WO2019124332A1 - Adhesive agent composition, double-sided adhesive sheet, and production method for layered product - Google Patents

Adhesive agent composition, double-sided adhesive sheet, and production method for layered product Download PDF

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Publication number
WO2019124332A1
WO2019124332A1 PCT/JP2018/046448 JP2018046448W WO2019124332A1 WO 2019124332 A1 WO2019124332 A1 WO 2019124332A1 JP 2018046448 W JP2018046448 W JP 2018046448W WO 2019124332 A1 WO2019124332 A1 WO 2019124332A1
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Prior art keywords
sensitive adhesive
pressure
meth
adhesive composition
mass
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PCT/JP2018/046448
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French (fr)
Japanese (ja)
Inventor
隼介 塩田
万智 伊藤
滋呂 清水
竜也 大里
大輔 黒田
誠司 瀬口
錦織　義治
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王子ホールディングス株式会社
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Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to KR1020207017335A priority Critical patent/KR102656758B1/en
Priority to JP2019561089A priority patent/JPWO2019124332A1/en
Priority to CN201880081790.7A priority patent/CN111492027B/en
Publication of WO2019124332A1 publication Critical patent/WO2019124332A1/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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a double-sided pressure-sensitive adhesive sheet, and a method of producing a laminate.
  • a display device such as a liquid crystal display (LCD) and a display device such as a touch panel
  • LCD liquid crystal display
  • a transparent double-sided adhesive sheet is used for the purpose of bonding optical members, and a transparent double-sided adhesive sheet is also used for bonding a display device and an input device. ing.
  • touch panels and liquid crystal displays described above include a component having a step caused by printing or the like.
  • a touch panel having a member subjected to frame-like printing is used.
  • the pressure-sensitive adhesive sheet is required to have a performance (adhesiveness) for bonding and fixing a member as well as a performance (step-following property) for filling a printing step.
  • patent document 1 it is a hot melt type adhesive sheet having the ability to easily follow a level difference by heating the pressure sensitive adhesive sheet, and the active energy ray is irradiated after the level difference is followed to cure the pressure sensitive adhesive sheet.
  • An after cure pressure-sensitive adhesive sheet has been proposed in which the tackiness is improved by doing this.
  • Touch panels and liquid crystal displays may be exposed to severe environments such as high temperature and high humidity. For this reason, there is a demand for a pressure-sensitive adhesive sheet in which the adhesion performance and the like do not change even in a severe environment such as high temperature and high humidity. That is, the pressure-sensitive adhesive sheet is also required to have durability in severe environments. However, in the conventional after-cure type pressure-sensitive adhesive sheet, there is a problem that when the durability is enhanced, the step following property is not sufficient.
  • the adhesive when attempting to improve the step following property, the adhesive may spread unintentionally at the time of bonding, and there was also a problem that the handling property at the time of bonding is inferior. .
  • the present inventors advanced examination for the purpose of providing the adhesive composition which has a level-difference followability and a handling property.
  • the glass transition temperature (Tg) of the main polymer is a hot melt type and after cure type pressure sensitive adhesive composition (pressure sensitive adhesive sheet).
  • Adhesive composition having both step followability and handling properties by setting the) to -50 ° C or higher, the main polymer weight average molecular weight to 300,000 to 450,000, and the thermal crosslinking agent content to a predetermined amount or less It was found that a thing (adhesive sheet) was obtained.
  • the present invention has the following configuration.
  • the content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer,
  • the adhesive composition whose gel fraction is 15.0% or less.
  • [3] A double-sided pressure-sensitive adhesive sheet obtained by converting the pressure-sensitive adhesive composition according to [1] or [2] into a sheet.
  • [4] A double-sided pressure-sensitive adhesive sheet with a release sheet comprising a release sheet on both sides of the double-sided pressure-sensitive adhesive sheet as described in [3].
  • a heat treatment is performed in a bonding process.
  • Step b A degassing step is included in a step after the bonding step, which is a step prior to the step of irradiating the active energy ray, and heat treatment is performed in the defoaming step.
  • [7] The method for producing a laminate according to [5] or [6], wherein the adherend is an optical member.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the release sheet-included double-sided pressure-sensitive adhesive sheet of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of the laminate.
  • the present invention relates to a photopolymerization initiator which initiates the polymerization reaction of a polyfunctional monomer by irradiation of active energy rays with 100 parts by mass of a (meth) acrylic copolymer, 0.1 to 10 parts by mass of a polyfunctional monomer.
  • the present invention relates to a pressure-sensitive adhesive composition containing 1 to 10 parts by mass.
  • the glass transition temperature (Tg) of the (meth) acrylic copolymer is ⁇ 50 ° C. or higher, and the weight average molecular weight is 300,000 to 450,000.
  • the content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. Furthermore, the gel fraction of the pressure-sensitive adhesive composition of the present invention is 15.0% or less.
  • the pressure-sensitive adhesive composition of the present invention has the above-described constitution, it has both step followability and handling properties.
  • the pressure-sensitive adhesive composition of the present invention can also form a pressure-sensitive adhesive sheet having both step followability and handling properties.
  • the glass transition temperature and the weight average molecular weight of the (meth) acrylic copolymer which is the main polymer are in the predetermined ranges, and the content of the thermal crosslinking agent is in the predetermined ranges. , The step following ability and the handling ability can be enhanced.
  • the content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer, and the pressure-sensitive adhesive composition is a thermal crosslinking agent A configuration not containing
  • the aging step can be omitted when forming a pressure-sensitive adhesive sheet from the pressure-sensitive adhesive composition, and the time required for producing the pressure-sensitive adhesive sheet can be shortened. .
  • the pressure-sensitive adhesive composition of the present invention exhibits excellent step followability.
  • the pressure-sensitive adhesive composition of the present invention can follow the step without gaps even if there is a step having a height of 35 ⁇ m or more in the attached portion, for example, and in such a case, the step following property is excellent. Can be evaluated.
  • the pressure-sensitive adhesive composition of the present invention is also excellent in durability. Specifically, even when the pressure-sensitive adhesive composition of the present invention is treated in an environment of 85 ° C. and a relative humidity of 85% for 240 hours, no deterioration occurs and no generation of air bubbles or the like is observed.
  • the pressure-sensitive adhesive composition of the present invention is also excellent in handleability.
  • the handling property of the pressure-sensitive adhesive composition can be evaluated by the protrusion (Ooz value) of the pressure-sensitive adhesive at the time of bonding.
  • the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive sheet having a thickness of 100 ⁇ m, the temperature of the press portion is set to 25 ° C., and the pressure-sensitive adhesive sheet spreads when pressed for 5 minutes at a pressure of 0.2 MPa.
  • (Ooz value) is small, it can be evaluated that the handling property is good.
  • the Worse value of the pressure-sensitive adhesive sheet is preferably 1.2 mm or less, more preferably 1.0 mm or less, and still more preferably 0.8 mm or less.
  • the Wooss value of an adhesive sheet is a value evaluated by the method as described in an Example.
  • the gel fraction of the pressure-sensitive adhesive composition of the present invention may be 15.0% or less, preferably 10.0% or less, more preferably 5.0% or less, and 4.0% or less Is more preferably 3.0% or less, still more preferably 2.0% or less. Further, the lower limit value of the gel fraction of the pressure-sensitive adhesive composition is not particularly limited, and may be, for example, 0%.
  • the gel fraction of the pressure-sensitive adhesive composition is preferably a gel fraction before the pressure-sensitive adhesive composition is completely cured by irradiation with active energy rays. By setting the gel fraction of the pressure-sensitive adhesive composition within the above range, it is possible to obtain a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet excellent in level difference followability.
  • the gel fraction of the pressure-sensitive adhesive composition of the present invention is as described above, and the pressure-sensitive adhesive composition is in a semi-cured state.
  • being in a semi-cured state means that the pressure-sensitive adhesive composition has an active energy ray curing ability. That is, the pressure-sensitive adhesive composition of the present invention is a composition in a soft state before irradiation with active energy rays.
  • the gel fraction of the pressure-sensitive adhesive composition is preferably 60% or more, more preferably 65% or more, and preferably 70% or more. Is more preferred.
  • the gel fraction of the adhesive composition after active energy ray irradiation is measured, for example, after irradiating an active energy ray so that an accumulated light quantity may be 2000 mJ / cm ⁇ 2 > or more to an adhesive composition.
  • the integrated light quantity of the active energy ray is taken as the light quantity which can completely cure the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention may be a sheet-like pressure-sensitive adhesive sheet as described later.
  • the pressure-sensitive adhesive composition of the present invention may be a gel-like pressure-sensitive adhesive composition, and may be, for example, a container-containing pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention When using the pressure-sensitive adhesive composition of the present invention, it is preferable to include a heat treatment step when the pressure-sensitive adhesive composition is brought into contact with the adherend surface and / or after being brought into contact. And it is preferable to include the process of irradiating an active energy ray after a heat treatment process. That is, the pressure-sensitive adhesive composition of the present invention is a hot-melt type pressure-sensitive adhesive composition and an after-cure type pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic copolymer.
  • the (meth) acrylic copolymer is a main polymer contained in the pressure-sensitive adhesive composition, and such a polymer may be referred to as a base polymer.
  • the (meth) acrylic copolymer has a (meth) acrylic acid alkyl ester unit.
  • the "unit” is a repeating unit (monomer unit) constituting the polymer.
  • the (meth) acrylic acid alkyl ester unit is derived from the (meth) acrylic acid alkyl ester.
  • (meth) acrylic acid alkyl ester methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, (meth
  • the (meth) acrylic copolymer may have another acrylic monomer unit other than the (meth) acrylic acid alkyl ester unit.
  • the acrylic monomer unit which has a crosslinkable functional group can be mentioned,
  • a hydroxyl group containing acrylic monomer unit, a glycidyl group containing acrylic monomer unit can be mentioned.
  • These monomer units may be used alone or in combination of two or more.
  • the hydroxy group-containing acrylic monomer unit is derived from the hydroxy group-containing acrylic monomer.
  • Examples of the hydroxy group-containing acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate such as (meth) acrylate.
  • (meth) acrylic acid lactones such as (meth) acrylic acid [(mono, di or poly) alkylene glycols] such as alkyl (meth) acrylic acid mono (diethylene glycol) and (meth) acrylic acid monocaprolactone.
  • Examples of the glycidyl group-containing acrylic monomer unit include those derived from glycidyl group-containing acrylic monomers such as glycidyl (meth) acrylate.
  • the content of the other acrylic monomer unit is (meth) acrylic copolymer
  • the content is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the polymer.
  • the content of the acrylic monomer unit having a crosslinkable functional group is preferably in the above range. If the content of the other acrylic monomer unit is equal to or more than the above lower limit value, the cohesion can be sufficiently increased, and if it is less than or equal to the above upper limit value, it becomes easy to secure sufficient adhesion.
  • the glass transition temperature (Tg) of the (meth) acrylic copolymer may be ⁇ 50 ° C. or higher, preferably ⁇ 49 ° C. or higher, and more preferably ⁇ 48 ° C. or higher. Further, the glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably ⁇ 10 ° C. or less, more preferably ⁇ 20 ° C. or less, and still more preferably ⁇ 30 ° C. or less It is particularly preferable that the temperature is ⁇ 40 ° C. or less.
  • Tg glass transition temperature
  • the weight average molecular weight (Mw) of the (meth) acrylic copolymer may be from 300,000 to 450,000, preferably from 350,000 to 450,000, and more preferably from 360,000 to 430,000.
  • Mw weight average molecular weight
  • the step following can be achieved by setting the weight average molecular weight of the (meth) acrylic copolymer within the above range. It is easy to achieve both of the properties and durability.
  • the weight average molecular weight of the (meth) acrylic copolymer is a value determined by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene.
  • the measurement conditions of gel permeation chromatography (GPC) are as follows.
  • Solvent Tetrahydrofuran column: Shodex KF801, KF803L, KF800L, KF800D (Showa Denko KK made four connection) Column temperature: 40 ° C Sample concentration: 0.5 mass% Detector: RI-2031 plus (made by JASCO) Pump: RI-2080plus (made by JASCO) Flow rate (flow rate): 0.8 ml / min Injection volume: 10 ⁇ l
  • a (meth) acrylic-type copolymer may use a commercially available thing, and may be manufactured by polymerizing an acryl monomer.
  • a commercially available product for example, OP-9200-1, OP-9200-3, OP-9200-4, OP-9200-5, OP-9200-7, etc. manufactured by Aika Kogyo Co., Ltd. can be used.
  • the polymerization method can be suitably selected from the polymerization method used normally.
  • a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and the like can be mentioned.
  • the pressure-sensitive adhesive composition of the present invention contains a polyfunctional monomer.
  • the polyfunctional monomer is a monomer having two or more reactive double bonds in the molecule.
  • polyfunctional monomers examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4-di (meth) acrylic acid.
  • a commercial item can be used for a polyfunctional monomer.
  • Examples of commercially available products include ATM-4PL and A-TMM-3L manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the pressure-sensitive adhesive composition may contain the polyfunctional monomer in an amount of 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, and preferably 2 to 4 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. It is more preferable to contain part.
  • the above-mentioned polyfunctional monomers may be used alone or in combination of two or more. When two or more are used in combination, the total mass is preferably in the above range.
  • the pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator may be any as long as it can start the polymerization reaction of the above-mentioned polyfunctional monomer by irradiation of active energy rays.
  • active energy ray means an electromagnetic wave or charged particle beam having energy quantum, and includes ultraviolet light, electron beam, visible light, X-ray, ion beam and the like. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
  • Examples of the photopolymerization initiator include acetophenone initiators, benzoin ether initiators, benzophenone initiators, hydroxyalkylphenone initiators, thioxanthone initiators, and amine initiators.
  • acetophenone initiators include diethoxyacetophenone, benzyl dimethyl ketal and the like.
  • Specific examples of the benzoin ether initiator include benzoin and benzoin methyl ether.
  • Specific examples of benzophenone initiators include benzophenone and methyl o-benzoylbenzoate.
  • hydroxyalkyl phenone initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
  • thioxanthone initiators include 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone and the like.
  • amine initiator examples include triethanolamine and ethyl 4-dimethylbenzoate.
  • a commercial item can be used for a photoinitiator.
  • Examples of commercially available products include TZT and Omnirad 184 manufactured by IGM Resin.
  • the pressure-sensitive adhesive composition may contain 0.1 to 10 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the (meth) acrylic copolymer, and preferably 0.1 to 3 parts by mass.
  • the photopolymerization initiators may be used alone or in combination of two or more. When two or more are used in combination, the total mass is preferably in the above range.
  • the content of the thermal crosslinking agent in the pressure-sensitive adhesive composition of the present invention is less than 0.5 parts by mass and not more than 0.3 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer.
  • the amount is preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less.
  • the content of the thermal crosslinking agent is particularly preferably 0 parts by mass.
  • the adhesive composition of this invention is an aspect which does not contain a thermal crosslinking agent substantially, In such a case, when forming an adhesive sheet from an adhesive composition, an aging process may be skipped. It is possible to reduce the time required for producing the pressure-sensitive adhesive sheet.
  • thermal crosslinking agents include, for example, isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, butylated melamine compounds, etc. And a thermal crosslinker of Among these, isocyanate compounds and epoxy compounds are preferably used.
  • the thermal crosslinking agent is selected in consideration of the reactivity with the crosslinkable functional group possessed by the (meth) acrylic copolymer. For example, when the (meth) acrylic copolymer contains a hydroxy group as a crosslinkable functional group, it is preferable to use an isocyanate compound in view of the reactivity of the hydroxy group.
  • One type of thermal crosslinking agent may be used alone, or two or more types may be used in combination.
  • isocyanate compound examples include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • an epoxy compound for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycid
  • polyfunctional acrylates such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,9 Nonanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol (tri / tetra) acrylate, etc. may be used.
  • the pressure-sensitive adhesive composition of the present invention may contain a solvent.
  • the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition.
  • Such solvents include, for example, hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene and dichloropropane; methanol Alcohols such as ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran etc.
  • hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone etc Methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate etc.
  • Ester ethers ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.
  • One solvent may be used alone, or two or more solvents may be used in combination.
  • the content of the solvent contained in the pressure-sensitive adhesive composition is preferably 80% by mass or less, more preferably 50% by mass or less, based on the total mass of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition of the present invention may contain other components other than the above as long as the effects of the present invention are not impaired.
  • components known as additives for pressure-sensitive adhesives can be mentioned.
  • it can be selected as required from light stabilizers such as plasticizers, antioxidants, metal corrosion inhibitors, tackifiers, silane coupling agents, ultraviolet absorbers and hindered amine compounds.
  • a nonfunctional acrylic polymer can be used as a plasticizer.
  • a nonfunctional acrylic polymer is a polymer consisting only of an acrylic monomer unit having no functional group other than an acrylate group, or an acrylic monomer unit having no functional group other than an acrylate group and a functional group It means a polymer composed of non-acrylic monomer units not having.
  • an acryl-type monomer unit which does not have functional groups other than an acrylate group the thing similar to a non-crosslinkable (meth) acrylic acid ester unit is mentioned, for example.
  • non-acrylic monomer units having no functional group examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, Examples thereof include vinyl stearates, vinyl cyclohexanecarboxylates, vinyl esters of carboxylic acids such as vinyl benzoate, and styrene.
  • antioxidants examples include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • benzotriazole resin can be mentioned.
  • tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
  • silane coupling agent a mercapto type silane coupling agent, a (meth) acrylic type silane coupling agent, an isocyanate type silane coupling agent, an epoxy type silane coupling agent, an amino type silane coupling agent etc. are mentioned, for example .
  • UV absorber include benzotriazole compounds and benzophenone compounds.
  • the present invention also relates to a double-sided pressure-sensitive adhesive sheet in which the above-described pressure-sensitive adhesive composition is formed into a sheet.
  • the double-sided pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive composition, or may be a double-sided pressure-sensitive adhesive sheet obtained by semi-curing the pressure-sensitive adhesive composition by heat or active energy rays. Good.
  • the gel fraction of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 15.0% or less, more preferably 10.0% or less, still more preferably 5.0% or less, and 4.0% The content is more preferably the following, still more preferably 3.0% or less, and particularly preferably 2.0% or less.
  • FIG. 1 is a schematic view showing a cross section of an example of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet 11 may be a double-sided pressure-sensitive adhesive sheet 1 provided with a release sheet 12a and a release sheet 12b on both sides thereof.
  • the double-sided pressure-sensitive adhesive sheet 11 may be a single-layer double-sided pressure-sensitive adhesive sheet as shown in FIG. 1 or may be a multilayer double-sided pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated.
  • the double-sided pressure-sensitive adhesive sheet 11 may be a double-sided pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on both sides of a substrate (preferably, a transparent substrate).
  • the surface of the double-sided pressure-sensitive adhesive sheet 11 is preferably covered with a release sheet 12a and a release sheet 12b.
  • a release sheet a peelable laminate sheet having a release sheet substrate and a release agent layer provided on one side of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substratecan be mentioned.
  • Papers and polymer films are used for the release sheet base in the release laminate sheet.
  • a general-purpose addition type or condensation type silicone release agent or a long chain alkyl group-containing compound is used as the release agent constituting the release agent layer.
  • an addition-type silicone release agent having high reactivity is preferably used.
  • Specific examples of silicone release agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774 and X62-2600, etc. Can be mentioned.
  • a silicone resin which is an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 CHCH (CH 3 ) SiO 1/2 unit in a silicone-based release agent preferable.
  • Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
  • a commercial item may be used as the peelable laminated sheet.
  • a heavy separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Ltd.
  • a light separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Ltd. it can.
  • the pressure-sensitive adhesive sheet of the present invention preferably has a pair of release sheets having different release forces. That is, in order to make it easy to peel off the release sheet, it is preferable that the release properties of the release sheet 12a and the release sheet 12b be different. When the releasability from one side and the releasability from the other are different, it becomes easy to peel off only the release sheet having the higher releasability first. In that case, the releasability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 5 to 500 ⁇ m, more preferably 30 to 300 ⁇ m, and still more preferably 50 to 200 ⁇ m.
  • the pressure-sensitive adhesive composition of the present invention When using the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition is brought into contact with the adherend surface. When the pressure-sensitive adhesive composition is brought into contact with the adherend surface and / or after being brought into contact, it is preferable to include a heat treatment step. Then, after the heat treatment step, a step of irradiating an active energy ray is included. Thus, a laminate is obtained. That is, the method for producing a laminate of the present invention includes a bonding step of bringing a pressure-sensitive adhesive composition into contact with the surface of an adherend, and a step of irradiating an active energy ray; And / or process step). (A process) A heat treatment is performed in a bonding process. (Step b) A degassing step is included in a step after the bonding step, which is a step prior to the step of irradiating the active energy ray, and heat treatment is performed in the defoaming step.
  • the pressure-sensitive adhesive composition of the present invention may be a double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive composition, and is a double-sided pressure-sensitive adhesive sheet obtained by semi-curing the pressure-sensitive adhesive composition by heat or active energy rays. It is also good.
  • the method for producing a laminate includes a bonding step of bringing a double-sided pressure-sensitive adhesive sheet into contact with the adherend surface, and a step of irradiating an active energy ray, and at least the steps (a) and (b) It may be one including any.
  • the pressure-sensitive adhesive composition or the double-sided pressure-sensitive adhesive sheet is bonded to an adherend.
  • a bonding method the roll bonding method, the vacuum bonding method, etc. can be mentioned, for example.
  • the heat treatment is preferably performed at 40 to 59.degree.
  • the heating temperature is also preferably 50 to 59.degree.
  • the treatment temperature at the time of performing the heat treatment in the bonding step and / or the subsequent step of the bonding step can be suppressed lower than usual, and even in such a case Therefore, the risk of damaging the adherend can be extremely low.
  • the photothermal cost at the time of manufacturing a laminated body can be suppressed, and the manufacturing efficiency of a laminated body can also be raised more effectively.
  • the heat treatment at 40 to 59 ° C. is preferably performed in the bonding step or in the defoaming step.
  • heat processing may be performed in both processes of a bonding process and a defoaming process.
  • a bonding process a roll bonding process and a vacuum bonding process can be mentioned, for example.
  • a degassing process an autoclave process can be mentioned, for example. That is, the heat treatment at 40 to 59 ° C. is preferably performed in at least one process selected from an autoclave treatment process, a roll bonding process and a vacuum bonding process.
  • the heating setting temperature in the autoclave treatment step, the roll bonding step and the vacuum bonding step is preferably 40 to 59 ° C.
  • an active energy ray is irradiated to the adhesion thing of an adhesive composition or a double-sided adhesive sheet, and a to-be-adhered body.
  • the step of irradiating the active energy ray can also be called a post-curing step.
  • an ultraviolet ray, an electron beam, a visible ray, an X ray, an ion beam etc. are mentioned, According to the photoinitiator contained in an adhesive layer, it can select suitably. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
  • a light source of ultraviolet light for example, a high pressure mercury lamp, low pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, electrodeless ultraviolet lamp and the like can be used.
  • the electron beam for example, electron beams emitted from various types of electron beam accelerators such as Cockloft Wald type, Bandeklav type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type and the like are used it can.
  • Radiation output of the UV light it is preferable that the integrated quantity of light is made to be a 100 ⁇ 10000mJ / cm 2, and more preferably made to be 500 ⁇ 5000mJ / cm 2.
  • the laminate produced by the above-described production method comprises a post-cured pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet) and an adherend.
  • the laminate of the present invention preferably has an adherend on both sides of the post-cured pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet).
  • the pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet) of the present invention is preferably used for bonding an adherend having a stepped portion.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of a laminate 30 in which the double-sided pressure-sensitive adhesive sheet 11 of the present invention is bonded to an adherend 31 having a step portion 32.
  • the adherend 31 has a stepped portion 32.
  • the thickness of the step portion 32 can be 5 to 60 ⁇ m.
  • the double-sided adhesive sheet 11 of this invention can be used for the bonding of the to-be-adhered body which has a level
  • the double-sided pressure-sensitive adhesive sheet 11 of the present invention can also be used for bonding an adherend having a thickness of the step portion 32 of 35 ⁇ m or more.
  • the adherend 31 is preferably an optical member.
  • an optical member each structural member in optical products, such as a touch panel and an image display device, can be mentioned.
  • an ITO film in which an ITO film is provided on a transparent resin film an ITO glass in which an ITO film is provided on the surface of a glass plate, a transparent conductive film obtained by coating a conductive polymer on a transparent resin film Hard coat films, fingerprint resistant films and the like can be mentioned.
  • the double-sided pressure-sensitive adhesive sheet of the present invention is preferably for sensor lamination of a touch panel, and more preferably for sensor lamination of a touch panel using a touch pen.
  • an ITO film in which an ITO film is provided on a transparent resin film an ITO glass in which an ITO film is provided on the surface of a glass plate, and a conductive resin Polymer-coated transparent conductive films are preferred.
  • the antireflection film used for a liquid crystal display device an orientation film, a polarizing film, retardation film, a brightness improvement film etc. are mentioned, for example.
  • materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, and cellulose acylate.
  • Example 1 Preparation of pressure-sensitive adhesive composition
  • 100 parts by mass of (meth) acrylic copolymer manufactured by Aika Kogyo Co., Ltd .: OP-9200-3
  • 3 parts by mass of polyfunctional monomer manufactured by Shin-Nakamura Chemical Co., Ltd .: ATM-4PL
  • photopolymerization initiator IGM Resins Co., Ltd.
  • Product 1.5 parts by mass of TZT was mixed, and stirred for 3 minutes under atmospheric pressure using a stirrer (SHASHIN KAGAKU: SK-200 TVS) to prepare a pressure-sensitive adhesive composition.
  • SHASHIN KAGAKU SK-200 TVS
  • a 38 ⁇ m-thick polyethylene terephthalate film (first release sheet) (a release sheet manufactured by Oji F-TEX, Inc .: 38RL-07) provided with a release agent layer treated with a silicone-based release agent, with the pressure-sensitive adhesive composition prepared as described above
  • the surface of (2) was uniformly coated with an applicator so that the coated film thickness after drying was 100 ⁇ m. Then, it dried in 100 degreeC of air circulation type thermostatic ovens for 3 minutes, and formed the adhesive layer on the surface of a 1st peeling sheet.
  • a second release sheet (manufactured by Oji F-TEX Co., Ltd .: 38RL-07 (L)) having a thickness of 38 ⁇ m is attached to the surface of the pressure-sensitive adhesive layer to form a pair of pressure-sensitive adhesive layers having a difference in release force.
  • a UV curable ink was screen printed on the surface of a glass plate (90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick) in a frame shape (90 mm long ⁇ 50 mm wide, 5 mm wide) so that the coating thickness would be 5 ⁇ m.
  • ultraviolet rays were irradiated to cure the printed ultraviolet curable ink. This process was repeated a predetermined number of times to obtain a printed stepped glass having a stepped portion with a predetermined thickness described in Tables 1 to 3.
  • the double-sided pressure-sensitive adhesive sheet with a release sheet obtained above is cut into a shape of 90 mm long ⁇ 50 mm wide, the first release sheet is peeled off, and a pressure-sensitive adhesive is used using a laminator (manufactured by Eubon Co., Ltd., IKO-650 EMT) A layer was pasted so that the frame-like printing whole surface of printing level difference glass might be covered. Thereafter, the second release sheet is peeled off, and a glass plate (90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick) is bonded to the surface of the exposed pressure-sensitive adhesive layer with the above laminator, and defoaming treatment (autoclave treatment: 40 ° C, 0.5 MPa, 10 minutes) was performed.
  • autoclave treatment 40 ° C, 0.5 MPa, 10 minutes
  • ultraviolet rays were irradiated from the side of the printing step glass with an ultraviolet irradiator (manufactured by Eye Graphics Co., Ltd., ECS-301G1) so as to obtain the integrated light amount described in Tables 1 to 3, to obtain a laminate.
  • an ultraviolet irradiator manufactured by Eye Graphics Co., Ltd., ECS-301G1
  • Example 2 When bonding a glass plate (90 mm in length ⁇ 50 mm in width ⁇ 0.5 mm in thickness) to the surface of the pressure-sensitive adhesive layer on the side of the second release sheet in (the method for producing a laminate) in Example 1; A laminate was obtained in the same manner as in Example 1 except that lamination was carried out in a heated state at ° C. and then defoaming treatment (autoclave treatment: 40 ° C., 0.5 MPa, 10 minutes) was not performed.
  • autoclave treatment 40 ° C., 0.5 MPa, 10 minutes
  • Example 3 When bonding a glass plate (90 mm in length ⁇ 50 mm in width ⁇ 0.5 mm in thickness) to the surface of the pressure-sensitive adhesive layer on the side of the second release sheet in (the method for producing a laminate) in Example 1; A laminate was obtained in the same manner as Example 1, except that the lamination was carried out in the heated state at ° C.
  • Example 4 A glass plate (90 mm in length) was formed on the surface of the pressure-sensitive adhesive layer exposed by using a vacuum bonding machine (manufactured by Joyo Engineering Co., Ltd .: vacuum laminating apparatus (JE2020B-MVH)) in (Production method of laminate) of Example 1 ⁇ 50 mm ⁇ 0.5 mm thickness 40 ° C, weak pressure 0.6 kN, strong pressure 1.2 kN, vacuum pressure 100 Pa, pressure holding time 10 s, degassing treatment (autoclave treatment: 40 ° C., A laminate was obtained in the same manner as Example 1 except that 0.5 MPa for 10 minutes was not performed.
  • a vacuum bonding machine manufactured by Joyo Engineering Co., Ltd .: vacuum laminating apparatus (JE2020B-MVH)
  • JE2020B-MVH vacuum laminating apparatus
  • Example 5 A glass plate (90 mm long ⁇ 50 mm wide ⁇ 0.5 mm thick) was bonded at 40 ° C. to the surface of the pressure-sensitive adhesive layer exposed using a vacuum bonding machine in (Production method of laminate) of Example 1 A laminate was obtained in the same manner as Example 1 except for the above.
  • Example 6 A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 55 ° C. in (Production method of laminate) of Example 1.
  • Example 7 A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 59 ° C. in (Production method of laminate) of Example 1.
  • Example 8 A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 55 ° C., and the time was changed to 30 minutes in (Production method of laminate) of Example 1.
  • Example 9 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-1 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Example 10 The (meth) acrylic copolymer was changed to OP-9200-1 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 and the temperature of autoclave treatment was used in (a method of preparing a laminate) A laminate was obtained in the same manner as in Example 1 except that 55.degree. C. was changed.
  • Example 11 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-5 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Example 12 The (meth) acrylic copolymer was changed to OP-9200-5 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 and the temperature of autoclave treatment was used in (a method of preparing a laminate) A laminate was obtained in the same manner as in Example 1 except that 55.degree. C. was changed.
  • Example 13 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-7 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Example 14 The (meth) acrylic copolymer is changed to OP-9200-7 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 (a method of preparing a laminate), which is an autoclave.
  • a laminate was obtained in the same manner as in Example 1 except that the treatment temperature was changed to 55 ° C.
  • Example 15 In Example 1 (preparation of a pressure-sensitive adhesive composition), 0.3 part by mass of a thermal crosslinking agent (manufactured by Tosoh Corporation: Coronate L-55E) is added with respect to 100 parts by mass of a (meth) acrylic copolymer.
  • a laminate was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive sheet was aged at 23 ⁇ 5 ° C. and 50 ⁇ 10% relative humidity for 7 days at the end of the process of (preparation of pressure-sensitive adhesive sheet).
  • Example 16 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-4 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Example 1 In (Preparation of pressure-sensitive adhesive composition) of Example 1, a thermal crosslinking agent (manufactured by Tosoh Corp .: Coronate L-55E) is added in an amount of 1.0 part by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. A laminate was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive sheet was aged at 23 ⁇ 5 ° C. and 50 ⁇ 10% relative humidity for 7 days at the end of the process of (preparation of pressure-sensitive adhesive sheet).
  • a thermal crosslinking agent manufactured by Tosoh Corp .: Coronate L-55E
  • Comparative Example 2 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-6 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Comparative Example 3 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-8 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Comparative Example 4 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-9 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • Comparative Example 5 A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-7000-V6 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
  • ⁇ Durability> The laminate was placed in an environment of 85 ° C. and relative humidity of 85% for 240 hours, and observed for no bubbles in the entire sample with a microscope (magnification: 25 times) and evaluated based on the following criteria. ⁇ : There is no generation of air bubbles at all. X: Air bubbles are generated.
  • a sheet piece was cut out in a size of 30 mm long ⁇ 30 mm wide from the double-sided pressure-sensitive adhesive sheet with a release sheet.
  • One side of the release sheet of the sheet piece was peeled off, and the pressure-sensitive adhesive layer peeled off was attached to the silicone-treated side of a release sheet (A71 100 ⁇ m: Teijin DuPont film) cut out in advance to 50 mm square.
  • the silicone-treated side of a release sheet (A38 # 50: Teijin DuPont film) which had been separately cut into 50 mm squares was placed on the other release sheet remaining on the sheet piece.
  • the weight average molecular weight of the (meth) acrylic copolymer is 300,000 to 450,000
  • the Tg of the (meth) acrylic copolymer is -50 ° C. or higher
  • the heat crosslinks It was found that when the additive amount of the agent is less than 0.5 parts by mass, level difference followability and good handling characteristics can be obtained.
  • Example 15 which added 0.3 mass part of thermal crosslinking agents with respect to the (meth) acrylic-type copolymer, although aging was required, the characteristic of level
  • Comparative Example 1 the thermal crosslinking agent was added in an amount of 1.0 part by mass with respect to the (meth) acrylic copolymer, so that the step followability was inferior.
  • Comparative Example 3 has a large molecular weight of the (meth) acrylic copolymer
  • Comparative Example 4 has a small molecular weight of the (meth) acrylic copolymer, but the Tg of the (meth) acrylic copolymer is high. As a result, the step followability was poor.
  • the Tg of the (meth) acrylic copolymer is low in Comparative Example 2, and the Tg of the (meth) acrylic copolymer is low in Comparative Example 5 and the molecular weight of the (meth) acrylic copolymer is small. The result was poor handling.

Abstract

The present invention addresses the problem of providing an adhesive agent composition which can form an adhesive sheet which has conformability to uneven surfaces, durability, and handling properties. The present invention pertains to an adhesive agent composition comprising: 100 parts by mass of a (meth)acrylic copolymer having a glass transition temperature (Tg) of -50°C or higher and a weight-average molecular weight of 300,000-450,000; 0.1-10 parts by mass of a polyfunctional monomer; and 0.1-10 parts by mass of a photopolymerization initiator which initiates a polymerization reaction of the polyfunctional monomer by irradiation with an active energy ray, wherein the contained amount of a thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth)acrylic copolymer, and the gel fraction of the adhesive agent composition is 15.0% or less.

Description

粘着剤組成物、両面粘着シート及び積層体の製造方法Pressure-sensitive adhesive composition, double-sided pressure-sensitive adhesive sheet and method for producing laminate
　本発明は粘着剤組成物、両面粘着シート及び積層体の製造方法に関する。 The present invention relates to a pressure-sensitive adhesive composition, a double-sided pressure-sensitive adhesive sheet, and a method of producing a laminate.
　近年、様々な分野で、液晶ディスプレイ（ＬＣＤ）などの表示装置や、タッチパネルなどの表示装置と組み合わせて用いられる入力装置が広く用いられるようになってきている。これらの表示装置や入力装置の製造等においては、光学部材を貼り合せる用途に透明な両面粘着シートが使用されており、表示装置と入力装置との貼合にも透明な両面粘着シートが使用されている。 BACKGROUND In recent years, input devices used in combination with a display device such as a liquid crystal display (LCD) and a display device such as a touch panel have been widely used in various fields. In the production of these display devices and input devices, a transparent double-sided adhesive sheet is used for the purpose of bonding optical members, and a transparent double-sided adhesive sheet is also used for bonding a display device and an input device. ing.
　上記タッチパネルや液晶ディスプレイの中には印刷等で生じる段差を有する構成部材を含んでいるものがある。例えば、携帯電話においては、枠状の印刷が施された部材を有するタッチパネルが用いられている。このような用途では、粘着シートには、部材を貼合固定する性能（粘着性）と同時に印刷段差を埋める性能（段差追従性）が求められる。 Some of the touch panels and liquid crystal displays described above include a component having a step caused by printing or the like. For example, in a mobile phone, a touch panel having a member subjected to frame-like printing is used. In such an application, the pressure-sensitive adhesive sheet is required to have a performance (adhesiveness) for bonding and fixing a member as well as a performance (step-following property) for filling a printing step.
　例えば、特許文献１では、粘着シートを加熱することにより段差に追従しやすくなる性能を有するホットメルト型の粘着シートであって、段差に追従した後に活性エネルギー線を照射し、粘着シートを後硬化することで粘着性を向上させたアフターキュア型の粘着シートが提案されている。このように粘着性と段差追従性を両立し得る粘着シートの開発が進められている。 For example, in patent document 1, it is a hot melt type adhesive sheet having the ability to easily follow a level difference by heating the pressure sensitive adhesive sheet, and the active energy ray is irradiated after the level difference is followed to cure the pressure sensitive adhesive sheet. An after cure pressure-sensitive adhesive sheet has been proposed in which the tackiness is improved by doing this. Thus, development of the adhesive sheet which can make adhesiveness and level | step difference tracking property compatible is furthered.
特開２０１６－２２２９１６号公報JP, 2016-222916, A
　タッチパネルや液晶ディスプレイは、高温高湿といった過酷環境下に曝されることもある。このため、高温高湿といった過酷環境下においても粘着性能等が変化しない粘着シートが求められている。すなわち、粘着シートには過酷環境下における耐久性も要求されるようになってきている。しかしながら、従来のアフターキュア型の粘着シートにおいては、その耐久性を高めた場合に、段差追従性が十分ではなくなるという課題があった。 Touch panels and liquid crystal displays may be exposed to severe environments such as high temperature and high humidity. For this reason, there is a demand for a pressure-sensitive adhesive sheet in which the adhesion performance and the like do not change even in a severe environment such as high temperature and high humidity. That is, the pressure-sensitive adhesive sheet is also required to have durability in severe environments. However, in the conventional after-cure type pressure-sensitive adhesive sheet, there is a problem that when the durability is enhanced, the step following property is not sufficient.
　また、従来のアフターキュア型の粘着シートにおいて、段差追従性を高めようとした場合、貼合時に粘着剤が意図せずに広がることがあり、貼合時のハンドリング性に劣るという課題もあった。 In addition, in the conventional after cure type adhesive sheet, when attempting to improve the step following property, the adhesive may spread unintentionally at the time of bonding, and there was also a problem that the handling property at the time of bonding is inferior. .
　そこで本発明者らは、このような従来技術の課題を解決するために、段差追従性及びハンドリング性を兼ね備える粘着剤組成物を提供することを目的として検討を進めた。 Then, in order to solve such a subject of a prior art, the present inventors advanced examination for the purpose of providing the adhesive composition which has a level-difference followability and a handling property.
　上記の課題を解決するために鋭意検討を行った結果、本発明者らは、ホットメルト型であり、かつアフターキュア型の粘着剤組成物（粘着シート）において、主ポリマーのガラス転移温度（Ｔｇ）を－５０℃以上とし、主ポリマーの重量平均分子量を３０万～４５万とし、さらに、熱架橋剤の含有量を所定量以下とすることによって、段差追従性及びハンドリング性を兼ね備える粘着剤組成物（粘着シート）が得られることを見出した。
　具体的に、本発明は、以下の構成を有する。 As a result of intensive studies to solve the above problems, the present inventors have found that the glass transition temperature (Tg) of the main polymer is a hot melt type and after cure type pressure sensitive adhesive composition (pressure sensitive adhesive sheet). Adhesive composition having both step followability and handling properties by setting the) to -50 ° C or higher, the main polymer weight average molecular weight to 300,000 to 450,000, and the thermal crosslinking agent content to a predetermined amount or less It was found that a thing (adhesive sheet) was obtained.
Specifically, the present invention has the following configuration.
［１］　ガラス転移温度（Ｔｇ）が－５０℃以上であり、重量平均分子量が３０万～４５万の（メタ）アクリル系共重合体１００質量部と、
　多官能モノマー０．１～１０質量部と、
　活性エネルギー線の照射により多官能モノマーの重合反応を開始させる光重合開始剤０．１～１０質量部と、を含有し、
　熱架橋剤の含有量が、（メタ）アクリル系共重合体１００質量部に対して０．５質量部未満であり、
　ゲル分率が１５．０％以下である粘着剤組成物。
［２］　活性エネルギー線の照射によりゲル分率が６０％以上となる［１］に記載の粘着剤組成物。
［３］　［１］又は［２］に記載の粘着剤組成物をシート状にした両面粘着シート。
［４］　［３］に記載の両面粘着シートの両面に剥離シートを備える剥離シート付き両面粘着シート。
［５］　［１］又は［２］に記載の粘着剤組成物、又は［３］に記載の両面粘着シートを被着体表面に接触させる貼合工程と、活性エネルギー線を照射する工程と、を含み、
　以下の（ａ工程）及び（ｂ工程）の少なくともいずれかを含む積層体の製造方法。
　（ａ工程）貼合工程において加熱処理を行う。
　（ｂ工程）貼合工程の後工程であって、活性エネルギー線を照射する工程の前工程において脱泡工程を含み、該脱泡工程で加熱処理を行う。
［６］　（ａ工程）及び（ｂ工程）における加熱処理では、４０～５９℃で加熱処理を行う［５］に記載の積層体の製造方法。
［７］　被着体が、光学部材である［５］又は［６］に記載の積層体の製造方法。 [1] 100 parts by mass of a (meth) acrylic copolymer having a glass transition temperature (Tg) of −50 ° C. or more and a weight average molecular weight of 300,000 to 450,000,
0.1 to 10 parts by mass of a polyfunctional monomer,
And 0.1 to 10 parts by mass of a photopolymerization initiator for initiating the polymerization reaction of a polyfunctional monomer by irradiation of active energy rays.
The content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer,
The adhesive composition whose gel fraction is 15.0% or less.
[2] The pressure-sensitive adhesive composition according to [1], wherein the gel fraction is 60% or more by irradiation of active energy rays.
[3] A double-sided pressure-sensitive adhesive sheet obtained by converting the pressure-sensitive adhesive composition according to [1] or [2] into a sheet.
[4] A double-sided pressure-sensitive adhesive sheet with a release sheet comprising a release sheet on both sides of the double-sided pressure-sensitive adhesive sheet as described in [3].
[5] A bonding step in which the pressure-sensitive adhesive composition according to [1] or [2] or the double-sided pressure-sensitive adhesive sheet according to [3] is brought into contact with the adherend surface; Including
The manufacturing method of the laminated body containing at least any one of the following (a process) and (b process).
(A process) A heat treatment is performed in a bonding process.
(Step b) A degassing step is included in a step after the bonding step, which is a step prior to the step of irradiating the active energy ray, and heat treatment is performed in the defoaming step.
[6] The method for producing a laminate according to [5], wherein the heat treatment is carried out at 40 to 59 ° C. in the heat treatment in (Step a) and (Step b).
[7] The method for producing a laminate according to [5] or [6], wherein the adherend is an optical member.
　本発明によれば、段差追従性及びハンドリング性を兼ね備える粘着剤組成物（粘着シート）を得ることができる。 According to the present invention, it is possible to obtain a pressure-sensitive adhesive composition (pressure-sensitive adhesive sheet) having both step followability and handling properties.
図１は、本発明の剥離シート付き両面粘着シートの構成の一例を表す断面図である。FIG. 1 is a cross-sectional view showing an example of the configuration of the release sheet-included double-sided pressure-sensitive adhesive sheet of the present invention. 図２は、積層体の構成の一例を表す断面図である。FIG. 2 is a cross-sectional view showing an example of the configuration of the laminate.
　以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。なお、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。また、「（メタ）アクリル」とは、アクリル及びメタクリルの両方を含むことを意味する。 Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value. Also, "(meth) acrylic" is meant to include both acrylic and methacrylic.
（粘着剤組成物）
　本発明は、（メタ）アクリル系共重合体１００質量部と、多官能モノマー０．１～１０質量部と、活性エネルギー線の照射により多官能モノマーの重合反応を開始させる光重合開始剤０．１～１０質量部と、を含有する粘着剤組成物に関する。ここで、（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）は－５０℃以上であり、重量平均分子量は３０万～４５万である。また、本発明の粘着剤組成物において、熱架橋剤の含有量は、（メタ）アクリル系共重合体１００質量部に対して０．５質量部未満である。さらに、本発明の粘着剤組成物のゲル分率は１５．０％以下である。 (Adhesive composition)
The present invention relates to a photopolymerization initiator which initiates the polymerization reaction of a polyfunctional monomer by irradiation of active energy rays with 100 parts by mass of a (meth) acrylic copolymer, 0.1 to 10 parts by mass of a polyfunctional monomer. The present invention relates to a pressure-sensitive adhesive composition containing 1 to 10 parts by mass. Here, the glass transition temperature (Tg) of the (meth) acrylic copolymer is −50 ° C. or higher, and the weight average molecular weight is 300,000 to 450,000. In the pressure-sensitive adhesive composition of the present invention, the content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. Furthermore, the gel fraction of the pressure-sensitive adhesive composition of the present invention is 15.0% or less.
　本発明の粘着剤組成物は、上記構成を有するものであるため、段差追従性及びハンドリング性を兼ね備えている。また、本発明の粘着剤組成物は、段差追従性及びハンドリング性を兼ね備えた粘着シートを形成することもできる。本発明の粘着剤組成物においては、主ポリマーである（メタ）アクリル系共重合体のガラス転移温度と重量平均分子量を所定範囲内とし、熱架橋剤の含有量を所定範囲内とすることにより、段差追従性及びハンドリング性を高めることができる。なお、本発明の粘着剤組成物においては、熱架橋剤の含有量が（メタ）アクリル系共重合体１００質量部に対して０．５質量部未満であり、粘着剤組成物が熱架橋剤を含まない構成も好ましい。本発明の粘着剤組成物が熱架橋剤を含まない場合、粘着剤組成物から粘着シートを形成する際にエージング工程を省略することができ、粘着シートの製造にかかる時間を短縮することができる。 Since the pressure-sensitive adhesive composition of the present invention has the above-described constitution, it has both step followability and handling properties. The pressure-sensitive adhesive composition of the present invention can also form a pressure-sensitive adhesive sheet having both step followability and handling properties. In the pressure-sensitive adhesive composition of the present invention, the glass transition temperature and the weight average molecular weight of the (meth) acrylic copolymer which is the main polymer are in the predetermined ranges, and the content of the thermal crosslinking agent is in the predetermined ranges. , The step following ability and the handling ability can be enhanced. In the pressure-sensitive adhesive composition of the present invention, the content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer, and the pressure-sensitive adhesive composition is a thermal crosslinking agent A configuration not containing When the pressure-sensitive adhesive composition of the present invention does not contain a thermal crosslinking agent, the aging step can be omitted when forming a pressure-sensitive adhesive sheet from the pressure-sensitive adhesive composition, and the time required for producing the pressure-sensitive adhesive sheet can be shortened. .
　本発明の粘着剤組成物は、優れた段差追従性を発揮する。本発明の粘着剤組成物は、例えば、貼着部分に高さが３５μｍ以上の段差があっても、その段差に隙間なく追従することができ、このような場合に、段差追従性が優れていると評価できる。また、本発明の粘着剤組成物は耐久性にも優れている。具体的には、本発明の粘着剤組成物を８５℃、相対湿度８５％の環境下で２４０時間処理した場合であっても、変質することがなく、気泡等の発生が見られない。 The pressure-sensitive adhesive composition of the present invention exhibits excellent step followability. The pressure-sensitive adhesive composition of the present invention can follow the step without gaps even if there is a step having a height of 35 μm or more in the attached portion, for example, and in such a case, the step following property is excellent. Can be evaluated. The pressure-sensitive adhesive composition of the present invention is also excellent in durability. Specifically, even when the pressure-sensitive adhesive composition of the present invention is treated in an environment of 85 ° C. and a relative humidity of 85% for 240 hours, no deterioration occurs and no generation of air bubbles or the like is observed.
　本発明の粘着剤組成物は、ハンドリング性にも優れている。本明細書において、粘着剤組成物のハンドリング性は、貼合時の粘着剤のはみ出し（ウーズ値）で評価することができる。具体的には、本発明の粘着剤組成物を、厚みが１００μｍの粘着シートとし、プレス部の温度を２５℃に設定し、０．２ＭＰａの圧力で５分間加圧した際の粘着シートの広がり（ウーズ値）が小さい場合に、ハンドリング性が良好であると評価できる。粘着シートのウーズ値は１．２ｍｍ以下であることが好ましく、１．０ｍｍ以下であることがより好ましく、０．８ｍｍ以下であることがさらに好ましい。なお、粘着シートのウーズ値は実施例に記載の方法で評価される値である。 The pressure-sensitive adhesive composition of the present invention is also excellent in handleability. In the present specification, the handling property of the pressure-sensitive adhesive composition can be evaluated by the protrusion (Ooz value) of the pressure-sensitive adhesive at the time of bonding. Specifically, the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive sheet having a thickness of 100 μm, the temperature of the press portion is set to 25 ° C., and the pressure-sensitive adhesive sheet spreads when pressed for 5 minutes at a pressure of 0.2 MPa. When (Ooz value) is small, it can be evaluated that the handling property is good. The Worse value of the pressure-sensitive adhesive sheet is preferably 1.2 mm or less, more preferably 1.0 mm or less, and still more preferably 0.8 mm or less. In addition, the Wooss value of an adhesive sheet is a value evaluated by the method as described in an Example.
　本発明の粘着剤組成物のゲル分率は１５．０％以下であればよく、１０．０％以下であることが好ましく、５．０％以下であることがより好ましく、４．０％以下であることがさらに好ましく、３．０％以下であることが一層好ましく、２．０％以下であることが特に好ましい。また、粘着剤組成物のゲル分率の下限値は特に限定されるものではなく、例えば０％であってもよい。なお、粘着剤組成物のゲル分率は、活性エネルギー線を照射して粘着剤組成物を完全に硬化させる前のゲル分率であることが好ましい。粘着剤組成物のゲル分率を上記範囲内とすることにより、段差追従性に優れた粘着剤組成物及び粘着シートを得ることができる。 The gel fraction of the pressure-sensitive adhesive composition of the present invention may be 15.0% or less, preferably 10.0% or less, more preferably 5.0% or less, and 4.0% or less Is more preferably 3.0% or less, still more preferably 2.0% or less. Further, the lower limit value of the gel fraction of the pressure-sensitive adhesive composition is not particularly limited, and may be, for example, 0%. The gel fraction of the pressure-sensitive adhesive composition is preferably a gel fraction before the pressure-sensitive adhesive composition is completely cured by irradiation with active energy rays. By setting the gel fraction of the pressure-sensitive adhesive composition within the above range, it is possible to obtain a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet excellent in level difference followability.
　粘着剤組成物のゲル分率は、以下の方法で測定した値である。
　まず、粘着剤組成物約０．１ｇをサンプル瓶に採取し、酢酸エチル３０ｍｌを加えて２４時間振とうする。その後、このサンプル瓶の内容物を１５０メッシュのステンレス製金網でろ別し、金網上の残留物を１００℃で１時間乾燥して乾燥重量Ｗ（ｇ）を測定する。得られた乾燥重量から下記式１によりゲル分率を求める。
ゲル分率（質量％）＝（乾燥重量Ｗ／粘着剤組成物の採取重量）×１００・・・式１ The gel fraction of the pressure-sensitive adhesive composition is a value measured by the following method.
First, about 0.1 g of the pressure-sensitive adhesive composition is collected in a sample bottle, and 30 ml of ethyl acetate is added and shaken for 24 hours. Thereafter, the contents of the sample bottle are separated by filtration with a stainless steel mesh of 150 mesh, and the residue on the metal mesh is dried at 100 ° C. for 1 hour to measure the dry weight W (g). The gel fraction is determined by the following equation 1 from the obtained dry weight.
Gel fraction (mass%) = (dry weight W / extracted weight of adhesive composition) × 100 .. Formula 1
　本発明の粘着剤組成物のゲル分率は上述したとおりであり、粘着剤組成物は半硬化状態である。ここで、半硬化状態であることは、粘着剤組成物が活性エネルギー線硬化能を有していることを言う。すなわち、本発明の粘着剤組成物は活性エネルギー線照射前の柔らかい状態の組成物である。 The gel fraction of the pressure-sensitive adhesive composition of the present invention is as described above, and the pressure-sensitive adhesive composition is in a semi-cured state. Here, being in a semi-cured state means that the pressure-sensitive adhesive composition has an active energy ray curing ability. That is, the pressure-sensitive adhesive composition of the present invention is a composition in a soft state before irradiation with active energy rays.
　本発明の粘着剤組成物に活性エネルギー線を照射した場合、粘着剤組成物のゲル分率は６０％以上になることが好ましく、６５％以上になることがより好ましく、７０％以上になることがさらに好ましい。なお、活性エネルギー線照射後の粘着剤組成物のゲル分率は、例えば、粘着剤組成物に積算光量が２０００ｍＪ／ｃｍ2以上となるように活性エネルギー線を照射した後に測定する。ここで、活性エネルギー線の積算光量は粘着剤組成物が完全に硬化し得る光量とする。 When the pressure-sensitive adhesive composition of the present invention is irradiated with active energy rays, the gel fraction of the pressure-sensitive adhesive composition is preferably 60% or more, more preferably 65% or more, and preferably 70% or more. Is more preferred. In addition, the gel fraction of the adhesive composition after active energy ray irradiation is measured, for example, after irradiating an active energy ray so that an accumulated light quantity may be 2000 mJ / cm < 2 > or more to an adhesive composition. Here, the integrated light quantity of the active energy ray is taken as the light quantity which can completely cure the pressure-sensitive adhesive composition.
　本発明の粘着剤組成物は、後述するようなシート状の粘着シートであってもよい。また、本発明の粘着剤組成物は、ゲル状の粘着剤組成物であってもよく、例えば容器入りの粘着剤組成物であってもよい。 The pressure-sensitive adhesive composition of the present invention may be a sheet-like pressure-sensitive adhesive sheet as described later. The pressure-sensitive adhesive composition of the present invention may be a gel-like pressure-sensitive adhesive composition, and may be, for example, a container-containing pressure-sensitive adhesive composition.
　本発明の粘着剤組成物を使用する際には、粘着剤組成物を被着体表面に接触させる際及び／又は接触させた後に加熱処理工程を含むことが好ましい。そして、加熱処理工程の後に、活性エネルギー線を照射する工程を含むことが好ましい。すなわち、本発明の粘着剤組成物はホットメルト型の粘着剤組成物であり、かつアフターキュア型の粘着剤組成物である。 When using the pressure-sensitive adhesive composition of the present invention, it is preferable to include a heat treatment step when the pressure-sensitive adhesive composition is brought into contact with the adherend surface and / or after being brought into contact. And it is preferable to include the process of irradiating an active energy ray after a heat treatment process. That is, the pressure-sensitive adhesive composition of the present invention is a hot-melt type pressure-sensitive adhesive composition and an after-cure type pressure-sensitive adhesive composition.
（（メタ）アクリル系共重合体）
　本発明の粘着剤組成物は（メタ）アクリル系共重合体を含む。（メタ）アクリル系共重合体は、粘着剤組成物に含まれる主ポリマーであり、このようなポリマーをベースポリマーと呼ぶこともある。 ((Meth) acrylic copolymer)
The pressure-sensitive adhesive composition of the present invention contains a (meth) acrylic copolymer. The (meth) acrylic copolymer is a main polymer contained in the pressure-sensitive adhesive composition, and such a polymer may be referred to as a base polymer.
　上記（メタ）アクリル系共重合体は、（メタ）アクリル酸アルキルエステル単位を有する。本明細書において、「単位」は重合体を構成する繰り返し単位（単量体単位）である。（メタ）アクリル酸アルキルエステル単位は、（メタ）アクリル酸アルキルエステルに由来するものである。（メタ）アクリル酸アルキルエステルとしては、（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）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ－ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ－ウンデシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボロニル等が挙げられる。これらは１種を単独で使用してもよいし、２種以上を併用してもよい。 The (meth) acrylic copolymer has a (meth) acrylic acid alkyl ester unit. In the present specification, the "unit" is a repeating unit (monomer unit) constituting the polymer. The (meth) acrylic acid alkyl ester unit is derived from the (meth) acrylic acid alkyl ester. As (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate n-nonyl, (meth) acrylate isononyl, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, (meth) N-dodecyl acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ) Ethoxyethyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and (meth) isobornyl acrylic acid. One of these may be used alone, or two or more may be used in combination.
　また、（メタ）アクリル系共重合体は、（メタ）アクリル酸アルキルエステル単位以外の他のアクリル系単量体単位を有してもよい。他のアクリル系単量体単位としては、架橋性官能基を有するアクリル系単量体単位を挙げることができ、例えば、ヒドロキシ基含有アクリル系単量体単位、グリシジル基含有アクリル系単量体単位を挙げることができる。これら単量体単位は１種でもよいし、２種以上でもよい。
　ヒドロキシ基含有アクリル系単量体単位は、ヒドロキシ基含有アクリル系単量体に由来するものである。ヒドロキシ基含有アクリル系単量体としては、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４－ヒドロキシブチル、（メタ）アクリル酸２－ヒドロキシプロピルなどの（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸モノ（ジエチレングリコール）などの（メタ）アクリル酸［（モノ、ジ又はポリ）アルキレングリコール］、（メタ）アクリル酸モノカプロラクトンなどの（メタ）アクリル酸ラクトンが挙げられる。
　グリシジル基含有アクリル系単量体単位は、（メタ）アクリル酸グリシジル等のグリシジル基含有アクリル系単量体に由来するものが挙げられる。 The (meth) acrylic copolymer may have another acrylic monomer unit other than the (meth) acrylic acid alkyl ester unit. As another acrylic monomer unit, the acrylic monomer unit which has a crosslinkable functional group can be mentioned, For example, a hydroxyl group containing acrylic monomer unit, a glycidyl group containing acrylic monomer unit Can be mentioned. These monomer units may be used alone or in combination of two or more.
The hydroxy group-containing acrylic monomer unit is derived from the hydroxy group-containing acrylic monomer. Examples of the hydroxy group-containing acrylic monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate such as (meth) acrylate. And (meth) acrylic acid lactones such as (meth) acrylic acid [(mono, di or poly) alkylene glycols] such as alkyl (meth) acrylic acid mono (diethylene glycol) and (meth) acrylic acid monocaprolactone.
Examples of the glycidyl group-containing acrylic monomer unit include those derived from glycidyl group-containing acrylic monomers such as glycidyl (meth) acrylate.
　（メタ）アクリル系共重合体が、（メタ）アクリル酸アルキルエステル単位以外の他のアクリル系単量体単位を有する場合、他のアクリル系単量体単位の含有量は（メタ）アクリル系共重合体の全質量に対して０．０１～２０質量％であることが好ましく、０．５～１０質量％であることがより好ましい。中でも、架橋性官能基を有するアクリル系単量体単位の含有量が上記範囲内であることが好ましい。他のアクリル系単量体単位の含有量が上記下限値以上であれば、凝集力を十分に高めることができ、上記上限値以下であれば、十分な粘着力を確保しやすくなる。 When the (meth) acrylic copolymer has another acrylic monomer unit other than the (meth) acrylic acid alkyl ester unit, the content of the other acrylic monomer unit is (meth) acrylic copolymer The content is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total mass of the polymer. Among them, the content of the acrylic monomer unit having a crosslinkable functional group is preferably in the above range. If the content of the other acrylic monomer unit is equal to or more than the above lower limit value, the cohesion can be sufficiently increased, and if it is less than or equal to the above upper limit value, it becomes easy to secure sufficient adhesion.
　（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）は－５０℃以上であればよく、－４９℃以上であることが好ましく、－４８℃以上であることがより好ましい。また、（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）は－１０℃以下であることが好ましく、－２０℃以下であることがより好ましく、－３０℃以下であることがさらに好ましく、－４０℃以下であることが特に好ましい。（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）を上記範囲内とすることにより、粘着剤組成物のハンドリング性を高めることができ、粘着剤組成物の加工がしやすくなる。さらに、（メタ）アクリル系共重合体のガラス転移温度（Ｔｇ）を上記範囲内とすることにより、粘着剤組成物を粘着シートとした際の凝集力をより高めることができ、耐久性と粘着性に優れた粘着シートを得ることができる。 The glass transition temperature (Tg) of the (meth) acrylic copolymer may be −50 ° C. or higher, preferably −49 ° C. or higher, and more preferably −48 ° C. or higher. Further, the glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably −10 ° C. or less, more preferably −20 ° C. or less, and still more preferably −30 ° C. or less It is particularly preferable that the temperature is −40 ° C. or less. By setting the glass transition temperature (Tg) of the (meth) acrylic copolymer within the above range, the handling properties of the pressure-sensitive adhesive composition can be enhanced, and processing of the pressure-sensitive adhesive composition becomes easy. Furthermore, by setting the glass transition temperature (Tg) of the (meth) acrylic copolymer within the above range, it is possible to further enhance the cohesion when the pressure-sensitive adhesive composition is made into a pressure-sensitive adhesive sheet, and the durability and adhesion It is possible to obtain a pressure-sensitive adhesive sheet with excellent properties.
　（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）は、３０万～４５万であればよく、３５万～４５万であることが好ましく、３６万～４３万であることがより好ましい。（メタ）アクリル系共重合体の重量平均分子量（Ｍｗ）を上記範囲内とすることにより、段差追従性と耐久性を両立させることができる。通常、粘着剤組成物において段差追従性と耐久性はトレードオフの関係にあるが、本発明においては、（メタ）アクリル系共重合体の重量平均分子量を上記範囲内とすることにより、段差追従性と耐久性の両立が容易となる。 The weight average molecular weight (Mw) of the (meth) acrylic copolymer may be from 300,000 to 450,000, preferably from 350,000 to 450,000, and more preferably from 360,000 to 430,000. By setting the weight average molecular weight (Mw) of the (meth) acrylic copolymer within the above range, it is possible to achieve both step followability and durability. Usually, in the pressure-sensitive adhesive composition, there is a trade-off relationship between the step following property and the durability, but in the present invention, the step following can be achieved by setting the weight average molecular weight of the (meth) acrylic copolymer within the above range. It is easy to achieve both of the properties and durability.
　なお、（メタ）アクリル系共重合体の重量平均分子量は、ゲル浸透クロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレン換算で求めた値である。
　ゲル浸透クロマトグラフィー（ＧＰＣ）の測定条件は以下のとおりである。
溶媒：テトラヒドロフラン
カラム：Ｓｈｏｄｅｘ ＫＦ８０１、ＫＦ８０３Ｌ、ＫＦ８００Ｌ、ＫＦ８００Ｄ（昭和電工（株）製を４本接続して使用した）
カラム温度：４０℃
試料濃度：０．５質量％
検出器：ＲＩ－２０３１ｐｌｕｓ（ＪＡＳＣＯ製）
ポンプ：ＲＩ－２０８０ｐｌｕｓ（ＪＡＳＣＯ製）
流量（流速）：０．８ｍｌ／ｍｉｎ
注入量：１０μｌ
校正曲線：標準ポリスチレンＳｈｏｄｅｘ ｓｔａｎｄａｒｄ ポリスチレン（昭和電工（株）製）Ｍｗ＝１３２０～２５０００００迄の１０サンプルによる校正曲線を使用した。 The weight average molecular weight of the (meth) acrylic copolymer is a value determined by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene.
The measurement conditions of gel permeation chromatography (GPC) are as follows.
Solvent: Tetrahydrofuran column: Shodex KF801, KF803L, KF800L, KF800D (Showa Denko KK made four connection)
Column temperature: 40 ° C
Sample concentration: 0.5 mass%
Detector: RI-2031 plus (made by JASCO)
Pump: RI-2080plus (made by JASCO)
Flow rate (flow rate): 0.8 ml / min
Injection volume: 10 μl
Calibration curve: Standard polystyrene Shodex standard A calibration curve with 10 samples of polystyrene (manufactured by Showa Denko KK) Mw = 1320 to 2.500000 was used.
　（メタ）アクリル系共重合体は、市販のものを用いてもよいし、アクリルモノマーを重合させることによって製造してもよい。市販品としては、例えば、アイカ工業社製のＯＰ－９２００－１、ＯＰ－９２００－３、ＯＰ－９２００－４、ＯＰ－９２００－５、ＯＰ－９２００－７等を用いることができる。また、（メタ）アクリル系共重合体を重合により製造する場合は、重合方法は通常用いられる重合方法から適宜選択できる。重合方法としては、溶液重合法、乳化重合法、懸濁重合法等が挙げられる。 A (meth) acrylic-type copolymer may use a commercially available thing, and may be manufactured by polymerizing an acryl monomer. As a commercially available product, for example, OP-9200-1, OP-9200-3, OP-9200-4, OP-9200-5, OP-9200-7, etc. manufactured by Aika Kogyo Co., Ltd. can be used. Moreover, when manufacturing a (meth) acrylic-type copolymer by superposition | polymerization, the polymerization method can be suitably selected from the polymerization method used normally. As the polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and the like can be mentioned.
（多官能モノマー）
　本発明の粘着剤組成物は、多官能モノマーを含む。多官能モノマーは、分子内に反応性二重結合を２つ以上有するモノマーである。 (Multifunctional monomer)
The pressure-sensitive adhesive composition of the present invention contains a polyfunctional monomer. The polyfunctional monomer is a monomer having two or more reactive double bonds in the molecule.
　多官能モノマーとしては、例えば、ジ（メタ）アクリル酸エチレングリコール、ジ（メタ）アクリル酸トリエチレングリコール、ジ（メタ）アクリル酸１，３－ブチレングリコール、ジ（メタ）アクリル酸１，４－ブチレングリコール、ジ（メタ）アクリル酸１，９－ノナンジオール、ジアクリル酸１，６－ヘキサンジオール、ジ（メタ）アクリル酸ポリブチレングリコール、ジ（メタ）アクリル酸ネオペンチルグリコール、ジ（メタ）アクリル酸テトラエチレングリコール、ジ（メタ）アクリル酸トリプロピレングリコール、ジ（メタ）アクリル酸ポリプロピレングリコール、ビスフェノールＡジグリシジルエーテルのジアクレート、トリ（メタ）アクリル酸トリメチロールプロパン、トリ（メタ）アクリル酸ペンタエリスリトール、テトラ（メタ）アクリル酸ペンタエリスリトール等の多価アルコールの（メタ）アクリル酸エステル類、メタクリル酸ビニル等が挙げられる。 Examples of polyfunctional monomers include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4-di (meth) acrylic acid. Butylene glycol, di (meth) acrylic acid 1,9-nonanediol, diacrylic acid 1,6-hexanediol, di (meth) acrylic acid polybutylene glycol, di (meth) acrylic acid neopentyl glycol, di (meth) acrylic acid Acid tetraethylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polypropylene glycol, bisphenol A diglycidyl ether diacrylate, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol , Te La (meth) polyhydric alcohol (meth) acrylic acid esters such as acrylic acid pentaerythritol, and vinyl methacrylate.
　多官能モノマーは、市販品を使用できる。市販品の例としては、新中村化学社製のＡＴＭ－４ＰＬやＡ－ＴＭＭ－３Ｌ等を挙げることができる。 A commercial item can be used for a polyfunctional monomer. Examples of commercially available products include ATM-4PL and A-TMM-3L manufactured by Shin-Nakamura Chemical Co., Ltd.
　粘着剤組成物は多官能モノマーを（メタ）アクリル系共重合体１００質量部に対して０．１～１０質量部含有すればよく、１～５質量部含有することが好ましく、２～４質量部含有することがより好ましい。上記多官能モノマーは１種類を単独で用いても２種類以上を併用してもよく、２種類以上を併用する場合は、合計質量が上記範囲内であることが好ましい。 The pressure-sensitive adhesive composition may contain the polyfunctional monomer in an amount of 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, and preferably 2 to 4 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. It is more preferable to contain part. The above-mentioned polyfunctional monomers may be used alone or in combination of two or more. When two or more are used in combination, the total mass is preferably in the above range.
（光重合開始剤）
　本発明の粘着剤組成物は、光重合開始剤を含む。光重合開始剤は、活性エネルギー線の照射により上述した多官能モノマーの重合反応を開始させ得るものであればよい。なお、活性エネルギー線とは電磁波または荷電粒子線の中でエネルギー量子を有するものを意味し、紫外線、電子線、可視光線、Ｘ線、イオン線等が挙げられる。中でも、汎用性の点から、紫外線または電子線が好ましく、紫外線が特に好ましい。 (Photopolymerization initiator)
The pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator may be any as long as it can start the polymerization reaction of the above-mentioned polyfunctional monomer by irradiation of active energy rays. The term "active energy ray" means an electromagnetic wave or charged particle beam having energy quantum, and includes ultraviolet light, electron beam, visible light, X-ray, ion beam and the like. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
　光重合開始剤としては、例えばアセトフェノン系開始剤、ベンゾインエーテル系開始剤、ベンゾフェノン系開始剤、ヒドロキシアルキルフェノン系開始剤、チオキサントン系開始剤、アミン系開始剤等が挙げられる。光重合開始剤としては１種を単独で用いてもよく、２種以上を併用してもよい。
　アセトフェノン系開始剤として具体的には、ジエトキシアセトフェノン、ベンジルジメチルケタール等が挙げられる。
　ベンゾインエーテル系開始剤として具体的には、ベンゾイン、ベンゾインメチルエーテル等が挙げられる。
　ベンゾフェノン系開始剤として具体的には、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル等が挙げられる。
　ヒドロキシアルキルフェノン系開始剤として具体的には、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン等が挙げられる。
　チオキサントン系開始剤として具体的には、２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン等が挙げられる。
　アミン系開始剤として具体的には、トリエタノールアミン、４－ジメチル安息香酸エチル等が挙げられる。 Examples of the photopolymerization initiator include acetophenone initiators, benzoin ether initiators, benzophenone initiators, hydroxyalkylphenone initiators, thioxanthone initiators, and amine initiators. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
Specific examples of acetophenone initiators include diethoxyacetophenone, benzyl dimethyl ketal and the like.
Specific examples of the benzoin ether initiator include benzoin and benzoin methyl ether.
Specific examples of benzophenone initiators include benzophenone and methyl o-benzoylbenzoate.
Specific examples of the hydroxyalkyl phenone initiator include 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
Specific examples of thioxanthone initiators include 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone and the like.
Specific examples of the amine initiator include triethanolamine and ethyl 4-dimethylbenzoate.
　光重合開始剤は、市販品を使用できる。市販品の例としては、ＩＧＭレジン社製のＴＺＴやＯｍｎｉｒａｄ１８４等を挙げることができる。 A commercial item can be used for a photoinitiator. Examples of commercially available products include TZT and Omnirad 184 manufactured by IGM Resin.
　粘着剤組成物は光重合開始剤を（メタ）アクリル系共重合体１００質量部に対して０．１～１０質量部含有すればよく、０．１～３質量部含有することが好ましい。なお、上記光重合開始剤は１種類を単独で用いても２種類以上を併用してもよく、２種類以上を併用する場合は、合計質量が上記範囲内であることが好ましい。 The pressure-sensitive adhesive composition may contain 0.1 to 10 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the (meth) acrylic copolymer, and preferably 0.1 to 3 parts by mass. The photopolymerization initiators may be used alone or in combination of two or more. When two or more are used in combination, the total mass is preferably in the above range.
（熱架橋剤）
　本発明の粘着剤組成物中における熱架橋剤の含有量は、（メタ）アクリル系共重合体１００質量部に対して０．５質量部未満であり、０．３質量部以下であることが好ましく、０．２質量部以下であることがより好ましく、０．１質量部以下であることがさらに好ましい。また、熱架橋剤の含有量は、０質量部であることが特に好ましい。熱架橋剤の含有量を上記範囲内とすることにより、粘着剤組成物の段差追従性をより効果的に高めることができる。なお、本発明の粘着剤組成物は熱架橋剤を実質的に含まない態様であることも好ましく、このような場合、粘着剤組成物から粘着シートを形成する際にエージング工程を省略することができ、粘着シートの製造にかかる時間を短縮することができる。 (Heat crosslinker)
The content of the thermal crosslinking agent in the pressure-sensitive adhesive composition of the present invention is less than 0.5 parts by mass and not more than 0.3 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. The amount is preferably 0.2 parts by mass or less, and more preferably 0.1 parts by mass or less. Further, the content of the thermal crosslinking agent is particularly preferably 0 parts by mass. By setting the content of the thermal crosslinking agent in the above range, it is possible to more effectively improve the level difference followability of the pressure-sensitive adhesive composition. In addition, it is also preferable that the adhesive composition of this invention is an aspect which does not contain a thermal crosslinking agent substantially, In such a case, when forming an adhesive sheet from an adhesive composition, an aging process may be skipped. It is possible to reduce the time required for producing the pressure-sensitive adhesive sheet.
　本発明の粘着剤組成物が熱架橋剤を上記範囲内で含有する場合、熱架橋剤としては、例えばイソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物などの公知の熱架橋剤を挙げることができる。中でも、イソシアネート化合物やエポキシ化合物は好ましく用いられる。熱架橋剤は、（メタ）アクリル系共重合体が有する架橋性官能基との反応性を考慮して選択される。たとえば（メタ）アクリル系共重合体が架橋性官能基としてヒドロキシ基を含む場合は、ヒドロキシ基の反応性から、イソシアネート化合物を用いることが好ましい。熱架橋剤としては１種を単独で用いてもよく、２種以上を併用してもよい。 When the pressure-sensitive adhesive composition of the present invention contains a thermal crosslinking agent in the above range, known thermal crosslinking agents include, for example, isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, butylated melamine compounds, etc. And a thermal crosslinker of Among these, isocyanate compounds and epoxy compounds are preferably used. The thermal crosslinking agent is selected in consideration of the reactivity with the crosslinkable functional group possessed by the (meth) acrylic copolymer. For example, when the (meth) acrylic copolymer contains a hydroxy group as a crosslinkable functional group, it is preferable to use an isocyanate compound in view of the reactivity of the hydroxy group. One type of thermal crosslinking agent may be used alone, or two or more types may be used in combination.
　イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシ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等が挙げられる。
　エポキシ化合物としては、例えば、エチレングリコールジ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、プロピレングリコールジグリシジルエーテル、ポリプロピ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、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、テトラグリシジルキシレンジアミン、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、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。 Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
As an epoxy compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. It can be mentioned.
　また、熱架橋剤としては、多官能のアクリレート、例えばポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、３－メチル－１，５－ペンタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，９－ノナンジオールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトール（トリ/テトラ）アクリレート等を用いてもよい。 Moreover, as a thermal crosslinking agent, polyfunctional acrylates such as polyethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,9 Nonanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol (tri / tetra) acrylate, etc. may be used.
（溶剤）
　本発明の粘着剤組成物には溶剤が含まれていてもよい。この場合、溶剤は、粘着剤組成物の塗工適性の向上のために用いられる。 (solvent)
The pressure-sensitive adhesive composition of the present invention may contain a solvent. In this case, the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition.
　このような溶剤としては、例えば、ヘキサン、ヘプタン、オクタン、トルエン、キシレン、エチルベンゼン、シクロヘキサン、メチルシクロヘキサン等の炭化水素類；ジクロロメタン、トリクロロエタン、トリクロロエチレン、テトラクロロエチレン、ジクロロプロパン等のハロゲン化炭化水素類；メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、ジアセトンアルコール等のアルコール類；ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸アミル、酪酸エチル等のエステル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセタート等のポリオール及びその誘導体が挙げられる。 Such solvents include, for example, hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene and dichloropropane; methanol Alcohols such as ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran etc. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone etc Methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate etc. Ester ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.
　溶剤としては１種を単独で用いてもよく、２種以上を併用してもよい。粘着剤組成物に含まれる溶剤の含有量は、粘着剤組成物の全質量に対して、８０質量％以下であることが好ましく、５０質量％以下であることがより好ましい。 One solvent may be used alone, or two or more solvents may be used in combination. The content of the solvent contained in the pressure-sensitive adhesive composition is preferably 80% by mass or less, more preferably 50% by mass or less, based on the total mass of the pressure-sensitive adhesive composition.
（任意成分）
　本発明の粘着剤組成物は、本発明の効果を損なわない範囲で、上記以外の他の成分を含有してもよい。他の成分としては、粘着剤用の添加剤として公知の成分を挙げることができる。例えば、可塑剤、酸化防止剤、金属腐食防止剤、粘着付与剤、シランカップリング剤、紫外線吸収剤、ヒンダードアミン系化合物等の光安定剤等の中から必要に応じて選択できる。 (Optional ingredient)
The pressure-sensitive adhesive composition of the present invention may contain other components other than the above as long as the effects of the present invention are not impaired. As other components, components known as additives for pressure-sensitive adhesives can be mentioned. For example, it can be selected as required from light stabilizers such as plasticizers, antioxidants, metal corrosion inhibitors, tackifiers, silane coupling agents, ultraviolet absorbers and hindered amine compounds.
　可塑剤としては、無官能性アクリル重合体を用いることができる。無官能性アクリル重合体とは、アクリレート基以外の官能基を有しないアクリル系単量体単位のみからなる重合体、又はアクリレート基以外の官能基を有しないアクリル系単量体単位と官能基を有しない非アクリル系単量体単位とからなる重合体を意味する。
　アクリレート基以外の官能基を有しないアクリル系単量体単位としては、例えば非架橋性（メタ）アクリル酸エステル単位と同様のものが挙げられる。
　官能基を有しない非アクリル系単量体単位としては、例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、シクロヘキサンカルボン酸ビニル、安息香酸ビニルのようなカルボン酸ビニルエステル類やスチレン等が挙げられる。 A nonfunctional acrylic polymer can be used as a plasticizer. A nonfunctional acrylic polymer is a polymer consisting only of an acrylic monomer unit having no functional group other than an acrylate group, or an acrylic monomer unit having no functional group other than an acrylate group and a functional group It means a polymer composed of non-acrylic monomer units not having.
As an acryl-type monomer unit which does not have functional groups other than an acrylate group, the thing similar to a non-crosslinkable (meth) acrylic acid ester unit is mentioned, for example.
Examples of non-acrylic monomer units having no functional group include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, Examples thereof include vinyl stearates, vinyl cyclohexanecarboxylates, vinyl esters of carboxylic acids such as vinyl benzoate, and styrene.
　酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は１種を単独で使用してもよいし、２種以上を併用してもよい。
　金属腐食防止剤としては、ベンゾリアゾール系樹脂を挙げることができる。
　粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
　シランカップリング剤としては、例えば、メルカプト系シランカップリング剤、（メタ）アクリル系シランカップリング剤、イソシアネート系シランカップリング剤、エポキシ系シランカップリング剤、アミノ系シランカップリング剤などが挙げられる。
　紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。 Examples of the antioxidant include phenol based antioxidants, amine based antioxidants, lactone based antioxidants, phosphorus based antioxidants, sulfur based antioxidants and the like. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
As a metal corrosion inhibitor, benzotriazole resin can be mentioned.
Examples of tackifiers include rosin resins, terpene resins, terpene phenol resins, coumarone indene resins, styrene resins, xylene resins, phenol resins, petroleum resins and the like.
As a silane coupling agent, a mercapto type silane coupling agent, a (meth) acrylic type silane coupling agent, an isocyanate type silane coupling agent, an epoxy type silane coupling agent, an amino type silane coupling agent etc. are mentioned, for example .
Examples of the UV absorber include benzotriazole compounds and benzophenone compounds.
（両面粘着シート）
　本発明は、上述した粘着剤組成物をシート状にした両面粘着シートに関するものでもある。本発明の両面粘着シートは、粘着剤組成物からなる両面粘着シートであってもよく、また、粘着剤組成物を熱や活性エネルギー線によって半硬化させることで得られる両面粘着シートであってもよい。本発明の両面粘着シートのゲル分率は１５．０％以下であることが好ましく、１０．０％以下であることがより好ましく、５．０％以下であることがさらに好ましく、４．０％以下であることが一層好ましく、３．０％以下であることがより一層好ましく、２．０％以下であることが特に好ましい。両面粘着シートのゲル分率を上記範囲内とすることにより、段差追従性に優れた両面粘着シートを得ることができる。 (Double-sided adhesive sheet)
The present invention also relates to a double-sided pressure-sensitive adhesive sheet in which the above-described pressure-sensitive adhesive composition is formed into a sheet. The double-sided pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive composition, or may be a double-sided pressure-sensitive adhesive sheet obtained by semi-curing the pressure-sensitive adhesive composition by heat or active energy rays. Good. The gel fraction of the double-sided pressure-sensitive adhesive sheet of the present invention is preferably 15.0% or less, more preferably 10.0% or less, still more preferably 5.0% or less, and 4.0% The content is more preferably the following, still more preferably 3.0% or less, and particularly preferably 2.0% or less. By setting the gel fraction of the double-sided pressure-sensitive adhesive sheet within the above range, it is possible to obtain a double-sided pressure-sensitive adhesive sheet excellent in step followability.
　図１は、本発明の両面粘着シートの一例の断面を表す概略図である。両面粘着シート１１は、その両面に剥離シート１２ａ及び剥離シート１２ｂを備える剥離シート付き両面粘着シート１であってもよい。両面粘着シート１１は、図１に示されるような単層の両面粘着シートであってもよく、粘着剤層を複数積層した多層の両面粘着シートであってもよい。また、両面粘着シート１１は、基材（好ましくは透明基材）の両面に粘着剤層を備えた両面粘着シートであってもよい。 FIG. 1 is a schematic view showing a cross section of an example of the double-sided pressure-sensitive adhesive sheet of the present invention. The double-sided pressure-sensitive adhesive sheet 11 may be a double-sided pressure-sensitive adhesive sheet 1 provided with a release sheet 12a and a release sheet 12b on both sides thereof. The double-sided pressure-sensitive adhesive sheet 11 may be a single-layer double-sided pressure-sensitive adhesive sheet as shown in FIG. 1 or may be a multilayer double-sided pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated. The double-sided pressure-sensitive adhesive sheet 11 may be a double-sided pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on both sides of a substrate (preferably, a transparent substrate).
　図１に示されるように両面粘着シート１１の表面は剥離シート１２ａ及び剥離シート１２ｂによって覆われていることが好ましい。剥離シートとしては、剥離シート用基材とこの剥離シート用基材の片面に設けられた剥離剤層とを有する剥離性積層シート、あるいは、低極性基材としてポリエチレンフィルムやポリプロピレンフィルム等のポリオレフィンフィルムが挙げられる。 As shown in FIG. 1, the surface of the double-sided pressure-sensitive adhesive sheet 11 is preferably covered with a release sheet 12a and a release sheet 12b. As a release sheet, a peelable laminate sheet having a release sheet substrate and a release agent layer provided on one side of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity substrate Can be mentioned.
　剥離性積層シートにおける剥離シート用基材には、紙類、高分子フィルムが使用される。剥離剤層を構成する剥離剤としては、例えば、汎用の付加型もしくは縮合型のシリコーン系剥離剤や長鎖アルキル基含有化合物が用いられる。特に、反応性が高い付加型シリコーン系剥離剤が好ましく用いられる。
　シリコーン系剥離剤としては、具体的には、東レ・ダウコーニングシリコーン社製のＢＹ２４－４５２７、ＳＤ－７２２０等や、信越化学工業（株）製のＫＳ－３６００、ＫＳ－７７４、Ｘ６２－２６００などが挙げられる。また、シリコーン系剥離剤中にＳｉＯ2単位と（ＣＨ3）3ＳｉＯ1/2単位あるいはＣＨ2＝ＣＨ（ＣＨ3）ＳｉＯ1/2単位を有する有機珪素化合物であるシリコーンレジンを含有することが好ましい。シリコーンレジンの具体例としては、東レ・ダウコーニングシリコーン社製のＢＹ２４－８４３、ＳＤ－７２９２、ＳＨＲ－１４０４等や、信越化学工業（株）製のＫＳ－３８００、Ｘ９２－１８３等が挙げられる。
　剥離性積層シートとして、市販品を用いてもよい。例えば、帝人デュポンフィルム（株）製の離型処理されたポリエチレンテレフタレートフィルムである重セパレータフィルムや、帝人デュポンフィルム（株）製の離型処理されたポリエチレンテレフタレートフィルムである軽セパレータフィルムを挙げることができる。 Papers and polymer films are used for the release sheet base in the release laminate sheet. As the release agent constituting the release agent layer, for example, a general-purpose addition type or condensation type silicone release agent or a long chain alkyl group-containing compound is used. In particular, an addition-type silicone release agent having high reactivity is preferably used.
Specific examples of silicone release agents include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774 and X62-2600, etc. Can be mentioned. In addition, a silicone resin which is an organic silicon compound having a SiO 2 unit and a (CH 3 ) 3 SiO 1/2 unit or a CH 2 CHCH (CH 3 ) SiO 1/2 unit in a silicone-based release agent preferable. Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.
A commercial item may be used as the peelable laminated sheet. For example, mention may be made of a heavy separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Ltd., and a light separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films Ltd. it can.
　本発明の粘着シートは、剥離力が互いに異なる１対の剥離シートを有することが好ましい。すなわち、剥離シートは、剥離しやすくするために、剥離シート１２ａと剥離シート１２ｂとの剥離性を異なるものとすることが好ましい。一方からの剥離性と他方からの剥離性とが異なると、剥離性が高い方の剥離シートだけを先に剥離することが容易となる。その場合、貼合方法や貼合順序に応じて剥離シート１２ａと剥離シート１２ｂの剥離性を調整すればよい。 The pressure-sensitive adhesive sheet of the present invention preferably has a pair of release sheets having different release forces. That is, in order to make it easy to peel off the release sheet, it is preferable that the release properties of the release sheet 12a and the release sheet 12b be different. When the releasability from one side and the releasability from the other are different, it becomes easy to peel off only the release sheet having the higher releasability first. In that case, the releasability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
　本発明の粘着シートの厚みは、５～５００μｍであることが好ましく、３０～３００μｍであることがより好ましく、５０～２００μｍであることがさらに好ましい。粘着シートの厚みを上記範囲内とすることにより、段差追従性と耐久性を十分に高めることができる。また、粘着剤のはみ出しやべたつきを抑制することができ、ハンドリング性を高めることができる。 The thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 5 to 500 μm, more preferably 30 to 300 μm, and still more preferably 50 to 200 μm. By setting the thickness of the pressure-sensitive adhesive sheet in the above range, the step following property and the durability can be sufficiently enhanced. Moreover, the protrusion and stickiness of the adhesive can be suppressed, and the handling property can be enhanced.
（積層体の製造方法）
　本発明の粘着剤組成物を使用する際には、粘着剤組成物を被着体表面に接触させる。粘着剤組成物を被着体表面に接触させる際及び／又は接触させた後、には加熱処理工程を含むことが好ましい。そして、加熱処理工程の後に、活性エネルギー線を照射する工程を含む。このようにして、積層体が得られる。すなわち、本発明の積層体の製造方法は、粘着剤組成物を被着体表面に接触させる貼合工程と、活性エネルギー線を照射する工程と、を含み、以下の（ａ工程）及び（ｂ工程）の少なくともいずれかを含む。
　（ａ工程）貼合工程において加熱処理を行う。
　（ｂ工程）貼合工程の後工程であって、活性エネルギー線を照射する工程の前工程において脱泡工程を含み、該脱泡工程で加熱処理を行う。 (Method of manufacturing laminate)
When using the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive composition is brought into contact with the adherend surface. When the pressure-sensitive adhesive composition is brought into contact with the adherend surface and / or after being brought into contact, it is preferable to include a heat treatment step. Then, after the heat treatment step, a step of irradiating an active energy ray is included. Thus, a laminate is obtained. That is, the method for producing a laminate of the present invention includes a bonding step of bringing a pressure-sensitive adhesive composition into contact with the surface of an adherend, and a step of irradiating an active energy ray; And / or process step).
(A process) A heat treatment is performed in a bonding process.
(Step b) A degassing step is included in a step after the bonding step, which is a step prior to the step of irradiating the active energy ray, and heat treatment is performed in the defoaming step.
　また、本発明の粘着剤組成物は、粘着剤組成物からなる両面粘着シートであってもよく、粘着剤組成物を熱や活性エネルギー線によって半硬化させることで得られる両面粘着シートであってもよい。このため、積層体の製造方法は、両面粘着シートを被着体表面に接触させる貼合工程と、活性エネルギー線を照射する工程と、を含み、上記（ａ工程）及び（ｂ工程）の少なくともいずれかを含むものでもあってもよい。 The pressure-sensitive adhesive composition of the present invention may be a double-sided pressure-sensitive adhesive sheet made of a pressure-sensitive adhesive composition, and is a double-sided pressure-sensitive adhesive sheet obtained by semi-curing the pressure-sensitive adhesive composition by heat or active energy rays. It is also good. For this reason, the method for producing a laminate includes a bonding step of bringing a double-sided pressure-sensitive adhesive sheet into contact with the adherend surface, and a step of irradiating an active energy ray, and at least the steps (a) and (b) It may be one including any.
　上記貼合工程では、粘着剤組成物もしくは両面粘着シートを被着体に貼合する。貼合方法としては、例えば、ロール貼合方法、真空貼合方法等を挙げることができる。 In the above bonding step, the pressure-sensitive adhesive composition or the double-sided pressure-sensitive adhesive sheet is bonded to an adherend. As a bonding method, the roll bonding method, the vacuum bonding method, etc. can be mentioned, for example.
　上記（ａ工程）及び上記（ｂ工程）における加熱処理では、４０～５９℃で加熱処理を行うことが好ましい。加熱温度は、５０～５９℃とすることも好ましい。積層体の製造工程において、このような加熱処理工程を設けることにより、粘着剤組成物または両面粘着シートの柔軟性をより高めることができ、段差に追従しやすくすることができる。 In the heat treatment in the step (a) and the step (b), the heat treatment is preferably performed at 40 to 59.degree. The heating temperature is also preferably 50 to 59.degree. By providing such a heat treatment step in the manufacturing process of the laminate, the flexibility of the pressure-sensitive adhesive composition or the double-sided pressure-sensitive adhesive sheet can be further enhanced, and the level difference can be easily made to follow.
　従来、ホットメルト型の粘着シートを使用する際には、６０℃以上で加熱処理を行うことが常法とされており、このような高温の加熱処理では被着体を損傷させる危険性があった。本発明の積層体の製造方法においては、貼合工程及び／又は貼合工程の後工程で加熱処理を行う際の処理温度を通常よりも低く抑えることができ、その場合でも十分な段差追従性を得ることができるため、被着体を損傷させる危険性を極めて低く抑えることができる。また、積層体を製造する際の光熱コストを抑制することができ、積層体の製造効率をより効果的に高めることもできる。 Conventionally, when using a hot-melt adhesive sheet, it is customary to carry out heat treatment at 60 ° C. or higher, and such high temperature heat treatment has a risk of damaging the adherend. The In the method for producing a laminate of the present invention, the treatment temperature at the time of performing the heat treatment in the bonding step and / or the subsequent step of the bonding step can be suppressed lower than usual, and even in such a case Therefore, the risk of damaging the adherend can be extremely low. Moreover, the photothermal cost at the time of manufacturing a laminated body can be suppressed, and the manufacturing efficiency of a laminated body can also be raised more effectively.
　なお、４０～５９℃の加熱処理は貼合工程で行われるか、脱泡工程で行われることが好ましい。なお、貼合工程と脱泡工程の両工程で加熱処理が行われてもよい。貼合工程としては、例えば、ロール貼合工程や真空貼合工程を挙げることができる。脱泡工程としては、例えば、オートクレーブ処理工程を挙げることができる。すなわち、４０～５９℃における加熱処理はオートクレーブ処理工程、ロール貼合工程及び真空貼合工程から選択される少なくとも１工程で行われることが好ましい。この場合、オートクレーブ処理工程、ロール貼合工程及び真空貼合工程における加熱設定温度を４０～５９℃とすることが好ましい。なお、加熱処理は貼合工程及び脱泡工程の両方の工程で行われることも好ましい。 The heat treatment at 40 to 59 ° C. is preferably performed in the bonding step or in the defoaming step. In addition, heat processing may be performed in both processes of a bonding process and a defoaming process. As a bonding process, a roll bonding process and a vacuum bonding process can be mentioned, for example. As a degassing process, an autoclave process can be mentioned, for example. That is, the heat treatment at 40 to 59 ° C. is preferably performed in at least one process selected from an autoclave treatment process, a roll bonding process and a vacuum bonding process. In this case, the heating setting temperature in the autoclave treatment step, the roll bonding step and the vacuum bonding step is preferably 40 to 59 ° C. In addition, it is also preferable that heat processing be performed in the process of both a bonding process and a degassing process.
　活性エネルギー線を照射する工程では、粘着剤組成物もしくは両面粘着シートと被着体の貼合物に活性エネルギー線を照射する。このように、活性エネルギー線を照射する工程は後硬化工程と呼ぶこともできる。活性エネルギー線で粘着剤組成物もしくは両面粘着シートを後硬化させることで、粘着剤の凝集力が高まり、被着体への粘着性が向上する。 At the process of irradiating an active energy ray, an active energy ray is irradiated to the adhesion thing of an adhesive composition or a double-sided adhesive sheet, and a to-be-adhered body. Thus, the step of irradiating the active energy ray can also be called a post-curing step. By post-curing the pressure-sensitive adhesive composition or the double-sided pressure-sensitive adhesive sheet with active energy rays, the cohesion of the pressure-sensitive adhesive is increased, and the adhesion to the adherend is improved.
　活性エネルギー線としては、紫外線、電子線、可視光線、Ｘ線、イオン線等が挙げられ、粘着剤層に含まれる光重合開始剤に応じて適宜選択できる。中でも、汎用性の点から、紫外線または電子線が好ましく、紫外線が特に好ましい。
　紫外線の光源としては、例えば、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、無電極紫外線ランプ等を使用できる。
　電子線としては、例えば、コックロフトワルト型、バンデクラフ型、共振変圧型、絶縁コア変圧器型、直線型、ダイナミトロン型、高周波型等の各種類の電子線加速器から放出される電子線を使用できる。
　紫外線の照射出力は、積算光量が１００～１００００ｍＪ／ｃｍ2となるようにすることが好ましく、５００～５０００ｍＪ／ｃｍ2となるようにすることがより好ましい。 As an active energy ray, an ultraviolet ray, an electron beam, a visible ray, an X ray, an ion beam etc. are mentioned, According to the photoinitiator contained in an adhesive layer, it can select suitably. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
As a light source of ultraviolet light, for example, a high pressure mercury lamp, low pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, electrodeless ultraviolet lamp and the like can be used.
As the electron beam, for example, electron beams emitted from various types of electron beam accelerators such as Cockloft Wald type, Bandeklav type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type and the like are used it can.
Radiation output of the UV light, it is preferable that the integrated quantity of light is made to be a 100 ~ 10000mJ / cm 2, and more preferably made to be 500 ~ 5000mJ / cm 2.
（積層体）
　上述した製造方法で製造された積層体は、後硬化した粘着剤組成物（両面粘着シート）及び被着体を備える。本発明の積層体は、後硬化した粘着剤組成物（両面粘着シート）の両方の面に被着体を備えるものであることが好ましい。特に、本発明の粘着剤組成物（両面粘着シート）は段差部を有する被着体の貼合に好ましく用いられる。 (Laminate)
The laminate produced by the above-described production method comprises a post-cured pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet) and an adherend. The laminate of the present invention preferably has an adherend on both sides of the post-cured pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet). In particular, the pressure-sensitive adhesive composition (double-sided pressure-sensitive adhesive sheet) of the present invention is preferably used for bonding an adherend having a stepped portion.
　図２は、本発明の両面粘着シート１１を、段差部３２を有する被着体３１に貼合した積層体３０の構成の一例を表す断面図である。図２に示されているように、被着体３１は段差部３２を有する。段差部３２の厚みは、５～６０μｍとすることができる。このように本発明の両面粘着シート１１は、段差部を有する被着体の貼合用に用いることができる。特に本発明の両面粘着シート１１は段差部３２の厚みが３５μｍ以上の被着体の貼合用にも用いることができる。 FIG. 2 is a cross-sectional view showing an example of the configuration of a laminate 30 in which the double-sided pressure-sensitive adhesive sheet 11 of the present invention is bonded to an adherend 31 having a step portion 32. As shown in FIG. 2, the adherend 31 has a stepped portion 32. The thickness of the step portion 32 can be 5 to 60 μm. Thus, the double-sided adhesive sheet 11 of this invention can be used for the bonding of the to-be-adhered body which has a level | step-difference part. In particular, the double-sided pressure-sensitive adhesive sheet 11 of the present invention can also be used for bonding an adherend having a thickness of the step portion 32 of 35 μm or more.
　被着体３１は、光学部材であることが好ましい。光学部材としては、タッチパネルや画像表示装置等の光学製品における各構成部材を挙げることができる。
　タッチパネルの構成部材としては、例えば透明樹脂フィルムにＩＴＯ膜が設けられたＩＴＯフィルム、ガラス板の表面にＩＴＯ膜が設けられたＩＴＯガラス、透明樹脂フィルムに導電性ポリマーをコーティングした透明導電性フィルム、ハードコートフィルム、耐指紋性フィルムなどが挙げられる。本発明の両面粘着シートは、タッチパネルのセンサー積層用であることが好ましく、タッチペンを用いるタッチパネルのセンサー積層用であることがより好ましい。この観点から、本発明の両面粘着シートの被着体としては、透明樹脂フィルムにＩＴＯ膜が設けられたＩＴＯフィルム、ガラス板の表面にＩＴＯ膜が設けられたＩＴＯガラス、透明樹脂フィルムに導電性ポリマーをコーティングした透明導電性フィルムが好ましい。
　画像表示装置の構成部材としては、例えば液晶表示装置に用いられる反射防止フィルム、配向フィルム、偏光フィルム、位相差フィルム、輝度向上フィルムなどが挙げられる。
　これらの部材に用いられる材料としては、ガラス、ポリカーボネート、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリエチレンナフタレート、シクロオレフィンポリマー、トリアセチルセルロース、ポリイミド、セルロースアシレートなどが挙げられる。 The adherend 31 is preferably an optical member. As an optical member, each structural member in optical products, such as a touch panel and an image display device, can be mentioned.
For example, an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on the surface of a glass plate, a transparent conductive film obtained by coating a conductive polymer on a transparent resin film Hard coat films, fingerprint resistant films and the like can be mentioned. The double-sided pressure-sensitive adhesive sheet of the present invention is preferably for sensor lamination of a touch panel, and more preferably for sensor lamination of a touch panel using a touch pen. From this viewpoint, as the adherend of the double-sided pressure-sensitive adhesive sheet of the present invention, an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on the surface of a glass plate, and a conductive resin Polymer-coated transparent conductive films are preferred.
As a structural member of an image display apparatus, the antireflection film used for a liquid crystal display device, an orientation film, a polarizing film, retardation film, a brightness improvement film etc. are mentioned, for example.
Examples of materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, and cellulose acylate.
　以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
［実施例１］
（粘着剤組成物の作製）
　（メタ）アクリル系共重合体（アイカ工業社製：ＯＰ－９２００－３）１００質量部、多官能モノマー（新中村化学社製：ＡＴＭ－４ＰＬ）３質量部、光重合開始剤（ＩＧＭレジン社製：ＴＺＴ）１．５質量部を混合し、攪拌機（ＳＨＡＳＨＩＮ　ＫＡＧＡＫＵ社製：ＳＫ－２００ＴＶＳ）を用い大気圧下で３分間攪拌し、粘着剤組成物を作製した。 Example 1
(Preparation of pressure-sensitive adhesive composition)
100 parts by mass of (meth) acrylic copolymer (manufactured by Aika Kogyo Co., Ltd .: OP-9200-3), 3 parts by mass of polyfunctional monomer (manufactured by Shin-Nakamura Chemical Co., Ltd .: ATM-4PL), photopolymerization initiator (IGM Resins Co., Ltd.) Product: 1.5 parts by mass of TZT was mixed, and stirred for 3 minutes under atmospheric pressure using a stirrer (SHASHIN KAGAKU: SK-200 TVS) to prepare a pressure-sensitive adhesive composition.
（粘着シートの作製）
　上記のように作製した粘着剤組成物を、シリコーン系剥離剤で処理された剥離剤層を備えた厚さ３８μｍのポリエチレンテレフタレートフィルム（第１の剥離シート）（王子エフテックス社製：３８ＲＬ－０７（２））の表面に、乾燥後の塗工膜厚が１００μｍになるようにアプリケーターで均一に塗工した。その後、１００℃の空気循環式恒温オーブンで３分間乾燥し、第１の剥離シートの表面に粘着剤層を形成した。次いで、この粘着剤層の表面に厚さ３８μｍの第２の剥離シート（王子エフテックス社製：３８ＲＬ－０７（Ｌ））を貼合して、粘着剤層が剥離力差のある１対の剥離シートに挟まれた第１の剥離シート／粘着剤層／第２の剥離シートの構成を備える剥離シート付き両面粘着シートを得た。 (Production of adhesive sheet)
A 38 μm-thick polyethylene terephthalate film (first release sheet) (a release sheet manufactured by Oji F-TEX, Inc .: 38RL-07) provided with a release agent layer treated with a silicone-based release agent, with the pressure-sensitive adhesive composition prepared as described above The surface of (2) was uniformly coated with an applicator so that the coated film thickness after drying was 100 μm. Then, it dried in 100 degreeC of air circulation type thermostatic ovens for 3 minutes, and formed the adhesive layer on the surface of a 1st peeling sheet. Then, a second release sheet (manufactured by Oji F-TEX Co., Ltd .: 38RL-07 (L)) having a thickness of 38 μm is attached to the surface of the pressure-sensitive adhesive layer to form a pair of pressure-sensitive adhesive layers having a difference in release force. A release sheet-included double-sided pressure-sensitive adhesive sheet having a configuration of a first release sheet / pressure-sensitive adhesive layer / second release sheet sandwiched between release sheets was obtained.
（積層体の作製方法）
　ガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）の表面に、紫外線硬化型インクを塗布厚が５μｍになるように額縁状（縦９０ｍｍ×横５０ｍｍ、幅５ｍｍ）にスクリーン印刷した。次いで、紫外線を照射して印刷した上記紫外線硬化型インクを硬化させた。この工程を所定の回数繰り返し、表１～３に記載した所定の厚みの段差部を有する印刷段差ガラスを得た。
　上記で得られた剥離シート付き両面粘着シートを、縦９０ｍｍ×横５０ｍｍの形状に裁断し、第１の剥離シートを剥離し、ラミネーター（株式会社ユーボン製、ＩＫＯ－６５０ＥＭＴ）を用いて、粘着剤層が印刷段差ガラスの額縁状の印刷全面を覆うように貼合した。その後、第２の剥離シートを剥離し、表出した粘着剤層の面にガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）を上記ラミネーターで貼合し、脱泡処理（オートクレーブ処理：４０℃、０．５ＭＰａ、１０分間）を実施した。次いで、印刷段差ガラス側から紫外線照射器（アイグラフィックス（株）製、ＥＣＳ－３０１Ｇ１）にて表１～３に記載した積算光量となるように紫外線を照射し、積層体を得た。 (Production method of laminate)
A UV curable ink was screen printed on the surface of a glass plate (90 mm long × 50 mm wide × 0.5 mm thick) in a frame shape (90 mm long × 50 mm wide, 5 mm wide) so that the coating thickness would be 5 μm. Next, ultraviolet rays were irradiated to cure the printed ultraviolet curable ink. This process was repeated a predetermined number of times to obtain a printed stepped glass having a stepped portion with a predetermined thickness described in Tables 1 to 3.
The double-sided pressure-sensitive adhesive sheet with a release sheet obtained above is cut into a shape of 90 mm long × 50 mm wide, the first release sheet is peeled off, and a pressure-sensitive adhesive is used using a laminator (manufactured by Eubon Co., Ltd., IKO-650 EMT) A layer was pasted so that the frame-like printing whole surface of printing level difference glass might be covered. Thereafter, the second release sheet is peeled off, and a glass plate (90 mm long × 50 mm wide × 0.5 mm thick) is bonded to the surface of the exposed pressure-sensitive adhesive layer with the above laminator, and defoaming treatment (autoclave treatment: 40 ° C, 0.5 MPa, 10 minutes) was performed. Next, ultraviolet rays were irradiated from the side of the printing step glass with an ultraviolet irradiator (manufactured by Eye Graphics Co., Ltd., ECS-301G1) so as to obtain the integrated light amount described in Tables 1 to 3, to obtain a laminate.
［実施例２］
　実施例１の（積層体の作製方法）で、粘着剤層の第２の剥離シート側の面にガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）を貼合する際に、ラミネーターを４０℃で加温した状態で貼合し、その後に脱泡処理（オートクレーブ処理：４０℃、０．５ＭＰａ、１０分間）を実施しなかったこと以外は、実施例１と同様にして積層体を得た。 Example 2
When bonding a glass plate (90 mm in length × 50 mm in width × 0.5 mm in thickness) to the surface of the pressure-sensitive adhesive layer on the side of the second release sheet in (the method for producing a laminate) in Example 1; A laminate was obtained in the same manner as in Example 1 except that lamination was carried out in a heated state at ° C. and then defoaming treatment (autoclave treatment: 40 ° C., 0.5 MPa, 10 minutes) was not performed. The
［実施例３］
　実施例１の（積層体の作製方法）で、粘着剤層の第２の剥離シート側の面にガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）を貼合する際に、ラミネーターを４０℃で加温した状態で貼合した以外は、実施例１と同様にして積層体を得た。 [Example 3]
When bonding a glass plate (90 mm in length × 50 mm in width × 0.5 mm in thickness) to the surface of the pressure-sensitive adhesive layer on the side of the second release sheet in (the method for producing a laminate) in Example 1; A laminate was obtained in the same manner as Example 1, except that the lamination was carried out in the heated state at ° C.
［実施例４］
　実施例１の（積層体の作製方法）で真空貼合機（常陽工学社製：真空重ね合せ装置（ＪＥ２０２０Ｂ－ＭＶＨ））を用いて、表出した粘着剤層の面にガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）を４０℃、弱加圧力０．６ｋＮ、強加圧力１．２ｋＮ、真空圧１００Ｐａ、加圧保持時間１０ｓで貼合し、脱泡処理（オートクレーブ処理：４０℃、０．５ＭＰａ、１０分間）を実施しなかったこと以外は、実施例１と同様にして積層体を得た。 Example 4
A glass plate (90 mm in length) was formed on the surface of the pressure-sensitive adhesive layer exposed by using a vacuum bonding machine (manufactured by Joyo Engineering Co., Ltd .: vacuum laminating apparatus (JE2020B-MVH)) in (Production method of laminate) of Example 1 × 50 mm × 0.5 mm thickness 40 ° C, weak pressure 0.6 kN, strong pressure 1.2 kN, vacuum pressure 100 Pa, pressure holding time 10 s, degassing treatment (autoclave treatment: 40 ° C., A laminate was obtained in the same manner as Example 1 except that 0.5 MPa for 10 minutes was not performed.
［実施例５］
　実施例１の（積層体の作製方法）で真空貼合機を用いて、表出した粘着剤層の面にガラス板（縦９０ｍｍ×横５０ｍｍ×厚み０．５ｍｍ）を４０℃で貼合した以外は、実施例１と同様にして積層体を得た。 [Example 5]
A glass plate (90 mm long × 50 mm wide × 0.5 mm thick) was bonded at 40 ° C. to the surface of the pressure-sensitive adhesive layer exposed using a vacuum bonding machine in (Production method of laminate) of Example 1 A laminate was obtained in the same manner as Example 1 except for the above.
［実施例６］
　実施例１の（積層体の作製方法）でオートクレーブ処理の温度を５５℃に変更した以外は、実施例１と同様にして積層体を得た。 [Example 6]
A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 55 ° C. in (Production method of laminate) of Example 1.
［実施例７］
　実施例１の（積層体の作製方法）でオートクレーブ処理の温度を５９℃に変更した以外は、実施例１と同様にして積層体を得た。 [Example 7]
A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 59 ° C. in (Production method of laminate) of Example 1.
［実施例８］
　実施例１の（積層体の作製方法）でオートクレーブ処理の温度を５５℃、時間を３０ｍｉｎに変更した以外は、実施例１と同様にして積層体を得た。 [Example 8]
A laminate was obtained in the same manner as in Example 1 except that the autoclave treatment temperature was changed to 55 ° C., and the time was changed to 30 minutes in (Production method of laminate) of Example 1.
［実施例９］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－１（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 [Example 9]
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-1 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［実施例１０］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－１（アイカ工業株式会社製）に変更し、（積層体の作製方法）でオートクレーブ処理の温度を５５℃に変更した以外は、実施例１と同様にして積層体を得た。 [Example 10]
The (meth) acrylic copolymer was changed to OP-9200-1 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 and the temperature of autoclave treatment was used in (a method of preparing a laminate) A laminate was obtained in the same manner as in Example 1 except that 55.degree. C. was changed.
［実施例１１］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－５（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 [Example 11]
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-5 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［実施例１２］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－５（アイカ工業株式会社製）に変更し、（積層体の作製方法）でオートクレーブ処理の温度を５５℃に変更した以外は、実施例１と同様にして積層体を得た。 [Example 12]
The (meth) acrylic copolymer was changed to OP-9200-5 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 and the temperature of autoclave treatment was used in (a method of preparing a laminate) A laminate was obtained in the same manner as in Example 1 except that 55.degree. C. was changed.
［実施例１３］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－７（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 [Example 13]
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-7 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［実施例１４］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－７（アイカ工業株式会社製）に変更し、（積層体の作製方法）であって、オートクレーブ処理の温度を５５℃に変更した以外は、実施例１と同様にして積層体を得た。 Example 14
The (meth) acrylic copolymer is changed to OP-9200-7 (manufactured by Aika Kogyo Co., Ltd.) in (preparation of a pressure-sensitive adhesive composition) in Example 1 (a method of preparing a laminate), which is an autoclave. A laminate was obtained in the same manner as in Example 1 except that the treatment temperature was changed to 55 ° C.
［実施例１５］
　実施例１の（粘着剤組成物の作製）で熱架橋剤（東ソー株式会社製：コロネートＬ－５５Ｅ）を（メタ）アクリル系共重合体１００質量部に対して０．３質量部添加し、（粘着シートの作成）の工程の最後に粘着シートを２３±５℃、相対湿度５０±１０％の条件下で７日間エージングした以外は、実施例１と同様にして積層体を得た。 [Example 15]
In Example 1 (preparation of a pressure-sensitive adhesive composition), 0.3 part by mass of a thermal crosslinking agent (manufactured by Tosoh Corporation: Coronate L-55E) is added with respect to 100 parts by mass of a (meth) acrylic copolymer. A laminate was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive sheet was aged at 23 ± 5 ° C. and 50 ± 10% relative humidity for 7 days at the end of the process of (preparation of pressure-sensitive adhesive sheet).
［実施例１６］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－４（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 [Example 16]
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-4 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［比較例１］
　実施例１の（粘着剤組成物の作製）で熱架橋剤（東ソー株式会社製：コロネートＬ－５５Ｅ）を（メタ）アクリル系共重合体１００質量部に対して１．０質量部添加し、（粘着シートの作成）の工程の最後に粘着シートを２３±５℃、相対湿度５０±１０％の条件下で７日間エージングした以外は、実施例１と同様にして積層体を得た。 Comparative Example 1
In (Preparation of pressure-sensitive adhesive composition) of Example 1, a thermal crosslinking agent (manufactured by Tosoh Corp .: Coronate L-55E) is added in an amount of 1.0 part by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. A laminate was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive sheet was aged at 23 ± 5 ° C. and 50 ± 10% relative humidity for 7 days at the end of the process of (preparation of pressure-sensitive adhesive sheet).
［比較例２］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－６（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 Comparative Example 2
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-6 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［比較例３］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－８（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 Comparative Example 3
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-8 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［比較例４］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－９２００－９（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 Comparative Example 4
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-9200-9 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
［比較例５］
　実施例１の（粘着剤組成物の作製）で（メタ）アクリル系共重合体をＯＰ－７０００－Ｖ６（アイカ工業株式会社製）に変更した以外は、実施例１と同様にして積層体を得た。 Comparative Example 5
A laminate was prepared in the same manner as in Example 1 except that (meth) acrylic copolymer was changed to OP-7000-V6 (manufactured by Aika Kogyo Co., Ltd.) in (Preparation of pressure-sensitive adhesive composition) in Example 1. Obtained.
（評価）
＜段差追従性評価＞
　積層体の印刷段差部をマイクロスコープ（倍率：２５倍）で観察し、貼合部に気泡が見られない（完全に段差が埋まっている）場合の印刷段差部の厚みを段差追従性の評価結果として記録した。 (Evaluation)
<Step followability evaluation>
Evaluation of difference in level following the thickness of the printing step portion when no bubbles are seen in the bonding portion (the step is completely buried) by observing the printing step portion of the laminate with a microscope (magnification: 25 times) Recorded as a result.
＜耐久性＞
　積層体を８５℃、相対湿度８５％の環境下に２４０時間置き、サンプル全体に気泡が生じていないかをマイクロスコープ（倍率：２５倍）で観察し、以下の基準で評価した。
○：気泡の発生がまったく無い。
×：気泡が発生している。 <Durability>
The laminate was placed in an environment of 85 ° C. and relative humidity of 85% for 240 hours, and observed for no bubbles in the entire sample with a microscope (magnification: 25 times) and evaluated based on the following criteria.
○: There is no generation of air bubbles at all.
X: Air bubbles are generated.
＜ハンドリング性＞
　剥離シート付き両面粘着シートから長さ３０ｍｍ×幅３０ｍｍのサイズでシート片を切り出した。シート片の剥離シートの片側を剥離し、剥き出しにした粘着剤層を、予め５０ｍｍ角に切り出しておいた剥離シート（Ａ７１ １００μｍ:帝人デュポンフィルム）のシリコーン処理面に貼り付けた。その後、シート片上に残っている他方の剥離シートの上に、別途５０ｍｍ角に切り出しておいた剥離シート(Ａ３８＃５０:帝人デュポンフィルム）のシリコーン処理面を被せた。その後、プレス試験機（東洋精機社製：ＭＰ－ＷＮＬ)を用いて、プレス部の温度を２５℃に設定し、０．２ＭＰａの圧力で５分間加圧した。その後、粘着剤層が剥離シートの各辺から外側に広がった距離を測定した。具体的には、剥離シートの各辺における粘着剤層が最も広がっている点との距離（最大距離）を測定し、四辺の平均値をウーズ値とした。なお、ハンドリング性は以下の評価基準で評価した。
○：ウーズ値が１．２ｍｍ以下
×：ウーズ値が１．２ｍｍ超え <Handling property>
A sheet piece was cut out in a size of 30 mm long × 30 mm wide from the double-sided pressure-sensitive adhesive sheet with a release sheet. One side of the release sheet of the sheet piece was peeled off, and the pressure-sensitive adhesive layer peeled off was attached to the silicone-treated side of a release sheet (A71 100 μm: Teijin DuPont film) cut out in advance to 50 mm square. Thereafter, the silicone-treated side of a release sheet (A38 # 50: Teijin DuPont film) which had been separately cut into 50 mm squares was placed on the other release sheet remaining on the sheet piece. Thereafter, using a press tester (manufactured by Toyo Seiki Co., Ltd .: MP-WNL), the temperature of the press part was set to 25 ° C., and pressure was applied for 5 minutes at a pressure of 0.2 MPa. Thereafter, the distance that the pressure-sensitive adhesive layer spread outward from each side of the release sheet was measured. Specifically, the distance (maximum distance) to the point at which the pressure-sensitive adhesive layer in each side of the release sheet is the most spread was measured, and the average value of the four sides was taken as the Ooz value. In addition, the handling property was evaluated by the following evaluation criteria.
○: Wooss value is 1.2 mm or less ×: Wooss value is over 1.2 mm
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例及び比較例の結果から、（メタ）アクリル系共重合体の重量平均分子量が３０万～４５万であり、（メタ）アクリル系共重合体のＴｇが－５０℃以上であり、熱架橋剤の添加量が０．５質量部未満である場合に、段差追従性及び良好なハンドリング特性が得られることが分かった。なお、熱架橋剤を（メタ）アクリル系共重合体に対して０．３質量部添加した実施例１５においては、エージングが必要ではあったが、段差追従性及び良好なハンドリング特性の特性が得られた。 From the results of Examples and Comparative Examples, the weight average molecular weight of the (meth) acrylic copolymer is 300,000 to 450,000, the Tg of the (meth) acrylic copolymer is -50 ° C. or higher, and the heat crosslinks It was found that when the additive amount of the agent is less than 0.5 parts by mass, level difference followability and good handling characteristics can be obtained. In addition, in Example 15 which added 0.3 mass part of thermal crosslinking agents with respect to the (meth) acrylic-type copolymer, although aging was required, the characteristic of level | step difference follow-up property and a favorable handling characteristic is acquired. It was done.
　なお、比較例１は、熱架橋剤を（メタ）アクリル系共重合体に対して１．０質量部添加しているため、段差追従性に劣る結果となった。また、比較例３は、（メタ）アクリル系共重合体の分子量が大きく、比較例４は（メタ）アクリル系共重合体の分子量が小さいが、（メタ）アクリル系共重合体のＴｇが高いため、段差追従性に劣る結果となった。比較例２は、（メタ）アクリル系共重合体のＴｇが低く、比較例５は、（メタ）アクリル系共重合体のＴｇが低く、かつ（メタ）アクリル系共重合体の分子量が小さいため、ハンドリング性が劣る結果となった。 In addition, in Comparative Example 1, the thermal crosslinking agent was added in an amount of 1.0 part by mass with respect to the (meth) acrylic copolymer, so that the step followability was inferior. Further, Comparative Example 3 has a large molecular weight of the (meth) acrylic copolymer, and Comparative Example 4 has a small molecular weight of the (meth) acrylic copolymer, but the Tg of the (meth) acrylic copolymer is high. As a result, the step followability was poor. The Tg of the (meth) acrylic copolymer is low in Comparative Example 2, and the Tg of the (meth) acrylic copolymer is low in Comparative Example 5 and the molecular weight of the (meth) acrylic copolymer is small. The result was poor handling.
　１          剥離シート付き両面粘着シート
　１１        両面粘着シート
　１２ａ      剥離シート
　１２ｂ      剥離シート
　３０        積層体
　３１        被着体
　３２        段差部 DESCRIPTION OF SYMBOLS 1 double-sided adhesive sheet with release sheet 11 double-sided adhesive sheet 12a release sheet 12b release sheet 30 laminated body 31 adherend 32 step portion

Claims (7)

  1. 　ガラス転移温度（Ｔｇ）が－５０℃以上であり、重量平均分子量が３０万～４５万の（メタ）アクリル系共重合体１００質量部と、
    　多官能モノマー０．１～１０質量部と、
    　活性エネルギー線の照射により前記多官能モノマーの重合反応を開始させる光重合開始剤０．１～１０質量部と、を含有し、
    　熱架橋剤の含有量が、（メタ）アクリル系共重合体１００質量部に対して０．５質量部未満であり、
    　ゲル分率が１５．０％以下である粘着剤組成物。     100 parts by mass of a (meth) acrylic copolymer having a glass transition temperature (Tg) of −50 ° C. or higher and a weight average molecular weight of 300,000 to 450,000,
    0.1 to 10 parts by mass of a polyfunctional monomer,
    And 0.1 to 10 parts by mass of a photopolymerization initiator for initiating the polymerization reaction of the polyfunctional monomer by irradiation of active energy rays.
    The content of the thermal crosslinking agent is less than 0.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer,
    The adhesive composition whose gel fraction is 15.0% or less.
  2. 　活性エネルギー線の照射によりゲル分率が６０％以上となる請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the gel fraction is 60% or more by irradiation of active energy rays.
  3. 　請求項１又は２に記載の粘着剤組成物をシート状にした両面粘着シート。 A double-sided pressure-sensitive adhesive sheet obtained by forming the pressure-sensitive adhesive composition according to claim 1 into a sheet.
  4. 　請求項３に記載の両面粘着シートの両面に剥離シートを備える剥離シート付き両面粘着シート。 A release sheet-provided double-sided pressure-sensitive adhesive sheet comprising release sheets on both sides of the double-sided pressure-sensitive adhesive sheet according to claim 3.
  5. 　請求項１又は２に記載の粘着剤組成物、又は請求項３に記載の両面粘着シートを被着体表面に接触させる貼合工程と、活性エネルギー線を照射する工程と、を含み、
    　以下の（ａ工程）及び（ｂ工程）の少なくともいずれかを含む積層体の製造方法。
    　（ａ工程）前記貼合工程において加熱処理を行う。
    　（ｂ工程）前記貼合工程の後工程であって、前記活性エネルギー線を照射する工程の前工程において脱泡工程を含み、該脱泡工程で加熱処理を行う。     A bonding step of bringing the pressure-sensitive adhesive composition according to claim 1 or 2 or the double-sided pressure-sensitive adhesive sheet according to claim 3 into contact with an adherend surface, and irradiating an active energy ray.
    The manufacturing method of the laminated body containing at least any one of the following (a process) and (b process).
    (A process) A heat treatment is performed in the said bonding process.
    (Step b) A degassing step is included in a step after the bonding step, which is a step prior to the step of irradiating the active energy ray, and heat treatment is performed in the defoaming step.
  6. 　前記（ａ工程）及び前記（ｂ工程）における加熱処理では、４０～５９℃で加熱処理を行う請求項５に記載の積層体の製造方法。 The method for producing a laminate according to claim 5, wherein the heat treatment in the step (a) and the step (b) is performed at 40 to 59 ° C.
  7. 　前記被着体が、光学部材である請求項５又は６に記載の積層体の製造方法。 The method for manufacturing a laminate according to claim 5, wherein the adherend is an optical member.
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