生剤において実質的に酸を発生させない波長を有する。当該活性エネルギー線の波長範囲の下限は、好ましくは365nm、より好ましくは370nm、一層好ましくは375nm、より一層好ましくは380nm、更に好ましくは385nm、こと更に好ましくは390nm、特に好ましくは395nmである。本実施形態では、好ましくは、このような波長の活性エネルギー線照射を受けることによって重合性化合物の重合反応を開始させる光重合開始剤が、粘着剤層10に配合される。
The wavelength range of the active energy ray as the second external stimulus is different from that of the active energy ray as the first external stimulus. In the present embodiment, the active energy ray as the second external stimulus has a wavelength that does not substantially generate an acid in the acid generator. The lower limit of the wavelength range of the active energy ray is preferably 365 nm, more preferably 370 nm, still more preferably 375 nm, still more preferably 380 nm, still more preferably 385 nm, still more preferably 390 nm, and particularly preferably 395 nm. In the present embodiment, preferably, a photopolymerization initiator that initiates the polymerization reaction of the polymerizable compound by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
本工程では、活性エネルギー線照射を受けた粘着剤層10において、光重合開始剤によって重合性化合物の重合反応が開始され、当該重合反応が進行する。これにより、粘着剤層10の弾性率が上昇する。
In this step, in the pressure-sensitive adhesive layer 10 irradiated with active energy rays, the polymerization reaction of the polymerizable compound is started by the photopolymerization initiator, and the polymerization reaction proceeds. As a result, the elastic modulus of the pressure-sensitive adhesive layer 10 increases.
粘着剤層10は、上述のように、光酸発生剤の吸光度Xに対する光重合開始剤の吸光度Yの比率が2以上である波長領域(波長領域R)を、波長300nm以上500nm以下の範囲内に有するのが好ましい。波長領域Rにおける前記比率(Y/X)は、好ましくは3以上、より好ましくは10以上、更に好ましくは100以上である。好ましくは、第2外部刺激として照射される活性エネルギー線の波長の少なくとも一部が波長領域R内にある。より好ましくは、第2外部刺激として照射される活性エネルギー線の波長の全てが波長領域R内にある。このような波長領域内の波長を有する活性エネルギー線を第2外部刺激として粘着剤層10に与える構成は、硬化工程において、粘着剤層10での変色を抑制しつつ粘着剤層10を硬化させるのに適する。硬化工程において、粘着剤層10での変色を抑制しつつ粘着剤層10を硬化させる観点からは、光酸発生剤の吸光度Xに対する光重合開始剤の吸光度Yの上記比率は、より大きい方が好ましい。
As described above, the pressure-sensitive adhesive layer 10 has a wavelength region (wavelength region R) in which the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is 2 or more within the range of a wavelength of 300 nm or more and 500 nm or less. It is preferable to have it in. The ratio (Y / X) in the wavelength region R is preferably 3 or more, more preferably 10 or more, and further preferably 100 or more. Preferably, at least a part of the wavelength of the active energy ray irradiated as the second external stimulus is in the wavelength region R. More preferably, all the wavelengths of the active energy rays irradiated as the second external stimulus are in the wavelength region R. Such a configuration in which an active energy ray having a wavelength within the wavelength region is given to the pressure-sensitive adhesive layer 10 as a second external stimulus cures the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step. Suitable for. From the viewpoint of curing the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step, the ratio of the absorbance Y of the photopolymerization initiator to the absorbance X of the photoacid generator is larger. preferable.
次に、変色部分形成工程では、図3Dに示すように、積層体Zにおける粘着剤層10に第1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に対して第1外部刺激としての活性エネルギー線(第1活性エネルギー線)を照射する。これにより、粘着剤層10における当該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。こうして形成される変色部分11の形状としては、例えば、線状の形状、点状の形状、矩形状、円形状、楕円形状、および不定形状が挙げられる。
Next, in the discoloration portion forming step, as shown in FIG. 3D, the pressure-sensitive adhesive layer 10 in the laminated body Z is given a first external stimulus to form the discoloration portion 11 in the pressure-sensitive adhesive layer 10. Specifically, as a first 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 active energy ray (first active energy ray). As a result, the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored. Examples of the shape of the discolored portion 11 thus formed include a linear shape, a dot shape, a rectangular shape, a circular shape, an elliptical shape, and an indefinite shape.
本工程での活性エネルギー線照射用の光源としては、例えば、紫外線LEDライト、高圧水銀ランプ、およびメタルハライドランプが挙げられる。また、本工程の活性エネルギー線照射においては、光源から出射される活性エネルギー線における一部の波長領域をカットするための波長カットフィルターを、必要に応じて用いてもよい。
Examples of the light source for irradiating the active energy beam in this step include an ultraviolet LED light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the activation energy ray irradiation in this step, a wavelength cut filter for cutting a part of the wavelength region in the active energy ray emitted from the light source may be used as needed.
第1活性エネルギー線は、第2外部刺激としての上述の活性エネルギー線(第2活性エネルギー線)とは波長範囲が異なる。第1活性エネルギー線の波長範囲は、好ましくは、少なくとも第2活性エネルギー線の波長範囲より小さい範囲(短波長側の波長範囲)を含む(第1活性エネルギー線の波長範囲は、第2活性エネルギー線の波長範囲と重複する範囲を含んでもよい)。第1活性エネルギー線が波長範囲に下限を有する場合、または、例えば波長カットフィルターを用いて第1活性エネルギー線の波長範囲に下限を設ける場合、当該第1活性エネルギー線の波長範囲の下限は、好ましくは300nm、より好ましくは305nm、一層好ましくは310nm、より一層好ましくは315nm、更に好ましくは320nm、こと更に好ましくは325nm、特に好ましくは330nmである。或いは、第1活性エネルギー線には、波長300nm未満の光が含まれてもよい。そのような光の光源としては、例えば、高圧水銀ランプおよびメタルハライドランプが挙げられる。第1活性エネルギー線が波長範囲に上限を有する場合、または、例えば波長カットフィルターを用いて第1活性エネルギー線の波長範囲に上限を設ける場合、当該第1活性エネルギー線の波長範囲の上限は、好ましくは400nm、より好ましくは395nm、一層好ましくは390nm、より一層好ましくは385nm、更に好ましくは380nm、こと更に好ましくは375nm、特に好ましくは370nmである。本実施形態では、好ましくは、このような波長の活性エネルギー線照射を受けることによって酸を発生する光酸発生剤が、粘着剤層10に配合される。
The wavelength range of the first active energy ray is different from that of the above-mentioned active energy ray (second active energy ray) as the second external stimulus. The wavelength range of the first active energy ray preferably includes at least a range smaller than the wavelength range of the second active energy ray (wavelength range on the short wavelength side) (the wavelength range of the first active energy ray is the second active energy). It may include a range that overlaps with the wavelength range of the line). When the first active energy ray has a lower limit in the wavelength range, or when the lower limit is set in the wavelength range of the first active energy ray by using, for example, a wavelength cut filter, the lower limit of the wavelength range of the first active energy ray is set. It is preferably 300 nm, more preferably 305 nm, more preferably 310 nm, still more preferably 315 nm, still more preferably 320 nm, still more preferably 325 nm, and particularly preferably 330 nm. Alternatively, the first active energy ray may contain light having a wavelength of less than 300 nm. Light sources of such light include, for example, high pressure mercury lamps and metal halide lamps. When the first active energy ray has an upper limit in the wavelength range, or when the upper limit is set in the wavelength range of the first active energy ray by using, for example, a wavelength cut filter, the upper limit of the wavelength range of the first active energy ray is It is preferably 400 nm, more preferably 395 nm, more preferably 390 nm, even more preferably 385 nm, still more preferably 380 nm, still more preferably 375 nm, and particularly preferably 370 nm. In the present embodiment, preferably, a photoacid generator that generates an acid by being irradiated with active energy rays having such a wavelength is blended in the pressure-sensitive adhesive layer 10.
本工程では、粘着剤層10において第1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、当該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 first active energy ray, and the color-developing compound is developed by the reaction with the acid. As a result, the discolored portion 11 is formed on the pressure-sensitive adhesive layer 10.
例えば以上のようにして、部材間の接合に粘着シートSを使用できる。第1部材31が有機ELパネルなどのディスプレイパネルである場合、当該パネルが備える画素パネル上に形成された金属配線に対応する(即ち対面する)パターン形状で変色部分11を設けることにより、当該金属配線での外光反射を抑制できる。
For example, as described above, the adhesive sheet S can be used for joining between members. When the first member 31 is a display panel such as an organic EL panel, the metal is provided by providing the discolored portion 11 in a pattern shape corresponding to (that is, facing) the metal wiring formed on the pixel panel included in the panel. External light reflection in wiring can be suppressed.
以上のような使用方法においては、粘着シートSの粘着剤層10が、第1外部刺激によって発色可能な着色剤を含有するため、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第1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 above-mentioned usage method, since the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S contains a colorant capable of developing a color by a first external stimulus, the pressure-sensitive adhesive sheet S is attached to an adherend ( members 31, 32 in this embodiment). ), The pressure-sensitive adhesive layer 10 can be locally discolored by applying a first external stimulus to the portion to be discolored in the pressure-sensitive adhesive layer 10. 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においては、粘着剤層10が、第1外部刺激とは異なる第2外部刺激によって硬化可能であり、当該粘着剤層10において、その硬化前の上記第1せん断貯蔵弾性率が0.1×105Pa以上10×105Pa以下であり、且つ当該第1せん断貯蔵弾性率に対する硬化後の上記第2せん断貯蔵弾性率の比率が2以上300以下である。このような粘着シートSは、被着体に対する貼り合わせに適した粘着特性を粘着剤層10(硬化前)において貼り合わせ時に確保しつつ、貼り合わせ後の粘着剤層10(硬化後)において着色剤の拡散を抑制するのに適する。変色部分11が形成された粘着剤層10は、着色剤の拡散が抑制されることにより、変色部分11の経時的な劣化(滲み、退色、色味の不均一化など)が抑制される。粘着剤層10における変色部分11の劣化の抑制は、意匠性、遮蔽性、反射防止性など、変色部分11が担う機能特性の維持に役立つ。
Further, in the pressure-sensitive adhesive sheet S, the pressure-sensitive adhesive layer 10 can be cured by a second external stimulus different from the first external stimulus, and in the pressure-sensitive adhesive layer 10, the first shear storage elastic modulus before curing is the same. It is 0.1 × 10 5 Pa or more and 10 × 10 5 Pa or less, and the ratio of the second shear storage elastic modulus after curing to the first shear storage elastic modulus is 2 or more and 300 or less. Such an adhesive sheet S is colored in the adhesive layer 10 (after curing) after bonding while ensuring the adhesive properties suitable for bonding to the adherend at the time of bonding in the adhesive layer 10 (before curing). Suitable for suppressing the diffusion of the agent. In the pressure-sensitive adhesive layer 10 on which the discolored portion 11 is formed, the diffusion of the colorant is suppressed, so that deterioration of the discolored portion 11 over time (bleeding, fading, non-uniformity of color, etc.) is suppressed. Suppressing the deterioration of the discolored portion 11 in the pressure-sensitive adhesive layer 10 is useful for maintaining the functional characteristics of the discolored portion 11 such as designability, shielding property, and antireflection property.
本発明について、以下に実施例を示して具体的に説明するが、本発明は、実施例に限定されない。また、以下に記載されている配合量(含有量)、物性値、パラメータなどの具体的数値は、上述の「発明を実施するための形態」において記載されている、それらに対応する配合量(含有量)、物性値、パラメータなどの上限(「以下」または「未満」として定義されている数値)または下限(「以上」または「超える」として定義されている数値)に代替できる。
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. In addition, the specific numerical values such as the compounding amount (content), the physical property value, the parameter, etc. described below are the compounding 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.
〔実施例1〕
〈ベースポリマーの調製〉 [Example 1]
<Preparation of base polymer>
〈ベースポリマーの調製〉 [Example 1]
<Preparation of base polymer>
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。
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.
〈粘着性組成物の調製〉
アクリルポリマーを含有する上述のポリマー溶液に、アクリルポリマー(ベースポリマー)100質量部あたり、重合性化合物としてのジペンタエリスリトールヘキサアクリレート(DPHA)(ダイセル・オルネクス社製)11.1質量部と、光重合開始剤(商品名「Omnirad 819」,ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド,IGM Resins B.V.社製)0.1質量部と、発色性化合物としてのロイコ色素(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)2.2質量部と、光酸発生剤(商品名「Sp-056」,スルホニウムとC4F9HSO3 -とのオニウム塩,ADEKA社製)7.8質量部と、架橋剤としてのイソシアネート架橋剤(商品名「タケネートD110N」,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)と、架橋触媒としてのジラウリン酸ジブチルスズ(商品名「OL-1」,1質量%酢酸エチル溶液,東京ファインケミカル社製)0.01質量部(固形分換算量)と、架橋抑制剤(架橋触媒に対する配位子)としてのアセチルアセトン3質量部とを加えて混合し、粘着性組成物を調製した。 <Preparation of adhesive composition>
In the above-mentioned polymer solution containing an acrylic polymer, 11.1 parts by mass of dipentaerythritol hexaacrylate (DPHA) (manufactured by Dycel Ornex) as a polymerizable compound per 100 parts by mass of the acrylic polymer (base polymer) and light. Polymerization initiator (trade name "Omnirad 819", bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by IGM Resins BV) 0.1 part by mass and leuco dye as a color-developing compound (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 .2 parts by mass, photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured by ADEKA), 7.8 parts by mass, and isocyanate cross-linking as a cross-linking agent. Agent (trade name "Takenate D110N", 75% ethyl acetate solution of trimethylolkane adduct polymer of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) 0.25 parts by mass (solid content equivalent amount) and dibutyltin dilaurate as a cross-linking catalyst ( Product name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemicals, 0.01 parts by mass (solid content equivalent) and 3 parts by mass of acetylacetone as a cross-linking inhibitor (ligand to a cross-linking catalyst). And mixed to prepare a tacky composition.
アクリルポリマーを含有する上述のポリマー溶液に、アクリルポリマー(ベースポリマー)100質量部あたり、重合性化合物としてのジペンタエリスリトールヘキサアクリレート(DPHA)(ダイセル・オルネクス社製)11.1質量部と、光重合開始剤(商品名「Omnirad 819」,ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド,IGM Resins B.V.社製)0.1質量部と、発色性化合物としてのロイコ色素(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)2.2質量部と、光酸発生剤(商品名「Sp-056」,スルホニウムとC4F9HSO3 -とのオニウム塩,ADEKA社製)7.8質量部と、架橋剤としてのイソシアネート架橋剤(商品名「タケネートD110N」,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)と、架橋触媒としてのジラウリン酸ジブチルスズ(商品名「OL-1」,1質量%酢酸エチル溶液,東京ファインケミカル社製)0.01質量部(固形分換算量)と、架橋抑制剤(架橋触媒に対する配位子)としてのアセチルアセトン3質量部とを加えて混合し、粘着性組成物を調製した。 <Preparation of adhesive composition>
In the above-mentioned polymer solution containing an acrylic polymer, 11.1 parts by mass of dipentaerythritol hexaacrylate (DPHA) (manufactured by Dycel Ornex) as a polymerizable compound per 100 parts by mass of the acrylic polymer (base polymer) and light. Polymerization initiator (trade name "Omnirad 819", bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by IGM Resins BV) 0.1 part by mass and leuco dye as a color-developing compound (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 .2 parts by mass, photoacid generator (trade name "Sp-056", onium salt of sulfonium and C4 F 9 HSO 3- , manufactured by ADEKA), 7.8 parts by mass, and isocyanate cross-linking as a cross-linking agent. Agent (trade name "Takenate D110N", 75% ethyl acetate solution of trimethylolkane adduct polymer of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) 0.25 parts by mass (solid content equivalent amount) and dibutyltin dilaurate as a cross-linking catalyst ( Product name "OL-1", 1% by mass ethyl acetate solution, manufactured by Tokyo Fine Chemicals, 0.01 parts by mass (solid content equivalent) and 3 parts by mass of acetylacetone as a cross-linking inhibitor (ligand to a cross-linking catalyst). And mixed to prepare a tacky composition.
〈粘着剤層の形成〉
表面が離型処理されている厚さ38μmのポリエチレンテレフタレートフィルム(基材フィルム)上に、ファウンテンロールによって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、セパレータ(一方面が離型処理されている厚さ38μmのポリエチレンテレフタレートフィルム)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。 <Formation of adhesive layer>
An adhesive composition was applied by a fountain roll onto a 38 μm-thick polyethylene terephthalate film (base film) whose surface had been mold-released to form a coating film. 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, the mold release-treated surface of the separator (a polyethylene terephthalate film having a thickness of 38 μm on which one surface was mold-released) was attached to the pressure-sensitive adhesive layer on the base film. Then, it was aged at 60 ° C. for 24 hours to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed.
表面が離型処理されている厚さ38μmのポリエチレンテレフタレートフィルム(基材フィルム)上に、ファウンテンロールによって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、セパレータ(一方面が離型処理されている厚さ38μmのポリエチレンテレフタレートフィルム)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。 <Formation of adhesive layer>
An adhesive composition was applied by a fountain roll onto a 38 μm-thick polyethylene terephthalate film (base film) whose surface had been mold-released to form a coating film. 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, the mold release-treated surface of the separator (a polyethylene terephthalate film having a thickness of 38 μm on which one surface was mold-released) was attached to the pressure-sensitive adhesive layer on the base film. Then, it was aged at 60 ° C. for 24 hours to allow the cross-linking reaction in the pressure-sensitive adhesive layer to proceed.
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(後記の実施例および比較例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 and Comparative Examples described later).
〔実施例2~5および比較例1〕
以下のこと以外は、実施例1の粘着シートと同様にして、実施例2~5および比較例1の各粘着シートを作製した。 [Examples 2 to 5 and Comparative Example 1]
Except for the following, each of the pressure-sensitive adhesive sheets of Examples 2 to 5 and Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1.
以下のこと以外は、実施例1の粘着シートと同様にして、実施例2~5および比較例1の各粘着シートを作製した。 [Examples 2 to 5 and Comparative Example 1]
Except for the following, each of the pressure-sensitive adhesive sheets of Examples 2 to 5 and Comparative Example 1 was prepared in the same manner as the pressure-sensitive adhesive sheet of Example 1.
実施例2~5の各粘着シートの作製過程では、粘着性組成物の調製において、表1に示す配合量で各成分を配合した。実施例4,5の粘着シート作製過程における粘着性組成物の調製において、重合性化合物としては、DPHAの代わりにトリメチロールプロパントリアクリレート(TMPTA)(大阪有機化学工業社製)を用いた。また、比較例1の粘着シートの作製過程では、粘着性組成物の調製において、表1に示す配合量で各成分を配合した(重合性化合物および光重合開始剤は配合しなかった)。
In the process of producing each of the pressure-sensitive adhesive sheets of Examples 2 to 5, each component was blended in the blending amount shown in Table 1 in the preparation of the tacky composition. In the preparation of the adhesive composition in the process of producing the adhesive sheet of Examples 4 and 5, trimethylolpropane triacrylate (TMPTA) (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used as the polymerizable compound instead of DPHA. Further, in the process of producing the pressure-sensitive adhesive sheet of Comparative Example 1, in the preparation of the pressure-sensitive adhesive composition, each component was blended in the blending amounts shown in Table 1 (the polymerizable compound and the photopolymerization initiator were not blended).
<光透過率>
実施例1~5および比較例1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400~700nmでの平均透過率を調べた。 <Light transmittance>
For the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the average transmittance at a wavelength of 400 to 700 nm was examined as follows.
実施例1~5および比較例1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400~700nmでの平均透過率を調べた。 <Light transmittance>
For the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the average transmittance at a wavelength of 400 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400~700nm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、測定用サンプルの波長400~700nm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。測定された粘着剤層の平均透過率T1(UV照射前の波長400~700nmでの平均透過率)を、表1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 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 to 700 nm was measured at a pitch of 1 nm. In this measurement, the transmittance spectrum obtained by measuring only the eagle glass under the same conditions was used as the baseline. The measured average transmittance T1 (average transmittance at a wavelength of 400 to 700 nm before UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1.
一方、実施例1~5および比較例1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400~700nm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 1 to 5 and Comparative Example 1, the average transmittance at a wavelength of 400 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染料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320~390nm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 pressure-sensitive adhesive sheet (adhesive layer) in the sample was irradiated with ultraviolet rays from the eagle glass side through the same glass in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive by the UV irradiation). The leuco 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 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400~700nm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400~700nmでの平均透過率)を、表1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1に示す。
Next, for the second measurement sample, the average transmittance at a wavelength of 400 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. The measured average transmittance T2 (average transmittance at a wavelength of 400 to 700 nm after UV irradiation) of the pressure-sensitive adhesive layer is shown in Table 1. Table 1 also shows the ratio of the average transmittance T2 to the above-mentioned average transmittance T1.
<粘着剤層(硬化処理前)のせん断貯蔵弾性率>
実施例1~5および比較例1の各粘着シートの粘着剤層について、せん断貯蔵弾性率を動的粘弾性測定(第1測定)によって調べた。 <Shear storage elastic modulus of adhesive layer (before hardening treatment)>
The shear storage elastic modulus of the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 was examined by dynamic viscoelasticity measurement (first measurement).
実施例1~5および比較例1の各粘着シートの粘着剤層について、せん断貯蔵弾性率を動的粘弾性測定(第1測定)によって調べた。 <Shear storage elastic modulus of adhesive layer (before hardening treatment)>
The shear storage elastic modulus of the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 was examined by dynamic viscoelasticity measurement (first measurement).
第1測定用の試料は、次のようにして作製した。まず、測定対象の粘着剤層ごとに、60枚の粘着剤層(厚さ25μm)を積層して積層粘着剤層(厚さ1.5mm)を得た。次に、積層粘着剤層に対する打抜き加工により、第1測定用試料としての円柱状のペレット(厚さ1.5mm,直径7.9mm)を得た。
The sample for the first measurement was prepared as follows. First, 60 pressure-sensitive adhesive layers (thickness 25 μm) were laminated for each pressure-sensitive adhesive layer to be measured to obtain a laminated pressure-sensitive adhesive layer (thickness 1.5 mm). Next, a columnar pellet (thickness 1.5 mm, diameter 7.9 mm) as a first measurement sample was obtained by punching the laminated pressure-sensitive adhesive layer.
動的粘弾性測定には、動的粘弾性測定装置(商品名「ARES」,レオメトリック社製)を使用した。具体的には、直径7.9mmパラレルプレートの治具に測定用試料を固定した後、前記装置によって動的粘弾性測定を実施した。本測定では、測定モードをせん断モードとし、測定温度範囲を-70℃~250℃とし、昇温速度を5℃/分とし、周波数を1Hzとした。粘着剤層(硬化処理前)の25℃でのせん断貯蔵弾性率E1を表1に示す。
A dynamic viscoelasticity measuring device (trade name "ARES", manufactured by Leometric Co., Ltd.) was used for the dynamic viscoelasticity measurement. Specifically, after fixing the measurement sample to the jig of the parallel plate having a diameter of 7.9 mm, the dynamic viscoelasticity measurement was carried out by the above-mentioned apparatus. In this measurement, the measurement mode was the shear mode, the measurement temperature range was −70 ° C. to 250 ° C., the temperature rise rate was 5 ° C./min, and the frequency was 1 Hz. Table 1 shows the shear storage elastic modulus E1 of the pressure-sensitive adhesive layer (before the curing treatment) at 25 ° C.
<粘着剤層(硬化処理後)のせん断貯蔵弾性率>
実施例1~5および比較例1の各粘着シートの粘着剤層について、硬化処理後のせん断貯蔵弾性率を動的粘弾性測定(第2測定)によって調べた。 <Shear storage elastic modulus of adhesive layer (after hardening treatment)>
For the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the shear storage elastic modulus after the curing treatment was examined by dynamic viscoelasticity measurement (second measurement).
実施例1~5および比較例1の各粘着シートの粘着剤層について、硬化処理後のせん断貯蔵弾性率を動的粘弾性測定(第2測定)によって調べた。 <Shear storage elastic modulus of adhesive layer (after hardening treatment)>
For the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the shear storage elastic modulus after the curing treatment was examined by dynamic viscoelasticity measurement (second measurement).
第2測定用の試料(厚さ1.5mmの積層粘着剤層に対する打抜き加工によって得られた円柱状ペレット)は、積層前の60枚の粘着剤層のそれぞれに対して紫外線照射(硬化処理)したこと以外は、第1測定用試料と同様にして作製した。硬化処理では、具体的には、23℃および相対湿度50%の環境下で、積層前の各粘着剤層に対して紫外線照射した。この紫外線照射では、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405nmのUV-LEDランプを光源として使用し、照射積算光量を2000mJ/cm2(波長395~445nmの範囲での照射積算光量)とした。
The sample for the second measurement (cylindrical pellet obtained by punching the laminated pressure-sensitive adhesive layer with a thickness of 1.5 mm) was irradiated with ultraviolet rays (curing treatment) on each of the 60 pressure-sensitive adhesive layers before stacking. Except for the above, it was prepared in the same manner as the first measurement sample. In the curing treatment, specifically, each pressure-sensitive adhesive layer before laminating was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50%. In this ultraviolet irradiation, a UV-LED lamp having a wavelength of 405 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 2000 mJ / cm. It was set to 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm).
第2測定は、第1測定と同様の装置および条件で実施した。粘着剤層(硬化処理後)の25℃、65℃、および85℃での各せん断貯蔵弾性率E2を表1に示す。
The second measurement was carried out with the same equipment and conditions as the first measurement. Table 1 shows the shear storage modulus E2 of the pressure-sensitive adhesive layer (after the curing treatment) at 25 ° C., 65 ° C., and 85 ° C.
<耐久性試験>
実施例1~5および比較例1の各粘着シートの粘着剤層について、以下のようにして、形成される変色部分の滲み抑制の程度を調べた。 <Durability test>
With respect to the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the degree of suppression of bleeding of the discolored portion formed was examined as follows.
実施例1~5および比較例1の各粘着シートの粘着剤層について、以下のようにして、形成される変色部分の滲み抑制の程度を調べた。 <Durability test>
With respect to the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1, the degree of suppression of bleeding of the discolored portion formed was examined as follows.
まず、実施例1~5および比較例1の粘着シートごとに、複数枚の粘着シートを用意した。
First, a plurality of adhesive sheets were prepared for each of the adhesive sheets of Examples 1 to 5 and Comparative Example 1.
次に、粘着シートの粘着剤層に対し、23℃および相対湿度50%の環境下において紫外線照射した(当該紫外線照射により、実施例1~5の各粘着シートの粘着剤層は硬化した)。この紫外線照射では、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405nmのUV-LEDランプを光源として使用し、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395~445nmの範囲での照射積算光量)とした(この紫外線照射条件は、上記第2測定の試料の作製過程における硬化処理での紫外線照射条件と同じである)。
Next, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was irradiated with ultraviolet rays in an environment of 23 ° C. and a relative humidity of 50% (the pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets of Examples 1 to 5 was cured by the UV irradiation). In this ultraviolet irradiation, a UV-LED lamp having a wavelength of 405 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 an adhesive is applied through the base film. The layer was irradiated with ultraviolet rays, and the integrated irradiation light amount was set to 2000 mJ / cm 2 (integrated irradiation light amount in the wavelength range of 395 to 445 nm). Same as UV irradiation conditions).
次に、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、当該フォトマスクの開口部の線幅は250~280μm程度である(開口部の線幅は、フォトマスクごとに異なる)。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320~390nmの範囲での照射積算光量)とした。
Next, 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 is formed from a dry film photoresist arranged on the surface of the pressure-sensitive adhesive sheet on the base film side, and the line width of the opening of the photomask is about 250 to 280 μm (the line width of the opening is the photomask). Different for each). 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 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(初期線幅の測定)。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、当該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(W1)を測定した。
Next, the line width of the linear discolored portion formed on the adhesive layer was measured (measurement of the initial line width). 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 observed. The area to be included 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 (W1) of the linear discolored 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。具体的な測定方法は、初期線幅の測定に関して上述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線幅W1、第1耐久性試験後の線状変色部分の線幅W2、および、前記線幅W1に対する線幅W2の増加率(W2/W1)を、表1に示す。また、粘着剤層の85℃でのせん断貯蔵弾性率(実施例1~5では、硬化した粘着剤層のせん断貯蔵弾性率)と、線幅の増加率(W2/W1)との関係を示すグラフを、図4に示す。
Next, the line width of the linear discolored portion in the adhesive layer of the adhesive sheet was measured. The specific measurement method is the same as the measurement method described above for the measurement of the initial line width. The line width W1 of the linear discolored portion before the first durability test, the line width W2 of the linear discolored portion after the first durability test, and the rate of increase of the line width W2 with respect to the line width W1 (W2 / W1). Is shown in Table 1. Further, the relationship between the shear storage elastic modulus of the pressure-sensitive adhesive layer at 85 ° C. (the shear storage elastic modulus of the cured pressure-sensitive adhesive layer in Examples 1 to 5) and the increase rate of the line width (W2 / W1) is shown. The graph is shown in FIG.
一方、実施例1~5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述の方法と同様にして、形成される線状変色部分の滲み抑制の程度を調べた。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、65℃および相対湿度90%で120時間、加熱処理した。第2耐久性試験前の線状変色部分の線幅W1、第2耐久性試験後の線状変色部分の線幅W3、および、前記線幅W1に対する線幅W3の増加率(W3/W1)を、表1に示す。また、粘着剤層の65℃でのせん断貯蔵弾性率(実施例1~5では、硬化した粘着剤層のせん断貯蔵弾性率)と、線幅の増加率(W3/W1)との関係を示すグラフを、図5に示す。
On the other hand, the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Examples 1 to 5 and Comparative Example 1 were formed in the same manner as described above except that the second durability test was performed instead of the first durability test. The degree of suppression of bleeding in the linear discolored part was investigated. 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 65 ° C. and 90% relative humidity for 120 hours. The line width W1 of the linear discolored portion before the second durability test, the line width W3 of the linear discolored portion after the second durability test, and the rate of increase of the line width W3 with respect to the line width W1 (W3 / W1). Is shown in Table 1. Further, the relationship between the shear storage elastic modulus of the pressure-sensitive adhesive layer at 65 ° C. (the shear storage elastic modulus of the cured pressure-sensitive adhesive layer in Examples 1 to 5) and the increase rate of the line width (W3 / W1) is shown. The graph is shown in FIG.
第1耐久性試験後の線状変色部分の線幅の増加率(W2/W1)は、実施例1~5の各粘着シート(25℃でのせん断貯蔵弾性率E1に対する25℃でのせん断貯蔵弾性率E2の比率(E2/E1)が2以上300以下)では、比較例1の粘着シートよりも、小さかった。第2耐久性試験後の線状変色部分の線幅の増加率(W3/W1)も、実施例1~5の各粘着シートでは、比較例1の粘着シートよりも、小さかった。すなわち、実施例1~5の各粘着シートでは、比較例1の粘着シートよりも、粘着剤層の変色部分の滲みが抑制された。
The rate of increase in line width (W2 / W1) of the linearly discolored portion after the first durability test is the shear storage at 25 ° C. with respect to the shear storage elastic modulus E1 of each of the adhesive sheets of Examples 1 to 5. The ratio of elastic modulus E2 (E2 / E1) was 2 or more and 300 or less), which was smaller than that of the pressure-sensitive adhesive sheet of Comparative Example 1. The rate of increase in the line width (W3 / W1) of the linearly discolored portion after the second durability test was also smaller in each of the pressure-sensitive adhesive sheets of Examples 1 to 5 than that of the pressure-sensitive adhesive sheet of Comparative Example 1. That is, in each of the pressure-sensitive adhesive sheets of Examples 1 to 5, bleeding of the discolored portion of the pressure-sensitive adhesive layer was suppressed as compared with the pressure-sensitive adhesive sheet of Comparative Example 1.
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 (6)
- 変色可能な粘着剤層を備える可変色粘着シートであって、
前記粘着剤層は、
第1外部刺激によって発色可能な着色剤を含有し、
前記第1外部刺激とは異なる第2外部刺激によって硬化可能であり、
硬化前の前記粘着剤層が、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℃での第1せん断貯蔵弾性率は、0.1×105Pa以上10×105Pa以下であり、
硬化後の前記粘着剤層が前記条件での動的粘弾性測定で示す25℃での第2せん断貯蔵弾性率の、前記第1せん断貯蔵弾性率に対する比率は、2以上300以下である、可変色粘着シート。 A variable color adhesive sheet with a discolorable adhesive layer.
The pressure-sensitive adhesive layer is
Contains a colorant that can be colored by the first external stimulus,
It can be cured by a second external stimulus different from the first external stimulus.
The first shear storage elastic modulus at 25 ° C., which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer before curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is 0.1 × 105 Pa. More than 10 × 10 5 Pa or less,
The ratio of the second shear storage elastic modulus at 25 ° C. shown by the dynamic viscoelasticity measurement under the above conditions to the first shear storage elastic modulus after curing is variable, which is 2 or more and 300 or less. Color adhesive sheet. - 硬化後の前記粘着剤層に対して前記第1外部刺激を線状に付与することによって当該粘着剤層内に形成された変色領域の第1変色幅W1、および、当該粘着剤層を更に85℃で120時間加熱処理した後の前記変色領域の第2変色幅W2が、0.5≦W2/W1≦2を満たす、請求項1に記載の可変色粘着シート。 The first discoloration width W1 of the discoloration region formed in the pressure-sensitive adhesive layer by linearly applying the first external stimulus to the pressure-sensitive adhesive layer after curing, and the pressure-sensitive adhesive layer further 85. The variable color adhesive sheet according to claim 1, wherein the second color change width W2 of the color change region after heat treatment at ° C. for 120 hours satisfies 0.5 ≦ W2 / W1 ≦ 2.
- 硬化後の前記粘着剤層に対して前記第1外部刺激を線状に付与することによって当該粘着剤層内に形成された変色領域の第1変色幅W1、および、当該粘着剤層を更に65℃および相対湿度90%で120時間加熱処理した後の前記変色領域の第3変色幅W3が、0.5≦W3/W1≦2.4を満たす、請求項1に記載の可変色粘着シート。 The first discoloration width W1 of the discoloration region formed in the pressure-sensitive adhesive layer by linearly applying the first external stimulus to the pressure-sensitive adhesive layer after curing, and the pressure-sensitive adhesive layer are further 65. The variable color adhesive sheet according to claim 1, wherein the third color change width W3 of the color change region after heat treatment at 90 ° C. and 90% relative humidity satisfies 0.5 ≦ W3 / W1 ≦ 2.4.
- 前記着色剤が、酸との反応により発色する化合物であり、
前記粘着剤層が、光酸発生剤を更に含有する、請求項1に記載の可変色粘着シート。 The colorant is a compound that develops color by reacting with an acid.
The variable color pressure-sensitive adhesive sheet according to claim 1, wherein the pressure-sensitive adhesive layer further contains a photoacid generator. - 前記粘着剤層が、10~300μmの厚さを有する、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 to 300 μm.
- 前記粘着剤層の厚さ方向一方側に配置された基材を更に備える、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.
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KR1020237007538A KR20230064611A (en) | 2020-09-10 | 2021-08-31 | variable color adhesive sheet |
CN202180061846.4A CN116057144A (en) | 2020-09-10 | 2021-08-31 | Color-changeable adhesive sheet |
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JP2021136861A JP2022046421A (en) | 2020-09-10 | 2021-08-25 | Color-changeable adhesive sheet |
JP2021-136861 | 2021-08-25 |
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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 |
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 |
JP2006243018A (en) * | 2005-02-28 | 2006-09-14 | Sekisui Chem Co Ltd | Liquid crystal display element, shading sealant therefor, and vertical conduction material |
US20160381821A1 (en) * | 2015-04-15 | 2016-12-29 | Boe Technology Group Co., Ltd. | Display panel, fabrication method thereof and display device |
WO2019065375A1 (en) * | 2017-09-28 | 2019-04-04 | 日東電工株式会社 | Reinforced film |
WO2020189390A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
Family Cites Families (1)
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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 (7)
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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 |
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 |
JP2006243018A (en) * | 2005-02-28 | 2006-09-14 | Sekisui Chem Co Ltd | Liquid crystal display element, shading sealant therefor, and vertical conduction material |
US20160381821A1 (en) * | 2015-04-15 | 2016-12-29 | Boe Technology Group Co., Ltd. | Display panel, fabrication method thereof and display device |
WO2019065375A1 (en) * | 2017-09-28 | 2019-04-04 | 日東電工株式会社 | Reinforced film |
WO2020189390A1 (en) * | 2019-03-15 | 2020-09-24 | 日東電工株式会社 | Adhesive agent composition, adhesive agent layer, and adhesive sheet |
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