WO2022054637A1 - Method for manufacturing adhesive sheet-attached article - Google Patents

Method for manufacturing adhesive sheet-attached article Download PDF

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Publication number
WO2022054637A1
WO2022054637A1 PCT/JP2021/031869 JP2021031869W WO2022054637A1 WO 2022054637 A1 WO2022054637 A1 WO 2022054637A1 JP 2021031869 W JP2021031869 W JP 2021031869W WO 2022054637 A1 WO2022054637 A1 WO 2022054637A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
meth
adhesive sheet
Prior art date
Application number
PCT/JP2021/031869
Other languages
French (fr)
Japanese (ja)
Inventor
大輔 水野
武史 仲野
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020237007539A priority Critical patent/KR20230062826A/en
Priority to CN202180061839.4A priority patent/CN116075567A/en
Publication of WO2022054637A1 publication Critical patent/WO2022054637A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a method for manufacturing an adhesive sheet-attached product.
  • 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 deterioration of the colored portion include deformation of the colored portion due to deformation of the pressure-sensitive adhesive layer.
  • Examples of the deterioration of the discolored portion include bleeding, fading, and non-uniformity of the color of the colored portion due to the diffusion of the coloring component contained in the colored portion.
  • the present invention provides a method for manufacturing an adhesive sheet-attached product, which is capable of discoloring at least a part of the adhesive sheet after being attached to an adherend and is suitable for suppressing deterioration of the discolored portion.
  • an adhesive sheet provided with an adhesive layer that can be discolored and cured by irradiation with a first active light beam and can be cured by irradiation with a second active light beam is attached to an adherend.
  • a method for producing an adhesive sheet-attached product which comprises a bonding step, wherein the pressure-sensitive adhesive layer on the adherend is irradiated with the second active light beam to cure the pressure-sensitive adhesive layer.
  • a discoloration step of forming a discolored portion in the pressure-sensitive adhesive layer by irradiating at least a part of the pressure-sensitive adhesive layer with the first active light beam after the curing step is further included, or the said on the adherend.
  • the present invention includes a method for producing an adhesive sheet-attached product, further comprising a second curing step of curing the second portion.
  • the pressure-sensitive adhesive layer contains a polymerizable compound, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator, according to the above [1].
  • a method for manufacturing adhesive sheet affixed products includes a method for manufacturing adhesive sheet affixed products.
  • the pressure-sensitive adhesive layer has a wavelength region 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 a wavelength range of 300 nm or more and 500 nm or less.
  • the method for producing the adhesive sheet-attached product according to the above [2] is included.
  • At least one light source selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp is used as the light source of the second active light in the curing step.
  • the present invention [6] is described in any one of the above [1] to [5], wherein the first active light ray in the discoloration step and / or the discoloration curing step contains light having a wavelength of less than 300 nm.
  • the first active light ray in the discoloration step and / or the discoloration curing step contains light having a wavelength of less than 300 nm.
  • the present invention [7] is selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp as a light source of the first active light in the discoloration step and / or the discoloration curing step.
  • an adhesive sheet provided with an adhesive layer that can be discolored by irradiation with a first active light beam is attached to an adherend in the bonding step. Therefore, after the bonding step, at least a part of the pressure-sensitive adhesive layer can be discolored by irradiating the portion to be discolored in the pressure-sensitive adhesive layer with the first active light beam (color-changing step, first discoloration curing step, Or a second discoloration curing step).
  • the pressure-sensitive adhesive layer is cured while suppressing the discoloration of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer has a desired pattern. Suitable for forming discolored parts of the shape.
  • the above configuration for carrying out the first discoloration curing step is suitable for efficiently discoloring and curing the entire pressure-sensitive adhesive layer.
  • a discolored portion having a desired pattern shape is formed in the pressure-sensitive adhesive layer, and discoloration other than the discolored portion in the pressure-sensitive adhesive layer is suppressed. Suitable for curing the adhesive layer while doing so.
  • these configurations suitable for forming a discolored portion in at least a part of the pressure-sensitive adhesive layer and curing the entire pressure-sensitive adhesive layer provide a softness suitable for bonding to an adherend. It is suitable for suppressing deterioration of the discolored portion in the pressure-sensitive adhesive layer (after curing) of the manufactured pressure-sensitive adhesive sheet-attached product while ensuring the layer (before curing) at the time of bonding.
  • FIG. 1A shows a step of preparing an adhesive sheet and a first member
  • FIG. 1B shows a step of attaching an adhesive sheet to a first member (bonding step)
  • FIG. 1C shows a first member and a second member.
  • FIG. 2A represents a step of curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (first curing step)
  • FIG. 2B represents a step of discoloring a part of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (color-changing step).
  • FIG. 4A shows a step of discoloring and curing a part of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (second discoloration curing step)
  • FIG. 4B shows a step of curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (second curing step).
  • the present manufacturing method includes a preparation step, a bonding step, a first curing step, and a discoloration step.
  • the adhesive sheet S and the first member M1 are prepared.
  • the adhesive sheet S includes an adhesive layer 10.
  • the adhesive sheet S has a sheet shape having a predetermined thickness and extends in a direction (plane direction) orthogonal to the thickness direction.
  • the pressure-sensitive adhesive layer 10 is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive layer 10 has transparency (visible light transmission). Further, the pressure-sensitive adhesive layer 10 can be discolored and cured by irradiation with a first active ray described later, and can be cured by irradiation with a second active ray described later different from the first active ray.
  • the tacky composition contains a base polymer, a polymerizable compound, and a photopolymerization initiator.
  • the photopolymerization initiator receives a second active light beam to initiate a polymerization reaction of the polymerizable compound.
  • a photoacid generator and a color-developing compound are used in the adhesive composition.
  • the photoacid generator receives the first active light beam to generate an acid.
  • the color-developing compound develops color by reacting with an acid. More specifically, the components of the adhesive composition are as described below, for example.
  • the first member M1 is, for example, a display panel such as an organic EL panel.
  • the first member M1 may be another electronic device and an optical device.
  • the adhesive sheet S is bonded to the first member M1 as shown in FIG. 1B.
  • the adhesive sheet S is attached to one side of the first member M1 in the thickness direction.
  • the adhesive sheet S is arranged on one surface of the first member M1 in the thickness direction.
  • the first member M1 and the second member M2 are joined via the adhesive sheet S (joining step).
  • the second member M2 is, for example, a transparent base material.
  • the transparent base material include a transparent plastic base material and a transparent glass base material.
  • the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is cured.
  • the pressure-sensitive adhesive layer 10 in the laminated body W is irradiated with a second active light beam to cure the pressure-sensitive adhesive layer 10.
  • the second active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2.
  • the light source for irradiating the second active light include an ultraviolet LED lamp (UV-LED lamp), a black 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 light ray emitted from the light source may be used as needed.
  • the type of the light source of the second active ray and the use of the wavelength cut filter at the time of irradiation with the second active ray are the same in the second curing step described later.
  • the wavelength range of the second active ray is different from that of the first active ray.
  • the second active ray has a wavelength that does not substantially generate an acid in the photoacid generator.
  • the second active ray preferably contains substantially no light with a wavelength less than 300 nm.
  • the lower limit of the wavelength range of the second active ray is preferably 300 nm, more preferably 320 nm, still more preferably 340 nm, still more preferably 360 nm, still more preferably 380 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 light having such a wavelength is used in the tacky composition.
  • the above configuration regarding the wavelength of the second active ray is the same for the second active ray used in the second curing step described later.
  • 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 used is 2 or more within the wavelength range of 300 nm or more and 500 nm or less. Is preferable.
  • 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 portion of the wavelength of the second active ray is within the wavelength region R. More preferably, all the wavelengths of the second active ray are in the wavelength region R.
  • Such a configuration in which the pressure-sensitive adhesive layer 10 is irradiated with a second active ray having a wavelength within the wavelength region is suitable for curing the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step. .. 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.
  • the shear storage elastic modulus (first shear storage elastic modulus) at 25 ° C. which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 after curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is preferable. Is 0.2 ⁇ 10 5 Pa or more, more preferably 2 ⁇ 10 5 Pa or more, and further preferably 5 ⁇ 10 5 Pa or more.
  • the 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. Further, the shear storage elastic modulus (second shear storage elastic modulus) at 25 ° C.
  • the first shear storage elastic modulus is preferably 10 ⁇ 10 5 Pa or less, more preferably 5 ⁇ 10 5 Pa or less, and further preferably 3 ⁇ 10 5 Pa or less.
  • the ratio of the first shear storage elastic modulus to the second shear storage elastic modulus is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more.
  • the ratio is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less.
  • the above configuration regarding the shear storage elastic modulus is suitable for suppressing deterioration of the discolored portion formed on the pressure-sensitive adhesive layer 10 which will be described later.
  • the discolored portion 11 is formed in the pressure-sensitive adhesive layer 10 by irradiating at least a part of the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam (in FIG. 2B, a part of the pressure-sensitive adhesive layer 10).
  • the case where the discolored portion 11 is formed in is shown as an example).
  • a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10 is used from the side of the transparent second member M2.
  • the pressure-sensitive adhesive layer 10 is irradiated with the first active light beam.
  • the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored.
  • Examples of the light source for irradiating the first active light include an ultraviolet LED lamp (UV-LED lamp), a black light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the irradiation of the first active ray, a wavelength cut filter for cutting a part of the wavelength region of the first active ray emitted from the light source may be used, if necessary.
  • the type of the light source of the first active ray and the use of the wavelength cut filter at the time of irradiation with the first active ray are the same in the first discoloration curing step and the second discoloration curing step described later.
  • the wavelength range of the first active ray is different from that of the second active ray.
  • the wavelength range of the first active ray preferably includes at least a range smaller than the wavelength range of the second active ray (wavelength range on the short wavelength side) (the wavelength range of the first active ray is the wavelength range of the second active ray). May include a range that overlaps with). That is, the first active ray preferably includes a high energy ray that is not included in the second active ray. For example, the first active ray includes light having a wavelength of less than 300 nm.
  • the lower limit of the wavelength range of the first active ray is preferably 200 nm. , More preferably 220 nm, even more preferably 240 nm, even more preferably 250 nm, still more preferably 260 nm, still more preferably 270 nm, and particularly preferably 280 nm.
  • the first active light ray may include light having a wavelength of less than 200 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 ray 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 preferably used in the adhesive composition.
  • the above configuration regarding the wavelength of the first active ray is the same for the first active ray used in the first color change curing step and the second color change curing step described later.
  • an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the color-developing compound is developed by the reaction with the acid.
  • the discolored portion 11 is formed on the pressure-sensitive adhesive layer 10.
  • the discolored portion 11 exhibits, for example, a dark color.
  • the adhesive sheet affixed product Z can be manufactured.
  • 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 following first discoloration curing step may be carried out instead of the steps shown in FIGS. 2A and 2B.
  • the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is discolored and cured. Specifically, by irradiating the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam, the entire pressure-sensitive adhesive layer 10 is cured and discolored. The first active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2.
  • an acid is generated from the photoacid generator in the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the color-developing compound is developed by the reaction with the acid.
  • the pressure-sensitive adhesive layer 10 is discolored (the discolored portion 11 is formed on the entire 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 adhesive sheet affixed product Z can also be manufactured by the above method.
  • a part of the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is discolored and cured. Specifically, by irradiating a part (first part) of the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam, a discolored portion 11 is formed in a part of the pressure-sensitive adhesive layer 10 and the part is cured. Let me. In this step, the pressure-sensitive adhesive layer 10 is irradiated with the first active light beam from the side of the transparent second member M2 via a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10. ..
  • an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the color-developing compound is developed by the reaction with the acid.
  • the discolored portion 11 is formed on the pressure-sensitive adhesive layer 10.
  • the polymerization reaction of the polymerizable compound is started by the photopolymerization initiator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the polymerization reaction proceeds. As a result, the elastic modulus of the portion increases.
  • the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is cured. Specifically, at least a part of the pressure-sensitive adhesive layer 10 in the laminated body W is irradiated with a second active ray to cure the pressure-sensitive adhesive layer 10.
  • the region of the pressure-sensitive adhesive layer 10 irradiated with the second active light beam includes any part (second part) other than the discolored portion 11 of the pressure-sensitive adhesive layer 10, and is preferably the entire pressure-sensitive adhesive layer 10.
  • the second active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2.
  • the pressure-sensitive adhesive sheet S provided with the pressure-sensitive adhesive layer 10 that can be discolored afterwards by irradiation with the first active light beam is bonded to the first member M1 as an adherend (bonding step). Further, the first member M1 and the second member M2 as an adherend are joined via the pressure-sensitive adhesive sheet S (bonding step). According to such a manufacturing method, the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the bonding step and before the formation of the discolored portion 11 of the pressure-sensitive adhesive layer 10. Can be inspected.
  • the pressure-sensitive adhesive layer 10 is cured while suppressing the discoloration of the pressure-sensitive adhesive layer 10. It is suitable for forming a discolored portion 11 having a desired pattern shape on the pressure-sensitive adhesive layer 10.
  • the above configuration (shown in FIG. 3) for carrying out the first discoloration curing step is suitable for efficiently discoloring and curing the entire pressure-sensitive adhesive layer 10. In the above configuration (shown in FIGS.
  • the discolored portion 11 having a desired pattern shape is formed on the pressure-sensitive adhesive layer 10 and the discolored portion 11 has a desired pattern shape. It is suitable for curing the pressure-sensitive adhesive layer 10 while suppressing discoloration of the pressure-sensitive adhesive layer 10 other than the discolored portion 11. Then, after the bonding step, these configurations suitable for forming the discolored portion 11 on the pressure-sensitive adhesive layer 10 and curing the entire pressure-sensitive adhesive layer 10 provide the pressure-sensitive adhesive layer with a softness suitable for bonding to an adherend.
  • Examples of the deterioration of the discolored portion 11 include deformation of the discolored portion 11 due to deformation of the pressure-sensitive adhesive layer 10.
  • Examples of the deterioration of the discolored portion 11 include bleeding, fading, and non-uniformity of the color tint of the discolored portion 11 due to the diffusion of the color-developing compound contained in the discolored portion 11.
  • the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S contains, for example, a base polymer, a polymerizable compound, a photopolymerization initiator, a photoacid generator, and a color-developing compound.
  • 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 (meth) acrylic acid 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 ester include (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester.
  • 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.
  • 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.
  • Examples of the (meth) acrylic acid alkoxyalkyl ester include a (meth) acrylic acid alkoxyalkyl ester having an alkoxy group having 1 to 4 carbon atoms and an alkylene group having 1 to 4 carbon atoms.
  • Examples of such (meth) acrylic acid alkoxyalkyl esters include (meth) acrylic acid 2-methoxymethyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxymethyl, and (meth) acrylic.
  • Examples thereof include 2-ethoxyethyl acid, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • the (meth) acrylic acid alkoxyalkyl ester preferably, (meth) acrylic acid 2-ethoxymethyl is used, and more preferably acrylic acid 2-ethoxymethyl is used.
  • the (meth) acrylic acid ester may be used alone or in combination of two or more.
  • the ratio of the (meth) acrylic acid 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. It 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 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. Further, 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.
  • Polymerizable functional groups include, for example, (meth) acryloyl groups, vinyl groups, and propenyl groups.
  • 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).
  • a compound having a (meth) acryloyl group as a polymerizable functional group is used from the viewpoint of reactivity.
  • the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • the polymerizable compound may be used alone or in combination of two or more.
  • 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 dipenta.
  • examples thereof include erythritol hexa (meth) acrylate, and isocyanuric acid EO-modified di and triacrylate.
  • the polymerizable compound is preferably a polyfunctional monomer, more preferably a tetrafunctional or higher-functional monomer, still more preferably a dipentaerythritol hexa (meth) acrylate, and particularly 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 initiates 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.
  • Examples of the photoacid generator include onium compounds that generate acid by irradiation with ultraviolet rays (first active light beam).
  • 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 blending amount of the photoacid 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 photoacid 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.
  • 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 having a polymerizable functional group and / or a color-developing compound having a polymerizable functional group may be used.
  • a photoacid generator having a polymerizable functional group and / or a color-developing compound having a polymerizable functional group may be used.
  • the monomer component forming the base polymer may contain a color-developing compound (second color-developing compound) having a polymerizable functional group. That is, the color-developing compound may be incorporated in the base polymer. The movement of such a color-developing compound in the pressure-sensitive adhesive layer 10 is suppressed.
  • a color-developing compound second color-developing compound having a polymerizable functional group. That is, the color-developing compound may be incorporated in the base polymer. The movement of such a color-developing compound in the pressure-sensitive adhesive layer 10 is suppressed.
  • the polymerizable compound blended with the base polymer in the adhesive composition may contain a color-developing compound having a polymerizable functional group (second color-developing compound). That is, the color-developing compound may be contained in the adhesive composition in a state in which it can be copolymerized as a polymerizable compound.
  • second color-developing compound Such a color-developing compound is incorporated into the polymer network after being cured by irradiation with a second active ray (that is, after the polymerization reaction of the polymerizable compound has proceeded), and the movement within the pressure-sensitive adhesive layer 10 is suppressed.
  • the monomer component forming the base polymer may contain a color-developing compound having a polymerizable functional group, and the polymerizable compound may contain a color-developing compound having a polymerizable functional group.
  • These configurations in which the movement of the color-developing compound (second color-developing compound) is suppressed are suitable for suppressing the diffusion of the color-developing compound in the discolored portion 11 formed on the pressure-sensitive adhesive layer 10, and therefore. It is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion 11.
  • Examples of the second color-developing compound (having a polymerizable functional group) include a leuco dye having a polymerizable functional group, a triarylmethane dye having a polymerizable functional group, a diphenylmethane dye having a polymerizable functional group, and polymerizable. Examples thereof include a fluorane dye having a functional group, a spiropyran dye having a polymerizable functional group, and a rhodamine dye 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.
  • Examples of the vinyl group include a styrene group.
  • the second color-developing compound may be used alone or in combination of two or more.
  • a leuco dye having a polymerizable functional group is preferably used, a leuco dye having a (meth) acryloyl group is more preferably used, and a leuco dye having an acryloyl group is more preferable. Used.
  • Examples of the leuco dye having a polymerizable functional group include the acryloyl group-containing leuco dye described in International Publication No. 2013/048993.
  • the second color-developing compound may be used together with the first color-developing compound, or may be used in place of the first color-developing compound.
  • the total amount of the first color-developing compound and the second color-developing compound used is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the base polymer. Is 10 parts by mass or less, more preferably 7 parts by mass or less.
  • the monomer component forming the base polymer may contain a photoacid generator having a polymerizable functional group (second photoacid generator). That is, the photoacid generator may be incorporated in the base polymer.
  • the movement of such a photoacid generator in the pressure-sensitive adhesive layer 10 is suppressed.
  • the movement of the color-developing compound in the pressure-sensitive adhesive layer 10 that develops color by the interaction with the acid generated by such a photoacid generator is also suppressed.
  • the polymerizable compound to be blended with the base polymer in the adhesive composition may contain a photoacid generator having a polymerizable functional group (second photoacid generator). That is, the photoacid generator may be contained in the tacky composition in a state in which it can be copolymerized as a polymerizable compound.
  • a photoacid generator is incorporated into the polymer network after being cured by irradiation with a second active ray (that is, after the polymerization reaction of the polymerizable compound has proceeded), and movement within the pressure-sensitive adhesive layer 10 is suppressed. Will be done. The movement of the color-developing compound in the pressure-sensitive adhesive layer 10 that develops color by the interaction with the acid generated by such a photoacid generator is also suppressed.
  • the monomer component forming the base polymer may contain a photoacid generator having a polymerizable functional group, and the polymerizable compound may contain a photoacid generator having a polymerizable functional group.
  • Examples of the second photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays and has a polymerizable functional group.
  • Examples of the polymerizable functional group include the above-mentioned polymerizable functional groups with respect to the second color-developing compound.
  • 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 the anion include a sulfonic acid derivative anion, a sulfonimide derivative anion, and a sulfonmethide derivative anion.
  • the anion has a polymerizable functional group.
  • an onium salt of a sulfonic acid derivative anion having a polymerizable functional group and sulfonium is preferably used, and more preferably, a sulfonic acid derivative anion having a (meth) acryloyl group and sulfonium.
  • the onium salt of and is used, and more preferably, triphenylsulfonium / 4-vinylbenzenesulfonate is used.
  • the method for synthesizing this photoacid generator is described in, for example, "Novel Polymeric anionic photoacid generators (PAGs) and corresponding polymers for 193 nm lithography" (Journal of Materials Chemistry, 2006, Vol. 16, p3701-3707). ..
  • the second photoacid generator may be used alone or in combination of two or more.
  • the second photoacid generator may be used together with the first photoacid generator or may be used in place of the first photoacid generator.
  • the amount of the first photoacid generator and the second photoacid generator to be used with respect to 100 parts by mass of the color-developing compound is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more. Is.
  • the amount used 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 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. 5).
  • 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 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 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 preferable. Is 90% or more.
  • 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 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 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. 6 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.
  • the pressure-sensitive adhesive sheet S shown in FIG. 6 a manufacturing method similar to that of the above-mentioned adhesive sheet-attached product can be carried out except that the above-mentioned joining step is not carried out with reference to FIG. 1C (the pressure-sensitive adhesive sheet shown in FIG. 6).
  • the base material 20 is arranged in place of the above-mentioned second member M2).
  • the pressure-sensitive adhesive sheet-attached product Z' can be manufactured as shown in FIG. 7.
  • the method for manufacturing an adhesive sheet-attached product of the present invention can be applied to, for example, the manufacturing process of a display panel.

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Abstract

This method for manufacturing an adhesive sheet-attached article includes a step for bonding an adhesive sheet (S) to an adherend. An adhesive layer (10) of the adhesive sheet (S) can change color and be cured by irradiation with first actinic light, and can be cured by irradiation with second actinic light. This method includes a step for curing an adhesive layer (10) by irradiation with second actinic light and a step for forming a color change portion in the adhesive layer (10) by irradiating at least a part of the adhesive layer (10) with first actinic light, or this method includes a step for changing color of and curing the adhesive layer (10) by irradiating with the first actinic light, or a step for changing color of and curing a first portion of the adhesive layer (10) by irradiation with the first actinic light and a step for curing a second portion of the adhesive layer (10) by irradiation with the second actinic light.

Description

粘着シート貼付品の製造方法Manufacturing method of adhesive sheet attached products
　本発明は、粘着シート貼付品の製造方法に関する。 The present invention relates to a method for manufacturing an adhesive sheet-attached product.
　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.
特開２０１７－２０３８１０号公報Japanese Unexamined Patent Publication No. 2017-203810
　しかしながら、ディスプレイパネルなどの物品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。物品の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, when an adhesive sheet having a colored portion formed in advance is used in the manufacturing process of an article such as a display panel, after the adhesive sheet is attached to the adherend, the adherend and the colored portion of the adhesive sheet are combined. The presence of foreign matter and air bubbles in between cannot be properly inspected. In order to bond the pressure-sensitive adhesive sheets in the process of manufacturing an article, it is required to be able to appropriately inspect the presence or absence of foreign matter and air bubbles between the adherend and the pressure-sensitive adhesive sheet after the bonding.
　一方、例えば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（変色部分）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。着色部分の劣化としては、例えば、粘着剤層の変形による着色部分の変形が挙げられる。変色部分の劣化としては、例えば、着色部分に含まれる着色成分の拡散に起因する着色部分の滲み、退色、および、色味の不均一化も挙げられる。 On the other hand, for example, from the viewpoint of ensuring the function of the colored portion (discolored portion) provided on the transparent adhesive sheet for the display panel, it is required to suppress the deterioration of the colored portion. Examples of the deterioration of the colored portion include deformation of the colored portion due to deformation of the pressure-sensitive adhesive layer. Examples of the deterioration of the discolored portion include bleeding, fading, and non-uniformity of the color of the colored portion due to the diffusion of the coloring component contained in the colored portion.
　本発明は、被着体への貼合わせ後の粘着シートの少なくとも一部を変色可能であって、当該変色部分の劣化を抑制するのに適した、粘着シート貼付品の製造方法を提供する。 The present invention provides a method for manufacturing an adhesive sheet-attached product, which is capable of discoloring at least a part of the adhesive sheet after being attached to an adherend and is suitable for suppressing deterioration of the discolored portion.
　本発明［１］は、第１活性光線の照射によって変色可能かつ硬化可能であり、且つ第２活性光線の照射によって硬化可能である粘着剤層を、備える粘着シートを、被着体に貼り合わせる貼合せ工程を含む、粘着シート貼付品の製造方法であって、前記被着体上の前記粘着剤層に対する前記第２活性光線の照射によって当該粘着剤層を硬化させる第１の硬化工程と、当該硬化工程より後の、前記粘着剤層の少なくとも一部に対する前記第１活性光線の照射によって前記粘着剤層に変色部分を形成する変色工程とを更に含む、または、前記被着体上の前記粘着剤層に対する前記第１活性光線の照射によって前記粘着剤層を変色させ且つ硬化させる第１の変色硬化工程を更に含む、または、前記被着体上の前記粘着剤層における第１部分に対する前記第１活性光線の照射によって前記第１部分を変色させ且つ硬化させる第２の変色硬化工程と、当該変色硬化工程より後の、前記粘着剤層における第２部分に対する前記第２活性光線の照射によって当該第２部分を硬化させる第２の硬化工程とを更に含む、粘着シート貼付品の製造方法を含む。 In the present invention [1], an adhesive sheet provided with an adhesive layer that can be discolored and cured by irradiation with a first active light beam and can be cured by irradiation with a second active light beam is attached to an adherend. A method for producing an adhesive sheet-attached product, which comprises a bonding step, wherein the pressure-sensitive adhesive layer on the adherend is irradiated with the second active light beam to cure the pressure-sensitive adhesive layer. A discoloration step of forming a discolored portion in the pressure-sensitive adhesive layer by irradiating at least a part of the pressure-sensitive adhesive layer with the first active light beam after the curing step is further included, or the said on the adherend. Further comprising a first discoloration curing step of discoloring and curing the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer with the first active light beam, or said to the first portion of the pressure-sensitive adhesive layer on the adherend. By a second color change curing step of discoloring and curing the first portion by irradiation with the first active light beam, and by irradiating the second portion of the pressure-sensitive adhesive layer with the second active light beam after the color change curing step. The present invention includes a method for producing an adhesive sheet-attached product, further comprising a second curing step of curing the second portion.
　本発明［２］は、前記粘着剤層は、重合性化合物と、光重合開始剤と、酸との反応により発色する化合物と、光酸発生剤とを含有する、上記［１］に記載の粘着シート貼付品の製造方法を含む。 In the present invention [2], the pressure-sensitive adhesive layer contains a polymerizable compound, a photopolymerization initiator, a compound that develops color by reaction with an acid, and a photoacid generator, according to the above [1]. Includes a method for manufacturing adhesive sheet affixed products.
　本発明［３］は、前記粘着剤層は、前記光酸発生剤の吸光度Ｘに対する前記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、上記［２］に記載の粘着シート貼付品の製造方法を含む。 In the present invention [3], the pressure-sensitive adhesive layer has a wavelength region 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 a wavelength range of 300 nm or more and 500 nm or less. The method for producing the adhesive sheet-attached product according to the above [2] is included.
　本発明［４］は、前記硬化工程における前記第２活性光線は、３００ｎｍ未満の波長の光を実質的に含まない、上記［１］から［３］のいずれか一つに記載の粘着シート貼付品の製造方法を含む。 In the present invention [4], the adhesive sheet attachment according to any one of the above [1] to [3], wherein the second active light ray in the curing step substantially does not contain light having a wavelength of less than 300 nm. Including the manufacturing method of the product.
　本発明［５］は、前記硬化工程では、前記第２活性光線の光源として、ＵＶ－ＬＥＤランプ、ブラックライト、高圧水銀ランプ、およびメタルハライドランプからなる群より選択される少なくとも一つの光源が使用され、且つ、前記光源からの光が波長カットフィルターを介して前記粘着剤層に照射される、上記［１］から［４］のいずれか一つに記載の粘着シート貼付品の製造方法を含む。 In the present invention [5], at least one light source selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp is used as the light source of the second active light in the curing step. The method for producing a pressure-sensitive adhesive sheet-attached product according to any one of the above [1] to [4], wherein the light from the light source is applied to the pressure-sensitive adhesive layer via a wavelength cut filter.
　本発明［６］は、前記変色工程および／または前記変色硬化工程における前記第１活性光線は、３００ｎｍ未満の波長の光を含む、上記［１］から［５］のいずれか一つに記載の粘着シート貼付品の製造方法を含む。 The present invention [6] is described in any one of the above [1] to [5], wherein the first active light ray in the discoloration step and / or the discoloration curing step contains light having a wavelength of less than 300 nm. Includes a method for manufacturing adhesive sheet affixed products.
　本発明［７］は、前記変色工程および／または前記変色硬化工程では、前記第１活性光線の光源として、ＵＶ－ＬＥＤランプ、ブラックライト、高圧水銀ランプ、およびメタルハライドランプからなる群より選択される少なくとも一つの光源が使用される、上記［１］から［６］のいずれか一つに記載の粘着シート貼付品の製造方法を含む。 The present invention [7] is selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp as a light source of the first active light in the discoloration step and / or the discoloration curing step. The method for manufacturing an adhesive sheet affixed product according to any one of the above [1] to [6], wherein at least one light source is used.
　本発明の粘着シート貼付品の製造方法では、貼合せ工程において、第１活性光線の照射によって変色可能な粘着剤層を備える粘着シートが、被着体に貼り合わせられる。そのため、当該貼合せ工程より後に、粘着剤層における変色予定部分に対する第１活性光線の照射により、当該粘着剤層の少なくとも一部を変色させることができる（変色工程、第１の変色硬化工程、または第２の変色硬化工程）。このような製造方法によると、被着体に対する粘着シートの貼合せ後であって、粘着剤層の変色部分形成前に、粘着シートと被着体との間における異物および気泡の有無を検査できる。 In the method for manufacturing an adhesive sheet-attached product of the present invention, an adhesive sheet provided with an adhesive layer that can be discolored by irradiation with a first active light beam is attached to an adherend in the bonding step. Therefore, after the bonding step, at least a part of the pressure-sensitive adhesive layer can be discolored by irradiating the portion to be discolored in the pressure-sensitive adhesive layer with the first active light beam (color-changing step, first discoloration curing step, Or a second discoloration curing step). According to such a manufacturing method, it is possible to inspect the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet and the adherend after the pressure-sensitive adhesive sheet is attached to the adherend and before the discolored portion of the pressure-sensitive adhesive layer is formed. ..
　また、本製造方法において、第１の硬化工程とその後の変色工程とを実施する上記構成は、粘着剤層の変色を抑制しつつ粘着剤層を硬化させ、且つ、粘着剤層に所望のパターン形状の変色部分を形成するのに適する。第１の変色硬化工程を実施する上記構成は、粘着剤層の全体を効率よく変色および硬化させるのに適する。第２の変色硬化工程とその後の第２の硬化工程とを実施する上記構成は、粘着剤層に所望のパターン形状の変色部分を形成し、且つ、粘着剤層における変色部分以外の変色を抑制しつつ粘着剤層を硬化させるのに適する。そして、貼合せ工程後に、粘着剤層の少なくとも一部に変色部分を形成し且つ粘着剤層の全体を硬化させるのに適するこれら構成は、被着体に対する貼り合わせに適した柔らかさを粘着剤層（硬化前）において貼り合わせ時に確保しつつ、製造される粘着シート貼付品の粘着剤層（硬化後）において、変色部分の劣化を抑制するのに適する。 Further, in the above configuration in which the first curing step and the subsequent discoloration step are carried out in the present manufacturing method, the pressure-sensitive adhesive layer is cured while suppressing the discoloration of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer has a desired pattern. Suitable for forming discolored parts of the shape. The above configuration for carrying out the first discoloration curing step is suitable for efficiently discoloring and curing the entire pressure-sensitive adhesive layer. In the above configuration in which the second discoloration curing step and the subsequent second curing step are carried out, a discolored portion having a desired pattern shape is formed in the pressure-sensitive adhesive layer, and discoloration other than the discolored portion in the pressure-sensitive adhesive layer is suppressed. Suitable for curing the adhesive layer while doing so. Then, after the bonding step, these configurations suitable for forming a discolored portion in at least a part of the pressure-sensitive adhesive layer and curing the entire pressure-sensitive adhesive layer provide a softness suitable for bonding to an adherend. It is suitable for suppressing deterioration of the discolored portion in the pressure-sensitive adhesive layer (after curing) of the manufactured pressure-sensitive adhesive sheet-attached product while ensuring the layer (before curing) at the time of bonding.
本発明の粘着シート貼付品の製造方法の一実施形態における一部の工程を表す。図１Ａは、粘着シートおよび第１部材を用意する工程を表し、図１Ｂは、粘着シートを第１部材に貼り合わせる工程（貼合せ工程）を表し、図１Ｃは、第１部材と第２部材とを粘着シートを介して接合する工程（接合工程）を表す。Represents a part of the steps in one embodiment of the method for manufacturing an adhesive sheet-attached product of the present invention. FIG. 1A shows a step of preparing an adhesive sheet and a first member, FIG. 1B shows a step of attaching an adhesive sheet to a first member (bonding step), and FIG. 1C shows a first member and a second member. Represents a step (joining step) of joining and with via an adhesive sheet. 図１Ｃに示す工程の後に続く工程を表す。図２Ａは、粘着シートの粘着剤層を硬化させる工程（第１の硬化工程）を表し、図２Ｂは、粘着シートの粘着剤層の一部を変色させる工程（変色工程）を表す。The process following the process shown in FIG. 1C is represented. FIG. 2A represents a step of curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (first curing step), and FIG. 2B represents a step of discoloring a part of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (color-changing step). 図１Ｃに示す工程の後に続く他の工程を表す。具体的には、粘着剤層を変色および硬化させる工程（第１の変色硬化工程）を表す。Represents another step following the step shown in FIG. 1C. Specifically, it represents a step of discoloring and curing the pressure-sensitive adhesive layer (first discoloration and curing step). 図１Ｃに示す工程の後に続く他の工程を表す。図４Ａは、粘着シートの粘着剤層の一部を変色および硬化させる工程（第２の変色硬化工程）を表し、図４Ｂは、粘着シートの粘着剤層を硬化させる工程（第２の硬化工程）を表す。Represents another step following the step shown in FIG. 1C. FIG. 4A shows a step of discoloring and curing a part of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (second discoloration curing step), and FIG. 4B shows a step of curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (second curing step). ). 本発明の粘着シート貼付品の製造方法に用いられる粘着シートの断面模式図である。It is sectional drawing of the adhesive sheet used in the manufacturing method of the adhesive sheet attached article of this invention. 本発明の粘着シート貼付品の製造方法に用いられる粘着シートの変形例（粘着シートが基材付き片面粘着シートである場合）の断面模式図である。It is sectional drawing of the modification (when the adhesive sheet is a single-sided adhesive sheet with a base material) of the adhesive sheet used in the manufacturing method of the adhesive sheet attached article of this invention. 図６に示す粘着シートを用いて製造される粘着シート貼付品を表す。It represents an adhesive sheet affixed product manufactured by using the adhesive sheet shown in FIG.
　図１Ａから図２Ｂは、本発明の粘着シート貼付品の製造方法の一実施形態を表す。本製造方法は、用意工程と、貼合せ工程と、第１の硬化工程と、変色工程とを含む。 1A to 2B show an embodiment of the method for manufacturing an adhesive sheet-attached product of the present invention. The present manufacturing method includes a preparation step, a bonding step, a first curing step, and a discoloration step.
　まず、用意工程では、図１Ａに示すように、粘着シートＳと、第１部材Ｍ１（被着体）とを用意する。 First, in the preparation process, as shown in FIG. 1A, the adhesive sheet S and the first member M1 (adhesive body) are prepared.
　粘着シートＳは、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。粘着剤層１０は、粘着性組成物から形成された感圧接着剤層である。粘着剤層１０は、透明性（可視光透過性）を有する。また、粘着剤層１０は、後述の第１活性光線の照射によって変色可能かつ硬化可能であり、且つ、第１活性光線とは異なる後述の第２活性光線の照射によって硬化可能である。粘着性組成物は、本実施形態では、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。光重合開始剤は、第２活性光線を受けて重合性化合物の重合反応を開始させる。また、本実施形態では、粘着性組成物において、光酸発生剤と、発色性化合物とが用いられる。光酸発生剤は、第１活性光線を受けて酸を発生させる。発色性化合物は、酸との反応によって発色する。粘着性組成物の成分は、より具体的には、例えば後述のとおりである。 The adhesive sheet S includes an adhesive layer 10. The adhesive sheet S has a sheet shape having a predetermined thickness and extends in a direction (plane direction) orthogonal to the thickness direction. The pressure-sensitive adhesive layer 10 is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. The pressure-sensitive adhesive layer 10 has transparency (visible light transmission). Further, the pressure-sensitive adhesive layer 10 can be discolored and cured by irradiation with a first active ray described later, and can be cured by irradiation with a second active ray described later different from the first active ray. In this embodiment, the tacky composition contains a base polymer, a polymerizable compound, and a photopolymerization initiator. The photopolymerization initiator receives a second active light beam to initiate a polymerization reaction of the polymerizable compound. Further, in the present embodiment, a photoacid generator and a color-developing compound are used in the adhesive composition. The photoacid generator receives the first active light beam to generate an acid. The color-developing compound develops color by reacting with an acid. More specifically, the components of the adhesive composition are as described below, for example.
　第１部材Ｍ１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Ｍ１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。 The first member M1 is, for example, a display panel such as an organic EL panel. The first member M1 may be another electronic device and an optical device.
　次に、貼合せ工程では、図１Ｂに示すように、第１部材Ｍ１に粘着シートＳを貼り合わせる。本実施形態では、第１部材Ｍ１の厚さ方向一方面に粘着シートＳを貼り合わせる。これにより、第１部材Ｍ１の厚さ方向一方面上に粘着シートＳが配置される。 Next, in the bonding step, the adhesive sheet S is bonded to the first member M1 as shown in FIG. 1B. In the present embodiment, the adhesive sheet S is attached to one side of the first member M1 in the thickness direction. As a result, the adhesive sheet S is arranged on one surface of the first member M1 in the thickness direction.
　貼合せ工程の後、必要に応じて、部材Ｍ１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 bonding step, if necessary, inspect for foreign matter and air bubbles between the member M1 and the adhesive sheet S.
　本実施形態では、次に、図１Ｃに示すように、粘着シートＳを介して第１部材Ｍ１および第２部材Ｍ２を接合する（接合工程）。第２部材Ｍ２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。本工程により、積層体Ｗが得られる。積層体Ｗにおいて、粘着シートＳは、第１部材Ｍ１の厚さ方向一方面に接触するように配置され、第２部材Ｍ２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ている。 In the present embodiment, next, as shown in FIG. 1C, the first member M1 and the second member M2 are joined via the adhesive sheet S (joining step). The second member M2 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. By this step, the laminated body W is obtained. In the laminated body W, the adhesive sheet S is arranged so as to be in contact with one surface in the thickness direction of the first member M1, and the second member M2 is arranged so as to be in contact with one surface in the thickness direction of the adhesive sheet S. Has been done.
　接合工程の後、必要に応じて、部材Ｍ１,Ｍ２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 M1 and M2 and the adhesive sheet S.
　次に、第１の硬化工程では、図２Ａに示すように、粘着シートＳの粘着剤層１０を硬化させる。具体的には、積層体Ｗにおける粘着剤層１０に第２活性光線を照射して粘着剤層１０を硬化させる。第２活性光線は、透明な第２部材Ｍ２の側から粘着剤層１０に対して照射される。第２活性光線照射用の光源としては、例えば、紫外線ＬＥＤランプ（ＵＶ-ＬＥＤランプ）、ブラックライト、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、第２活性光線の照射においては、光源から出射される光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。第２活性光線の光源の種類、および、第２活性光線照射時の波長カットフィルターの利用については、後述の第２の硬化工程においても同様である。 Next, in the first curing step, as shown in FIG. 2A, the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is cured. Specifically, the pressure-sensitive adhesive layer 10 in the laminated body W is irradiated with a second active light beam to cure the pressure-sensitive adhesive layer 10. The second active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2. Examples of the light source for irradiating the second active light include an ultraviolet LED lamp (UV-LED lamp), a black light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the irradiation of the second active light ray, a wavelength cut filter for cutting a part of the wavelength region in the light ray emitted from the light source may be used as needed. The type of the light source of the second active ray and the use of the wavelength cut filter at the time of irradiation with the second active ray are the same in the second curing step described later.
　第２活性光線は、第１活性光線とは波長範囲が異なる。第２活性光線は、本実施形態では、光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。第２活性光線は、好ましくは、３００ｎｍ未満の波長の光を実質的に含まない。第２活性光線の波長範囲の下限は、好ましくは３００ｎｍ、より好ましくは３２０ｎｍ、一層好ましくは３４０ｎｍ、より一層好ましくは３６０ｎｍ、更に好ましくは３８０ｎｍ、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、このような波長の光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、粘着性組成物において用いられる。第２活性光線の波長に関する以上の構成については、後述の第２の硬化工程で用いられる第２活性光線においても同様である。 The wavelength range of the second active ray is different from that of the first active ray. In the present embodiment, the second active ray has a wavelength that does not substantially generate an acid in the photoacid generator. The second active ray preferably contains substantially no light with a wavelength less than 300 nm. The lower limit of the wavelength range of the second active ray is preferably 300 nm, more preferably 320 nm, still more preferably 340 nm, still more preferably 360 nm, still more preferably 380 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 light having such a wavelength is used in the tacky composition. The above configuration regarding the wavelength of the second active ray is the same for the second active ray used in the second curing step described later.
　本工程では、第２活性光線の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 the second active light, 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、用いられる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活性光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活性光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第２活性光線を粘着剤層１０に照射する構成は、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。 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 used is 2 or more within the wavelength range of 300 nm or more and 500 nm or less. Is preferable. 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 portion of the wavelength of the second active ray is within the wavelength region R. More preferably, all the wavelengths of the second active ray are in the wavelength region R. Such a configuration in which the pressure-sensitive adhesive layer 10 is irradiated with a second active ray having a wavelength within the wavelength region is suitable for curing the pressure-sensitive adhesive layer 10 while suppressing discoloration in the pressure-sensitive adhesive layer 10 in the curing step. .. 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.
　硬化後の粘着剤層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、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。当該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。また、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２せん断貯蔵弾性率）は、好ましくは０.１×１０５Ｐａ以上、より好ましくは０.２×１０５Ｐａ以上、更に好ましくは０.３×１０５Ｐａ以上である。第１せん断貯蔵弾性率は、好ましくは１０×１０５Ｐａ以下、より好ましくは５×１０５Ｐａ以下、更に好ましくは３×１０５Ｐａ以下である。第２せん断貯蔵弾性率に対する第１せん断貯蔵弾性率の比率は、好ましくは２以上、より好ましくは５以上、更に好ましくは１０以上である。同比率は、好ましくは１００以下、より好ましくは５０以下、更に好ましくは３０以下である。せん断貯蔵弾性率に関する以上の構成は、粘着剤層１０に形成される変色部分の後述の劣化を抑制するのに適する。 The shear storage elastic modulus (first shear storage elastic modulus) at 25 ° C., which is shown by the dynamic viscoelasticity measurement of the pressure-sensitive adhesive layer 10 after curing under the conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min, is preferable. Is 0.2 × 10 5 Pa or more, more preferably 2 × 10 5 Pa or more, and further preferably 5 × 10 5 Pa or more. The 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. Further, the shear storage elastic modulus (second 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 It is preferably 0.1 × 10 5 Pa or more, more preferably 0.2 × 10 5 Pa or more, and further preferably 0.3 × 10 5 Pa or more. The first shear storage elastic modulus is preferably 10 × 10 5 Pa or less, more preferably 5 × 10 5 Pa or less, and further preferably 3 × 10 5 Pa or less. The ratio of the first shear storage elastic modulus to the second shear storage elastic modulus is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more. The ratio is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less. The above configuration regarding the shear storage elastic modulus is suitable for suppressing deterioration of the discolored portion formed on the pressure-sensitive adhesive layer 10 which will be described later.
　次に、変色工程では、図２Ｂに示すように、粘着シートＳの粘着剤層１０の少なくとも一部を変色させる。具体的には、積層体Ｗにおける粘着剤層１０の少なくとも一部に対する第１活性光線の照射によって、粘着剤層１０に変色部分１１を形成する（図２Ｂには、粘着剤層１０の一部に変色部分１１を形成する場合を例示的に図示する）。本工程において、粘着剤層１０の一部に変色部分１１を形成する場合、透明な第２部材Ｍ２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活性光線を照射する。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。 Next, in the discoloration step, as shown in FIG. 2B, at least a part of the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is discolored. Specifically, the discolored portion 11 is formed in the pressure-sensitive adhesive layer 10 by irradiating at least a part of the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam (in FIG. 2B, a part of the pressure-sensitive adhesive layer 10). The case where the discolored portion 11 is formed in is shown as an example). In this step, when the discolored portion 11 is formed on a part of the pressure-sensitive adhesive layer 10, a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10 is used from the side of the transparent second member M2. Then, the pressure-sensitive adhesive layer 10 is irradiated with the first active light beam. As a result, the portion of the pressure-sensitive adhesive layer 10 that is not masked by the mask pattern is discolored.
　第１活性光線照射用の光源としては、例えば、紫外線ＬＥＤランプ（ＵＶ-ＬＥＤランプ）、ブラックライト、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、第１活性光線の照射においては、光源から出射される第１活性光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。第１活性光線の光源の種類、および、第１活性光線照射時の波長カットフィルターの利用については、後述の第１の変色硬化工程および第２の変色硬化工程においても同様である。 Examples of the light source for irradiating the first active light include an ultraviolet LED lamp (UV-LED lamp), a black light, a high-pressure mercury lamp, and a metal halide lamp. Further, in the irradiation of the first active ray, a wavelength cut filter for cutting a part of the wavelength region of the first active ray emitted from the light source may be used, if necessary. The type of the light source of the first active ray and the use of the wavelength cut filter at the time of irradiation with the first active ray are the same in the first discoloration curing step and the second discoloration curing step described later.
　第１活性光線は、第２活性光線とは波長範囲が異なる。第１活性光線の波長範囲は、好ましくは、少なくとも第２活性光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活性光線の波長範囲は、第２活性光線の波長範囲と重複する範囲を含んでもよい）。すなわち、第１活性光線は、好ましくは、第２活性光線には含まれない高エネルギーの光線を含む。例えば、第１活性光線は、３００ｎｍ未満の波長の光を含む。 The wavelength range of the first active ray is different from that of the second active ray. The wavelength range of the first active ray preferably includes at least a range smaller than the wavelength range of the second active ray (wavelength range on the short wavelength side) (the wavelength range of the first active ray is the wavelength range of the second active ray). May include a range that overlaps with). That is, the first active ray preferably includes a high energy ray that is not included in the second active ray. For example, the first active ray includes light having a wavelength of less than 300 nm.
　第１活性光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活性光線の波長範囲に下限を設ける場合、当該第１活性光線の波長範囲の下限は、好ましくは２００ｎｍ、より好ましくは２２０ｎｍ、一層好ましくは２４０ｎｍ、より一層好ましくは２５０ｎｍ、更に好ましくは２６０ｎｍ、こと更に好ましくは２７０ｎｍ、特に好ましくは２８０ｎｍである。或いは、第１活性光線には、波長２００ｎｍ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活性光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活性光線の波長範囲に上限を設ける場合、当該第１活性光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、粘着性組成物において用いられる。第１活性光線の波長に関する以上の構成については、後述の第１の変色硬化工程および第２の変色硬化工程で用いられる第１活性光線においても同様である。 When the first active ray has a lower limit in the wavelength range, or when the lower limit is set in the wavelength range of the first active ray by using, for example, a wavelength cut filter, the lower limit of the wavelength range of the first active ray is preferably 200 nm. , More preferably 220 nm, even more preferably 240 nm, even more preferably 250 nm, still more preferably 260 nm, still more preferably 270 nm, and particularly preferably 280 nm. Alternatively, the first active light ray may include light having a wavelength of less than 200 nm. Light sources of such light include, for example, high pressure mercury lamps and metal halide lamps. When the first active ray has an upper limit in the wavelength range, or when the upper limit is set in the wavelength range of the first active ray by using, for example, a wavelength cut filter, the upper limit of the wavelength range of the first active ray 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, a photoacid generator that generates an acid by being irradiated with active energy rays having such a wavelength is preferably used in the adhesive composition. The above configuration regarding the wavelength of the first active ray is the same for the first active ray used in the first color change curing step and the second color change curing step described later.
　本工程では、粘着剤層１０において第１活性光線が照射された部分で、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。これにより、粘着剤層１０に変色部分１１が形成される。変色部分１１は、例えば暗色を呈する。 In this step, an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, 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. The discolored portion 11 exhibits, for example, a dark color.
　以上のようにして、粘着シート貼付品Ｚを製造できる。第１部材Ｍ１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。 As described above, the adhesive sheet affixed product Z can be manufactured. When the first member M1 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.
　本製造方法では、図１Ｃに示す工程の後、図２Ａおよび図２Ｂに示す工程の代わりに、以下のような第１の変色硬化工程を実施してもよい。 In this manufacturing method, after the step shown in FIG. 1C, the following first discoloration curing step may be carried out instead of the steps shown in FIGS. 2A and 2B.
　第１の変色硬化工程では、図３に示すように、粘着シートＳの粘着剤層１０を変色および硬化させる。具体的には、積層体Ｗにおける粘着剤層１０に対する第１活性光線の照射によって、粘着剤層１０の全体を硬化させるとともに変色させる。第１活性光線は、透明な第２部材Ｍ２の側から粘着剤層１０に対して照射される。 In the first discoloration curing step, as shown in FIG. 3, the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is discolored and cured. Specifically, by irradiating the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam, the entire pressure-sensitive adhesive layer 10 is cured and discolored. The first active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2.
　本工程では、第１活性光線の照射を受けた粘着剤層１０において、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。これにより、粘着剤層１０が変色される（粘着剤層１０の全体に変色部分１１が形成される）。また、本工程では、第１活性光線の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, an acid is generated from the photoacid generator in the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the color-developing compound is developed by the reaction with the acid. As a result, the pressure-sensitive adhesive layer 10 is discolored (the discolored portion 11 is formed on the entire pressure-sensitive adhesive layer 10). Further, in this step, in the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, 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.
　以上の方法によっても、粘着シート貼付品Ｚを製造できる。 The adhesive sheet affixed product Z can also be manufactured by the above method.
　本製造方法では、図１Ｃに示す工程の後、図２Ａおよび図２Ｂに示す工程の代わりに、以下のような第２の変色硬化工程と、第２の硬化工程とを実施してもよい。 In this manufacturing method, after the step shown in FIG. 1C, instead of the steps shown in FIGS. 2A and 2B, the following second discoloration curing step and the second curing step may be carried out.
　第２の変色硬化工程では、図４Ａに示すように、粘着シートＳの粘着剤層１０の一部を変色および硬化させる。具体的には、積層体Ｗにおける粘着剤層１０の一部（第１部分）に対する第１活性光線の照射によって、粘着剤層１０の一部に変色部分１１を形成し且つ当該一部を硬化させる。本工程では、透明な第２部材Ｍ２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活性光線を照射する。 In the second discoloration curing step, as shown in FIG. 4A, a part of the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is discolored and cured. Specifically, by irradiating a part (first part) of the pressure-sensitive adhesive layer 10 in the laminated body W with the first active light beam, a discolored portion 11 is formed in a part of the pressure-sensitive adhesive layer 10 and the part is cured. Let me. In this step, the pressure-sensitive adhesive layer 10 is irradiated with the first active light beam from the side of the transparent second member M2 via a mask pattern (not shown) for masking a predetermined region in the pressure-sensitive adhesive layer 10. ..
　本工程では、粘着剤層１０において第１活性光線の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。これにより、粘着剤層１０に変色部分１１が形成される。また、本工程では、粘着剤層１０において第１活性光線の照射を受けた部分で、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、当該部分の弾性率が上昇する。 In this step, an acid is generated from the photoacid generator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, 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. Further, in this step, the polymerization reaction of the polymerizable compound is started by the photopolymerization initiator at the portion of the pressure-sensitive adhesive layer 10 irradiated with the first active light beam, and the polymerization reaction proceeds. As a result, the elastic modulus of the portion increases.
　第２の硬化工程では、図４Ｂに示すように、粘着シートＳの粘着剤層１０を硬化させる。具体的には、積層体Ｗにおける粘着剤層１０の少なくとも一部に第２活性光線を照射して粘着剤層１０を硬化させる。粘着剤層１０において第２活性光線が照射される領域は、粘着剤層１０の変色部分１１以外のいずれかの部分（第２部分）を含み、好ましくは粘着剤層１０の全体である。第２活性光線は、透明な第２部材Ｍ２の側から粘着剤層１０に対して照射される。 In the second curing step, as shown in FIG. 4B, the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S is cured. Specifically, at least a part of the pressure-sensitive adhesive layer 10 in the laminated body W is irradiated with a second active ray to cure the pressure-sensitive adhesive layer 10. The region of the pressure-sensitive adhesive layer 10 irradiated with the second active light beam includes any part (second part) other than the discolored portion 11 of the pressure-sensitive adhesive layer 10, and is preferably the entire pressure-sensitive adhesive layer 10. The second active ray is applied to the pressure-sensitive adhesive layer 10 from the side of the transparent second member M2.
　本工程では、第２活性光線の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（図４Ｂには、粘着剤層１０の全体が硬化される場合を例示的に図示する）。 In this step, in the pressure-sensitive adhesive layer 10 irradiated with the second active light, 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 (FIG. 4B illustrates a case where the entire pressure-sensitive adhesive layer 10 is cured).
　以上の製造方法では、第１活性光線の照射によって事後的に変色可能な粘着剤層１０を備える粘着シートＳが、被着体としての第１部材Ｍ１に貼り合わせられる（貼合せ工程）。また、当該粘着シートＳを介して、被着体としての第１部材Ｍ１と第２部材Ｍ２とが接合される（接合工程）。このような製造方法によると、貼合せ工程後において、また、接合工程後において、粘着剤層１０の変色部分１１の形成前に、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 manufacturing method, the pressure-sensitive adhesive sheet S provided with the pressure-sensitive adhesive layer 10 that can be discolored afterwards by irradiation with the first active light beam is bonded to the first member M1 as an adherend (bonding step). Further, the first member M1 and the second member M2 as an adherend are joined via the pressure-sensitive adhesive sheet S (bonding step). According to such a manufacturing method, the presence or absence of foreign matter and air bubbles between the pressure-sensitive adhesive sheet S and the adherend after the bonding step and before the formation of the discolored portion 11 of the pressure-sensitive adhesive layer 10. Can be inspected.
　また、本製造方法において、第１の硬化工程とその後の変色工程とを実施する上記構成（図２Ａおよび図２Ｂに示す）は、粘着剤層１０の変色を抑制しつつ粘着剤層１０を硬化させ、且つ、粘着剤層１０に所望のパターン形状の変色部分１１を形成するのに適する。第１の変色硬化工程を実施する上記構成（図３に示す）は、粘着剤層１０の全体を効率よく変色および硬化させるのに適する。第２の変色硬化工程とその後の第２の硬化工程とを実施する上記構成（図４Ａおよび図４Ｂに示す）は、粘着剤層１０に所望のパターン形状の変色部分１１を形成し、且つ、粘着剤層１０における変色部分１１以外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。そして、貼合せ工程後に、粘着剤層１０に変色部分１１を形成し且つ粘着剤層１０の全体を硬化させるのに適するこれら構成は、被着体に対する貼り合わせに適した柔らかさを粘着剤層１０（硬化前）において確保しつつ、粘着剤層１０（硬化後）において、変色部分１１の劣化を抑制するのに適する。変色部分１１の劣化としては、例えば、粘着剤層１０の変形による変色部分１１の変形が挙げられる。変色部分１１の劣化としては、例えば、変色部分１１に含まれる発色性化合物の拡散に起因する変色部分１１の滲み、退色、および、色味の不均一化も挙げられる。 Further, in the above-mentioned configuration (shown in FIGS. 2A and 2B) in which the first curing step and the subsequent discoloration step are carried out in the present manufacturing method, the pressure-sensitive adhesive layer 10 is cured while suppressing the discoloration of the pressure-sensitive adhesive layer 10. It is suitable for forming a discolored portion 11 having a desired pattern shape on the pressure-sensitive adhesive layer 10. The above configuration (shown in FIG. 3) for carrying out the first discoloration curing step is suitable for efficiently discoloring and curing the entire pressure-sensitive adhesive layer 10. In the above configuration (shown in FIGS. 4A and 4B) in which the second discoloration curing step and the subsequent second curing step are carried out, the discolored portion 11 having a desired pattern shape is formed on the pressure-sensitive adhesive layer 10 and the discolored portion 11 has a desired pattern shape. It is suitable for curing the pressure-sensitive adhesive layer 10 while suppressing discoloration of the pressure-sensitive adhesive layer 10 other than the discolored portion 11. Then, after the bonding step, these configurations suitable for forming the discolored portion 11 on the pressure-sensitive adhesive layer 10 and curing the entire pressure-sensitive adhesive layer 10 provide the pressure-sensitive adhesive layer with a softness suitable for bonding to an adherend. It is suitable for suppressing deterioration of the discolored portion 11 in the pressure-sensitive adhesive layer 10 (after curing) while ensuring at 10 (before curing). Examples of the deterioration of the discolored portion 11 include deformation of the discolored portion 11 due to deformation of the pressure-sensitive adhesive layer 10. Examples of the deterioration of the discolored portion 11 include bleeding, fading, and non-uniformity of the color tint of the discolored portion 11 due to the diffusion of the color-developing compound contained in the discolored portion 11.
　粘着シートＳの粘着剤層１０を形成する粘着性組成物は、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、光酸発生剤と、発色性化合物とを含む。 The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 10 of the pressure-sensitive adhesive sheet S contains, for example, a base polymer, a polymerizable compound, a photopolymerization initiator, a photoacid generator, and a color-developing compound.
　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 (meth) acrylic acid ester in a proportion of 50% by mass or more. "(Meta) acrylic acid" means acrylic acid and / or methacrylic acid.
　（メタ）アクリル酸エステルとしては、（メタ）アクリル酸アルキルエステルおよび（メタ）アクリル酸アルコキシアルキルエステルが挙げられる。 Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester.
　（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. 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.
　（メタ）アクリル酸アルコキシアルキルエステルとしては、例えば、炭素数１～４のアルコキシ基および炭素数１～４のアルキレン基を有する（メタ）アクリル酸アルコキシアルキルエステルが挙げられる。そのような（メタ）アクリル酸アルコキシアルキルエステルとしては、例えば、（メタ）アクリル酸２－メトキシメチル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシメチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸３－メトキシプロピル、（メタ）アクリル酸３－エトキシプロピル、（メタ）アクリル酸４－メトキシブチル、および（メタ）アクリル酸４－エトキシブチルが挙げられる。（メタ）アクリル酸アルコキシアルキルエステルとしては、好ましくは、好ましくは（メタ）アクリル酸２－エトキシメチルが用いられ、より好ましくはアクリル酸２－エトキシメチルが用いられる。 Examples of the (meth) acrylic acid alkoxyalkyl ester include a (meth) acrylic acid alkoxyalkyl ester having an alkoxy group having 1 to 4 carbon atoms and an alkylene group having 1 to 4 carbon atoms. Examples of such (meth) acrylic acid alkoxyalkyl esters include (meth) acrylic acid 2-methoxymethyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxymethyl, and (meth) acrylic. Examples thereof include 2-ethoxyethyl acid, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. As the (meth) acrylic acid alkoxyalkyl ester, preferably, (meth) acrylic acid 2-ethoxymethyl is used, and more preferably acrylic acid 2-ethoxymethyl is used.
　（メタ）アクリル酸エステルは、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。 The (meth) acrylic acid ester may be used alone or in combination of two or more.
　モノマー成分における（メタ）アクリル酸エステルの割合は、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 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. It 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 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。また、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. Further, 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、(メタ)アクリロイル基、ビニル基、およびプロペニル基が挙げられる。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。また、重合性化合物としては、反応性の観点から、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用いられる。(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。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. Polymerizable functional groups include, for example, (meth) acryloyl groups, vinyl groups, and propenyl groups. 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). Further, as the polymerizable compound, a compound having a (meth) acryloyl group as a polymerizable functional group is used from the viewpoint of reactivity. The (meth) acryloyl group means an acryloyl group and / or a methacryloyl group. The polymerizable compound may be used alone or in combination of two or more.
　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、ジペンタエリスリトールヘキサ(メタ)アクリレート、およびイソシアヌル酸ＥＯ変性ジ及びトリ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 dipenta. Examples thereof include erythritol hexa (meth) acrylate, and isocyanuric acid EO-modified di and triacrylate.
　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、より好ましくは四官能以上の多官能モノマー、更に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、特に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 tetrafunctional or higher-functional monomer, still more preferably a dipentaerythritol hexa (meth) acrylate, and particularly 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、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 initiates 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.
　光酸発生剤（第１の光酸発生剤）としては、例えば、紫外線照射（第１活性光線）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 (first photoacid generator) include onium compounds that generate acid by irradiation with ultraviolet rays (first active light beam). 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.
　ベースポリマー１００質量部に対する光酸発生剤の配合量は、好ましくは１質量部以上、より好ましくは２質量部以上、更に好ましくは５質量部以上、特に好ましくは７質量部以上である。同配合量は、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１２質量部以下である。 The blending amount of the photoacid 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質量部に対する光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 photoacid 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.
　発色性化合物（第１の発色性化合物）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 (first 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.
　粘着性組成物においては、重合性官能基を有する光酸発生剤、および／または、重合性官能基を有する発色性化合物を用いてもよい。例えば、以下のとおりである。 In the adhesive composition, a photoacid generator having a polymerizable functional group and / or a color-developing compound having a polymerizable functional group may be used. For example:
　ベースポリマーを形成するモノマー成分は、重合性官能基を有する発色性化合物（第２の発色性化合物）を含んでもよい。すなわち、発色性化合物は、ベースポリマーに組み込まれた状態を採ってもよい。このような発色性化合物は、粘着剤層１０内での移動が抑制される。 The monomer component forming the base polymer may contain a color-developing compound (second color-developing compound) having a polymerizable functional group. That is, the color-developing compound may be incorporated in the base polymer. The movement of such a color-developing compound in the pressure-sensitive adhesive layer 10 is suppressed.
　粘着性組成物にベースポリマーと共に配合される重合性化合物は、重合性官能基を有する発色性化合物（第２の発色性化合物）を含んでもよい。すなわち、発色性化合物は、重合性化合物として共重合可能な状態で粘着性組成物に含有されていてもよい。このような発色性化合物は、第２活性光線の照射によって硬化した後（即ち、重合性化合物の重合反応が進行した後）、ポリマーネットワークに組み込まれ、粘着剤層１０内での移動が抑制される。 The polymerizable compound blended with the base polymer in the adhesive composition may contain a color-developing compound having a polymerizable functional group (second color-developing compound). That is, the color-developing compound may be contained in the adhesive composition in a state in which it can be copolymerized as a polymerizable compound. Such a color-developing compound is incorporated into the polymer network after being cured by irradiation with a second active ray (that is, after the polymerization reaction of the polymerizable compound has proceeded), and the movement within the pressure-sensitive adhesive layer 10 is suppressed. To.
　ベースポリマーを形成するモノマー成分が、重合性官能基を有する発色性化合物を含み、且つ、重合性化合物が、重合性官能基を有する発色性化合物を含んでもよい。 The monomer component forming the base polymer may contain a color-developing compound having a polymerizable functional group, and the polymerizable compound may contain a color-developing compound having a polymerizable functional group.
　発色性化合物（第２の発色性化合物）の移動が抑制されるこれら構成は、粘着剤層１０に形成された変色部分１１において、発色した発色性化合物の拡散を抑制するのに適し、従って、変色部分１１の劣化（滲み、退色、色味の不均一化など）を抑制するのに適する。 These configurations in which the movement of the color-developing compound (second color-developing compound) is suppressed are suitable for suppressing the diffusion of the color-developing compound in the discolored portion 11 formed on the pressure-sensitive adhesive layer 10, and therefore. It is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion 11.
　第２の発色性化合物（重合性官能基を有する）としては、例えば、重合性官能基を有するロイコ色素、重合性官能基を有するトリアリールメタン色素、重合性官能基を有するジフェニルメタン色素、重合性官能基を有するフルオラン色素、重合性官能基を有するスピロピラン色素、および、重合性官能基を有するローダミン色素が挙げられる。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。ビニル基としては、例えばスチレン基が挙げられる。第２の発色性化合物は、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。第２の発色性化合物としては、好ましくは、重合性官能基を有するロイコ色素が用いられ、より好ましくは(メタ)アクリロイル基を有するロイコ色素が用いられ、更に好ましくはアクリロイル基を有するロイコ色素が用いられる。重合性官能基を有するロイコ色素としては、例えば、国際公開第２０１３／０４８９９３号に記載のアクリロイル基含有ロイコ色素が挙げられる。 Examples of the second color-developing compound (having a polymerizable functional group) include a leuco dye having a polymerizable functional group, a triarylmethane dye having a polymerizable functional group, a diphenylmethane dye having a polymerizable functional group, and polymerizable. Examples thereof include a fluorane dye having a functional group, a spiropyran dye having a polymerizable functional group, and a rhodamine dye 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. Examples of the vinyl group include a styrene group. The second color-developing compound may be used alone or in combination of two or more. As the second color-developing compound, a leuco dye having a polymerizable functional group is preferably used, a leuco dye having a (meth) acryloyl group is more preferably used, and a leuco dye having an acryloyl group is more preferable. Used. Examples of the leuco dye having a polymerizable functional group include the acryloyl group-containing leuco dye described in International Publication No. 2013/048993.
　第２の発色性化合物は、第１の発色性化合物と共に用いられてもよいし、第１の発色性化合物の代わりに用いられてもよい。 The second color-developing compound may be used together with the first color-developing compound, or may be used in place of the first color-developing compound.
　第１の発色性化合物および第２の発色性化合物の合計使用量は、ベースポリマー１００質量部に対して、好ましくは０.５質量部以上、より好ましくは１質量部以上であり、また、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 total amount of the first color-developing compound and the second color-developing compound used is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the base polymer. Is 10 parts by mass or less, more preferably 7 parts by mass or less.
　ベースポリマーを形成するモノマー成分は、重合性官能基を有する光酸発生剤（第２の光酸発生剤）を含んでもよい。すなわち、光酸発生剤は、ベースポリマーに組み込まれた状態を採ってもよい。このような光酸発生剤は、粘着剤層１０内での移動が抑制される。このような光酸発生剤が生じる酸との相互作用によって発色する発色性化合物の粘着剤層１０内での移動も、抑制される。 The monomer component forming the base polymer may contain a photoacid generator having a polymerizable functional group (second photoacid generator). That is, the photoacid generator may be incorporated in the base polymer. The movement of such a photoacid generator in the pressure-sensitive adhesive layer 10 is suppressed. The movement of the color-developing compound in the pressure-sensitive adhesive layer 10 that develops color by the interaction with the acid generated by such a photoacid generator is also suppressed.
　粘着性組成物にベースポリマーと共に配合される重合性化合物は、重合性官能基を有する光酸発生剤（第２の光酸発生剤）を含んでもよい。すなわち、光酸発生剤は、重合性化合物として共重合可能な状態で粘着性組成物に含有されていてもよい。このような光酸発生剤は、第２活性光線の照射によって硬化した後（即ち、重合性化合物の重合反応が進行した後）、ポリマーネットワークに組み込まれ、粘着剤層１０内での移動が抑制される。このような光酸発生剤が生じる酸との相互作用によって発色する発色性化合物の粘着剤層１０内での移動も、抑制される。 The polymerizable compound to be blended with the base polymer in the adhesive composition may contain a photoacid generator having a polymerizable functional group (second photoacid generator). That is, the photoacid generator may be contained in the tacky composition in a state in which it can be copolymerized as a polymerizable compound. Such a photoacid generator is incorporated into the polymer network after being cured by irradiation with a second active ray (that is, after the polymerization reaction of the polymerizable compound has proceeded), and movement within the pressure-sensitive adhesive layer 10 is suppressed. Will be done. The movement of the color-developing compound in the pressure-sensitive adhesive layer 10 that develops color by the interaction with the acid generated by such a photoacid generator is also suppressed.
　ベースポリマーを形成するモノマー成分が、重合性官能基を有する光酸発生剤を含み、且つ、重合性化合物が、重合性官能基を有する光酸発生剤を含んでもよい。 The monomer component forming the base polymer may contain a photoacid generator having a polymerizable functional group, and the polymerizable compound may contain a photoacid generator having a polymerizable functional group.
　光酸発生剤（第２の光酸発生剤）の移動が抑制されるこれら構成は、粘着剤層１０に形成された変色部分１１において、発色した光酸発生剤の拡散を抑制するのに適し、従って、変色部分１１の劣化（滲み、退色、色味の不均一化など）を抑制するのに適する。 These configurations in which the movement of the photoacid generator (second photoacid generator) is suppressed are suitable for suppressing the diffusion of the colored photoacid generator in the discolored portion 11 formed on the pressure-sensitive adhesive layer 10. Therefore, it is suitable for suppressing deterioration (bleeding, fading, non-uniformity of color, etc.) of the discolored portion 11.
　第２の光酸発生剤としては、例えば、紫外線照射によって酸を発生し且つ重合性官能基を有するオニウム化合物が挙げられる。重合性官能基としては、第２の発色性化合物に関して上述した重合性官能基が挙げられる。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、スルホン酸誘導体アニオン、スルホンイミド誘導体アニオン、およびスルホンメチド誘導体アニオンが挙げられる。好ましくは、アニオンが重合性官能基を有する。第２の光酸発生剤としては、好ましくは、重合性官能基を有するスルホン酸誘導体アニオンとスルホニウムとのオニウム塩が用いられ、より好ましくは、(メタ)アクリロイル基を有するスルホン酸誘導体アニオンとスルホニウムとのオニウム塩が用いられ、更に好ましくは、トリフェニルスルホニウム・４－ビニルベンゼンスルホネートが用いられる。この光酸発生剤の合成方法は、例えば、“Novel polymeric anionic photoacid generators (PAGs) and corresponding polymers for 193 nm lithography”（Journal of Materials Chemistry, 2006, Vol. 16, p3701-3707）に記載されている。第２の光酸発生剤は、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。 Examples of the second photoacid generator include an onium compound that generates an acid by irradiation with ultraviolet rays and has a polymerizable functional group. Examples of the polymerizable functional group include the above-mentioned polymerizable functional groups with respect to the second color-developing compound. 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 the anion include a sulfonic acid derivative anion, a sulfonimide derivative anion, and a sulfonmethide derivative anion. Preferably, the anion has a polymerizable functional group. As the second photoacid generator, an onium salt of a sulfonic acid derivative anion having a polymerizable functional group and sulfonium is preferably used, and more preferably, a sulfonic acid derivative anion having a (meth) acryloyl group and sulfonium. The onium salt of and is used, and more preferably, triphenylsulfonium / 4-vinylbenzenesulfonate is used. The method for synthesizing this photoacid generator is described in, for example, "Novel Polymeric anionic photoacid generators (PAGs) and corresponding polymers for 193 nm lithography" (Journal of Materials Chemistry, 2006, Vol. 16, p3701-3707). .. The second photoacid generator may be used alone or in combination of two or more.
　第２の光酸発生剤は、第１の光酸発生剤と共に用いられてもよいし、第１の光酸発生剤の代わりに用いられてもよい。 The second photoacid generator may be used together with the first photoacid generator or may be used in place of the first photoacid generator.
　発色性化合物１００質量部に対する、第１の光酸発生剤および第２の光酸発生剤の使用量は、好ましくは１００質量部以上、より好ましくは２００質量部以上、更に好ましくは３００質量部以上である。同使用量は、好ましくは１０００質量部以下、より好ましくは７００質量部以下、更に好ましくは５００質量部以下である。 The amount of the first photoacid generator and the second photoacid generator to be used with respect to 100 parts by mass of the color-developing compound is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, still more preferably 300 parts by mass or more. Is. The amount used 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５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. 5). 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（粘着剤層１０に第１活性光線を照射する前の平均透過率）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。このような構成は、粘着シートＳを被着体に貼り合わせた後に粘着シートＳと被着体との間における異物および気泡の有無を検査するのに適する。 The average transmittance of the pressure-sensitive adhesive layer 10 at a wavelength of 400 to 700 nm (the average transmittance before irradiating the pressure-sensitive adhesive layer 10 with the first active light beam) is preferably 80% or more, more preferably 85% or more, still more preferable. Is 90% or more. 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.
　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.
　粘着シートＳは、図６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. 6, 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６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. 6 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６に示す粘着シートＳによると、図１Ｃを参照して上述した接合工程を実施しないこと以外は上述の粘着シート貼付品の製造方法と同様の製造方法を実施できる（図６に示す粘着シートＳを用いた粘着シート貼付品の製造方法では、上述の第２部材Ｍ２の代わりに基材２０が配置される）。その結果、図６に示す粘着シートＳによると、図７に示すよう粘着シート貼付品Ｚ’を製造できる。 According to the pressure-sensitive adhesive sheet S shown in FIG. 6, a manufacturing method similar to that of the above-mentioned adhesive sheet-attached product can be carried out except that the above-mentioned joining step is not carried out with reference to FIG. 1C (the pressure-sensitive adhesive sheet shown in FIG. 6). In the method for manufacturing an adhesive sheet-attached product using S, the base material 20 is arranged in place of the above-mentioned second member M2). As a result, according to the pressure-sensitive adhesive sheet S shown in FIG. 6, the pressure-sensitive adhesive sheet-attached product Z'can be manufactured as shown in FIG. 7.
　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.
　本発明の粘着シート貼付品の製造方法は、例えば、ディスプレイパネルの製造過程に適用できる。 The method for manufacturing an adhesive sheet-attached product of the present invention can be applied to, for example, the manufacturing process of a display panel.
Ｍ１　　　第１部材
Ｍ２　　　第２部材
Ｓ　　　　粘着シート
１０　　　粘着剤層
１１　　　変色部分
２０　　　基材
Ｚ，Ｚ’　粘着シート貼付品 M1 1st member M2 2nd member S Adhesive sheet 10 Adhesive layer 11 Discolored part 20 Base material Z, Z'Adhesive sheet attached product

Claims (7)

  1. 　第１活性光線の照射によって変色可能かつ硬化可能であり、且つ第２活性光線の照射によって硬化可能である粘着剤層を、備える粘着シートを、被着体に貼り合わせる貼合せ工程を含む、粘着シート貼付品の製造方法であって、
    　前記被着体上の前記粘着剤層に対する前記第２活性光線の照射によって当該粘着剤層を硬化させる第１の硬化工程と、当該第１の硬化工程より後の、前記粘着剤層の少なくとも一部に対する前記第１活性光線の照射によって前記粘着剤層に変色部分を形成する変色工程とを更に含む、または、
    　前記被着体上の前記粘着剤層に対する前記第１活性光線の照射によって前記粘着剤層を変色させ且つ硬化させる第１の変色硬化工程を更に含む、または、
    　前記被着体上の前記粘着剤層における第１部分に対する前記第１活性光線の照射によって前記第１部分を変色させ且つ硬化させる第２の変色硬化工程と、当該変色硬化工程より後の、前記粘着剤層における第２部分に対する前記第２活性光線の照射によって当該第２部分を硬化させる第２の硬化工程とを更に含む、粘着シート貼付品の製造方法。     Adhesive including a bonding step of attaching an adhesive sheet provided with an adhesive layer that can be discolored and cured by irradiation with a first active light beam and can be cured by irradiation with a second active light beam to an adherend. It is a manufacturing method of sheet-attached products.
    A first curing step of curing the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer on the adherend with the second active light beam, and at least one of the pressure-sensitive adhesive layers after the first curing step. Further including a discoloration step of forming a discolored portion in the pressure-sensitive adhesive layer by irradiating the portion with the first active light beam, or
    Further including, or a first discoloration curing step of discoloring and curing the pressure-sensitive adhesive layer by irradiating the pressure-sensitive adhesive layer on the adherend with the first active light beam.
    A second discoloration curing step of discoloring and curing the first portion by irradiating the first portion of the pressure-sensitive adhesive layer on the adherend with the first active light beam, and a second discoloration curing step after the discoloration curing step. A method for producing a pressure-sensitive adhesive sheet, further comprising a second curing step of curing the second portion by irradiating the second portion of the pressure-sensitive adhesive layer with the second active light beam.
  2. 　前記粘着剤層は、重合性化合物と、光重合開始剤と、酸との反応により発色する化合物と、光酸発生剤とを含有する、請求項１に記載の粘着シート貼付品の製造方法。 The method for producing a pressure-sensitive adhesive sheet attached product according to claim 1, wherein the pressure-sensitive adhesive layer contains a polymerizable compound, a photopolymerization initiator, a compound that develops color by a reaction with an acid, and a photoacid generator.
  3. 　前記粘着剤層は、前記光酸発生剤の吸光度Ｘに対する前記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、請求項２に記載の粘着シート貼付品の製造方法。 The second aspect of the present invention, wherein the pressure-sensitive adhesive layer has a wavelength region 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 a wavelength range of 300 nm or more and 500 nm or less. How to manufacture adhesive sheet affixed products.
  4. 　前記硬化工程における前記第２活性光線は、３００ｎｍ未満の波長の光を実質的に含まない、請求項１に記載の粘着シート貼付品の製造方法。 The method for manufacturing an adhesive sheet affixed product according to claim 1, wherein the second active light ray in the curing step does not substantially contain light having a wavelength of less than 300 nm.
  5. 　前記硬化工程では、前記第２活性光線の光源として、ＵＶ－ＬＥＤランプ、ブラックライト、高圧水銀ランプ、およびメタルハライドランプからなる群より選択される少なくとも一つの光源が使用され、且つ、前記光源からの光が波長カットフィルターを介して前記粘着剤層に照射される、請求項１に記載の粘着シート貼付品の製造方法。 In the curing step, at least one light source selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp is used as the light source of the second active light, and the light source is from the light source. The method for manufacturing a pressure-sensitive adhesive sheet-attached product according to claim 1, wherein light is applied to the pressure-sensitive adhesive layer via a wavelength cut filter.
  6. 　前記変色工程および／または前記変色硬化工程における前記第１活性光線は、３００ｎｍ未満の波長の光を含む、請求項１に記載の粘着シート貼付品の製造方法。 The method for manufacturing an adhesive sheet-attached product according to claim 1, wherein the first active light ray in the discoloration step and / or the discoloration curing step contains light having a wavelength of less than 300 nm.
  7. 　前記変色工程および／または前記変色硬化工程では、前記第１活性光線の光源として、ＵＶ－ＬＥＤランプ、ブラックライト、高圧水銀ランプ、およびメタルハライドランプからなる群より選択される少なくとも一つの光源が使用される、請求項１に記載の粘着シート貼付品の製造方法。
          In the discoloration step and / or the discoloration curing step, at least one light source selected from the group consisting of a UV-LED lamp, a black light, a high-pressure mercury lamp, and a metal halide lamp is used as the light source of the first active light beam. The method for manufacturing an adhesive sheet-attached product according to claim 1.
PCT/JP2021/031869 2020-09-10 2021-08-31 Method for manufacturing adhesive sheet-attached article WO2022054637A1 (en)

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