WO2021200293A1 - 赤外光透過粘着剤組成物 - Google Patents

赤外光透過粘着剤組成物 Download PDF

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WO2021200293A1
WO2021200293A1 PCT/JP2021/011524 JP2021011524W WO2021200293A1 WO 2021200293 A1 WO2021200293 A1 WO 2021200293A1 JP 2021011524 W JP2021011524 W JP 2021011524W WO 2021200293 A1 WO2021200293 A1 WO 2021200293A1
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Prior art keywords
sensitive adhesive
pressure
mass
infrared light
less
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PCT/JP2021/011524
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English (en)
French (fr)
Japanese (ja)
Inventor
真由 尾▲崎▼
昌之 岡本
香織 赤松
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日東電工株式会社
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Priority to CN202180023628.1A priority Critical patent/CN115335485A/zh
Priority to KR1020227032811A priority patent/KR20220156553A/ko
Publication of WO2021200293A1 publication Critical patent/WO2021200293A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

  • the present invention relates to an infrared light transmitting pressure-sensitive adhesive composition, an infrared light transmitting pressure-sensitive adhesive layer, and an infrared light transmitting pressure-sensitive adhesive sheet.
  • an adhesive also referred to as a pressure-sensitive adhesive; the same applies hereinafter
  • adhesives are widely used for the purpose of joining, fixing, and protecting members in portable electronic devices such as mobile phones.
  • an adhesive sheet having a light-shielding property is used for the purpose of preventing light leakage from a light source such as a backlight module.
  • Patent Documents 1 to 6 are mentioned as documents relating to this kind of technology.
  • Patent Documents 1 to 5 disclose an adhesive sheet in which a black printing layer is provided on one side of a resin film base material.
  • Patent Document 6 is a prior art document that discloses a single-sided adhesive sheet laminated on a graphite sheet.
  • Japanese Patent Application Laid-Open No. 2013-87246 Japanese Patent Application Laid-Open No. 2013-166891 Japanese Patent Application Laid-Open No. 2015-83660 Japanese Patent Application Laid-Open No. 2017-57375 Japanese Patent Application Laid-Open No. 2018-2898 Japanese Patent Application Laid-Open No. 2017-52835
  • the conventional adhesive sheet with light-shielding property blocks infrared light as well as visible light. Therefore, when the adhesive sheet is used for a sensing device or the like that emits infrared light, even the infrared light is shielded, so that the infrared light is not irradiated to the object and the desired effect cannot be obtained. there were.
  • the present invention has been made to solve the above-mentioned problems in the prior art, and is an infrared light capable of forming an infrared light transmitting pressure-sensitive adhesive layer that blocks (absorbs) visible light and transmits infrared light.
  • One object of the present invention is to provide a transmissive pressure-sensitive adhesive composition, an infrared light-transmitting pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition, and an infrared light-transmitting pressure-sensitive adhesive sheet including the pressure-sensitive adhesive layer.
  • the present inventors have determined that the pressure-sensitive adhesive composition contains a near-infrared light-transmitting black color material and a base polymer having a glass transition temperature in a specific range.
  • a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet that have sufficient adhesiveness, block visible light, and transmit infrared light can be obtained, and have completed the present invention.
  • the present invention is as follows.
  • An infrared light transmitting pressure-sensitive adhesive composition containing a base polymer and a near-infrared light transmitting black color material.
  • the glass transition temperature (Tg) of the base polymer is ⁇ 40 ° C. or lower.
  • Infrared light transmitting pressure-sensitive adhesive composition is a near infrared light transmitting black dye.
  • An infrared light transmitting pressure-sensitive adhesive layer comprising the infrared light transmitting pressure-sensitive adhesive composition according to any one of [1] to [4].
  • an infrared light transmitting pressure-sensitive adhesive composition having sufficient adhesiveness, which can block visible light and form an infrared light transmitting pressure-sensitive adhesive layer through which infrared light is transmitted, the pressure-sensitive adhesive.
  • An infrared light transmitting pressure-sensitive adhesive layer composed of a composition and an infrared light transmitting pressure-sensitive adhesive sheet provided with the pressure-sensitive adhesive layer can be provided.
  • FIG. 1 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to the embodiment of the present invention.
  • FIG. 2 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to another embodiment of the present invention.
  • FIG. 3 is an example of a schematic cross-sectional view of the pressure-sensitive adhesive sheet according to another embodiment of the present invention.
  • adheresive refers to a material that exhibits a soft solid state (viscoelastic body) in a temperature range near room temperature and has the property of easily adhering to an adherend by pressure.
  • the pressure-sensitive adhesive referred to here is generally defined as "CA Dahlquist,” Adhesion: Fundamental and Practice “, McLaren & Sons, (1966) P.143", and generally has a complex tensile modulus E *. It can be a material having the property of satisfying (1 Hz) ⁇ 107 dyne / cm 2 (typically, a material having the above property at 25 ° C.).
  • adheresive sheet may include what is called “adhesive tape”, “adhesive label”, “adhesive film” and the like.
  • the "main component” refers to a component contained in excess of 50% by mass unless otherwise specified.
  • the percentage based on mass is synonymous with the percentage etc. based on weight.
  • the infrared light-transmitting pressure-sensitive adhesive composition of the embodiment of the present invention (hereinafter, may be simply referred to as a pressure-sensitive adhesive composition) is a base polymer and a near-infrared light-transmitting black color material (hereinafter, simply referred to as a black color material).
  • the base polymer has a glass transition temperature (Tg) of ⁇ 40 ° C. or lower.
  • the pressure-sensitive adhesive layer formed by using the infrared light-transmitting pressure-sensitive adhesive composition of the present embodiment has a property of blocking (absorbing) visible light and transmitting infrared light.
  • an infrared transmission filter or the like which is a colored cured film obtained by polymerizing and curing a colored composition, has been mainly used for an infrared sensor or the like.
  • an air layer is formed at the interface between the cured film such as the filter and the like, there is a problem that it is easily affected by interfacial reflection and the transmittance of infrared light is lowered.
  • the present embodiment is a pressure-sensitive adhesive composition, and by forming the pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition, the formation of the air layer is suppressed, and by extension, the interfacial reflection is reduced, so that the transmittance of infrared light is reduced. Can be raised.
  • Visible light means light having a short wavelength limit of 360 to 400 nm and a long wavelength limit of 760 to 830 nm based on JIS 8120: 2001.
  • the pressure-sensitive adhesive layer preferably has an average visible light transmittance of 30% or less, more preferably 20% or less, and further preferably 10% or less.
  • the average transmittance of visible light having a wavelength range of 400 to 700 nm is preferably 30% or less, more preferably 20% or less, still more preferably 10% or less.
  • the pressure-sensitive adhesive layer preferably has a light transmittance of 25% or less, more preferably 20% or less, still more preferably 15% or less over a wavelength range of 380 to 500 nm. It is more preferably less than or equal to%.
  • Infrared light means light having a wavelength longer than the wavelength range of visible light.
  • near-infrared light is preferably light having a wavelength in the wavelength range of 800 to 2500 nm.
  • the pressure-sensitive adhesive layer preferably has an average transmittance of infrared light, particularly near-infrared light, of 80% or more, more preferably 83% or more, and further preferably 85% or more.
  • the pressure-sensitive adhesive layer preferably has an average transmittance of 80% or more, more preferably 83% or more, of the near-infrared light having a wavelength range of 850 to 1500 nm. More preferably, it is 85% or more.
  • the pressure-sensitive adhesive layer preferably has a light transmittance of 60% or more, more preferably 65% or more, further preferably 70% or more, and further preferably 75% or more over a wavelength range of 800 to 2500 nm. It is more preferably% or more.
  • the light transmittance of the pressure-sensitive adhesive sheet of the present embodiment can be obtained by measuring the absorption spectrum using a spectrophotometer.
  • a spectrophotometer manufactured by Hitachi High-Technologies Corporation
  • a measurement wavelength of 380 to 2500 nm can be measured.
  • the type and content of the near-infrared light transmitting black color material which is one component of the pressure-sensitive adhesive composition of the present embodiment are adjusted. It can be realized by. Specifically, the coloring material has various colors such as red, yellow, green, blue, purple, and black, and each exhibits a unique light transmittance behavior. By selecting a black color material that blocks visible light and transmits infrared light from various color materials that exhibit various light transmittance behaviors, or by combining two or more types of color materials. , A near-infrared light transmitting black color material can be prepared. Further, the content and the content ratio of various coloring materials may be adjusted. The light transmittance behavior is the same even when it is contained in the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet.
  • the Young's modulus of the pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive composition is preferably 10 MPa or less.
  • Young's modulus is 10 MPa or less, the pressure-sensitive adhesive layer can be formed well, and the followability with the adherend is excellent. Further, even when the adherend is attached to the wet surface, the dimensional change due to swelling can be suppressed and the adherend can be adhered to the wet surface.
  • the Young's modulus is more preferably 8 MPa or less, further preferably 5 MPa or less, and particularly preferably 3 MPa or less.
  • the lower limit of the Young's modulus is not particularly limited, but from the viewpoint of ease of processing, it is preferably 0.001 MPa or more, more preferably 0.01 MPa or more, and 0.05 MPa or more. Is even more preferable.
  • the Young's modulus in this embodiment is a value at 25 ° C.
  • the Young's modulus of the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer is formed can be within the above range by adjusting the type and blending ratio of the base polymer.
  • the Young's modulus of the pressure-sensitive adhesive layer formed by using the infrared light-transmitting pressure-sensitive adhesive composition of the present embodiment is obtained by preparing a sample in which the pressure-sensitive adhesive layer is formed in a string shape and using a tensile tester (manufactured by Shimadzu Corporation). It can be calculated from the stress-strain curve measured when pulled at a speed of 50 mm / min using AG-IS).
  • the infrared light transmitting pressure-sensitive adhesive composition of the present embodiment has a peeling adhesive strength of 3 N / 20 mm or more when it is attached to a glass plate according to JIS Z 0237: 2009 in the pressure-sensitive adhesive layer formed by using the same. It is preferable to have.
  • the above adhesive strength can be realized by adjusting the glass transition temperature of the base polymer described later.
  • the adhesive strength is in the above range, the formation of an air layer between the pressure-sensitive adhesive layer and the object to be attached can be further suppressed, interfacial reflection can be reduced, and the transmittance of infrared light can be increased.
  • the adhesive strength is more preferably 4N / 20 mm or more, still more preferably 5N / 20 mm or more.
  • the above adhesive strength can be measured by performing the following peeling adhesive strength test according to JIS Z 0237: 2009.
  • a PET film having a thickness of 25 ⁇ m is attached to one adhesive surface of the double-sided adhesive sheet, lined, and cut to a width of 20 mm to prepare a measurement sample.
  • the other adhesive surface of the measurement sample is attached to a glass plate as an adherend by reciprocating a 2 kg roller once with an adhesive area of 20 mm in width and 100 mm in length.
  • the measurement sample attached to the adherend in this way is left at an ambient temperature of 40 ° C. for 3 days. Then, the force (N / 20 mm) when the measurement sample is peeled off from the adherend at a peeling angle of 180 ° and a tensile speed of 300 mm / min is measured.
  • the infrared light transmitting pressure-sensitive adhesive composition of the present embodiment contains a base polymer and a near infrared light transmitting black color material.
  • a base polymer contains a base polymer and a near infrared light transmitting black color material.
  • each component contained in the pressure-sensitive adhesive composition of the present embodiment will be described.
  • the “base polymer” in the present embodiment means the main component of the rubber-like polymer contained in the pressure-sensitive adhesive.
  • the rubber-like polymer refers to a polymer that exhibits rubber elasticity in a temperature range near room temperature.
  • the glass transition temperature (Tg) of the base polymer is ⁇ 40 ° C. or lower.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the base polymer is preferably ⁇ 43 ° C. or lower, more preferably ⁇ 45 ° C. or lower.
  • the Tg of the base polymer can be adjusted by appropriately changing the monomer composition (that is, the type and amount ratio of the monomers used in the synthesis of the polymer).
  • the lower limit of the glass transition temperature (Tg) of the base polymer is not particularly limited, but from the viewpoint of ease of processing, it is preferably ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher.
  • the Tg of the base polymer means a Tg obtained by the Fox formula based on the composition of the monomer component used for the synthesis of the polymer.
  • Tg is the glass transition temperature (unit: K) of the copolymer
  • Wi is the mass fraction of the monomer i in the copolymer (copolymerization ratio based on the mass)
  • Tgi is the monomer i. Represents the glass transition temperature (unit: K) of a homopolymer.
  • the glass transition temperature of the homopolymer used for calculating Tg the value described in publicly known materials shall be used.
  • the monomers listed below the following values are used as the glass transition temperature of the homopolymer of the monomer.
  • 2-Ethylhexyl acrylate-70 ° C Isononyl acrylate -60 ° C n-Butyl acrylate-55 ° C Ethyl acrylate-22 ° C Methyl acrylate 8 °C Methyl methacrylate 105 ° C 2-Hydroxyethyl acrylate -15 ° C 4-Hydroxybutyl acrylate-40 ° C Vinyl acetate 32 ° C Acrylic acid 106 °C Methacrylic acid 228 ° C
  • the type of base polymer is not particularly limited as long as the above glass transition temperature is satisfied, and those known in the field of adhesives can be used.
  • rubber-like polymers such as acrylic polymer, rubber polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, polyamide polymer, and fluorine polymer. It can be included as a polymer.
  • an acrylic polymer or a rubber polymer as a base polymer.
  • an acrylic polymer it is more preferable to use an acrylic polymer as a base polymer from the viewpoint of dispersibility of a black color material (particularly a black pigment) described later.
  • the pressure-sensitive adhesive composition containing an acrylic polymer as a base polymer will be mainly described, but it is not intended to limit the pressure-sensitive adhesive composition in the present embodiment to one composed of an acrylic polymer.
  • the "acrylic polymer” refers to a polymer containing a monomer unit derived from a monomer having at least one (meth) acryloyl group in one molecule as a monomer unit constituting the polymer.
  • a monomer having at least one (meth) acryloyl group in one molecule is also referred to as an “acrylic monomer”. Therefore, the acrylic polymer in this specification is defined as a polymer containing a monomer unit derived from an acrylic monomer.
  • a typical example of the acrylic polymer is an acrylic polymer in which the proportion of the acrylic monomer in the total monomer components used in the synthesis of the acrylic polymer is more than 50% by mass.
  • (meth) acryloyl means to comprehensively refer to acryloyl and methacryloyl.
  • (meth) acrylate means acrylate and methacrylate, and
  • (meth) acrylic means acrylic and methacrylic, respectively.
  • the acrylic polymer for example, a polymer of a monomer raw material containing an alkyl (meth) acrylate as a main monomer and further containing a submonomer having copolymerizability with the main monomer is preferable.
  • the main monomer means a component that occupies more than 50% by mass of the monomer composition in the above-mentioned monomer raw material.
  • alkyl (meth) acrylate for example, a compound represented by the following formula (1) can be preferably used.
  • CH 2 C (R 1 ) COOR 2 (1)
  • R 1 in the above formula (1) is a hydrogen atom or a methyl group.
  • R 2 is a chain alkyl group having 1 to 20 carbon atoms.
  • such a range of the number of carbon atoms may be expressed as "C 1-20".
  • alkyl (meth) acrylate in which R 2 is a chain alkyl group of C 1-14 (for example, C 2-10 , typically C 4-8 ) is used as the main monomer. It is appropriate to do.
  • a R 1 is a hydrogen atom an alkyl acrylate
  • R 2 is a linear alkyl group of C 4-8 (hereinafter, simply referred to as C 4-8 alkyl acrylates.)
  • C 4-8 alkyl acrylates To the main monomer Is preferable.
  • alkyl (meth) acrylate in which R 2 is a C 1-20 chain alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl.
  • alkyl (meth) acrylate can be used alone or in combination of two or more.
  • Preferred alkyl (meth) acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
  • the proportion of alkyl (meth) acrylate in the monomer components constituting the acrylic polymer is typically more than 50% by mass, for example, 70% by mass or more, 85% by mass or more, and 90% by mass. It may be mass% or more. Further, the ratio of alkyl (meth) acrylate to the monomer component is typically less than 100% by mass, and from the viewpoint of cohesive force and the like, it is usually appropriate to be 99.5% by mass or less, 98. It may be less than mass% or less than 97% by mass.
  • the monomer component contains 50% by mass or more of C 1-4 alkyl (meth) acrylate.
  • the ratio of C 1-4 alkyl (meth) acrylate in the monomer component may be 70% by mass or more, 85% by mass or more, or 90% by mass or more.
  • the ratio of C 1-4 alkyl (meth) acrylate to the monomer component is usually preferably 99.5% by mass or less, and may be 98% by mass or less. It may be less than 97% by mass.
  • the monomer component may contain 50% by mass or more of C2-4 alkyl acrylate, 70% by mass or more, 85% by mass or more, or 90% by mass or more.
  • C 2-4 alkyl acrylate examples include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, s-butyl acrylate and t-butyl acrylate.
  • the C 2-4 alkyl acrylate may be used alone or in combination of two or more. According to such an aspect, it is easy to realize an adhesive sheet having good adhesion to an adherend.
  • the monomer component may contain BA in an amount of more than 50% by mass, 70% by mass or more, 85% by mass or more, or 90% by mass or more.
  • BA C2-4 alkyl acrylate
  • Adhesive properties such as adhesive strength can be maintained satisfactorily while being dispersed.
  • the ratio of C 1-4 alkyl (meth) acrylate in the monomer component is usually preferably 99.5% by mass or less, and 98% by mass or less. It may be less than 97% by mass.
  • the monomer component may contain 50% by mass or more of C 5-20 alkyl (meth) acrylate, 70% by mass or more, 85% by mass or more, or 90% by mass or more. good.
  • C 5-20 alkyl (meth) acrylate C 6-14 alkyl (meth) acrylate is preferable. In one embodiment, C 6-10 alkyl acrylate or C 8-10 alkyl acrylate can be preferably employed.
  • the monomer component constituting the base polymer may contain a carboxy group-containing monomer.
  • the monomer component contains a carboxy group-containing monomer, it becomes easy to obtain a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting good durability against impact in the shearing direction.
  • it may be advantageous to improve the adhesion between the pressure-sensitive adhesive layer and the adherend.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, crotonic acid and isocrotonic acid; maleic acid, itaconic acid and citracon.
  • ethylenically unsaturated dicarboxylic acids such as acids and their anhydrides (maleic anhydride, itaconic anhydride, etc.); and the like. These can be used alone or in combination of two.
  • preferable carboxy group-containing monomers include acrylic acid (AA) and methacrylic acid (MAA). AA is particularly preferred.
  • the content of the carboxy group-containing monomer in the monomer component constituting the base polymer is not particularly limited.
  • it can be 0.2% by mass or more (typically 0.5% by mass or more) of the monomer component, usually 1% by mass or more, and even 2% by mass or more. It may be 3% by mass or more.
  • the content of the carboxy group-containing monomer can be 3.2% by mass or more of the monomer component, more preferably 3.5% by mass or more, still more preferably 4% by mass or more. It may be 4.5% by mass or more.
  • the upper limit of the content of the carboxy group-containing monomer is not particularly limited, and may be, for example, 15% by mass or less, 12% by mass or less, or 10% by mass or less.
  • the content of the carboxy group-containing monomer may be 7% by mass or less, less than 7% by mass, 6.8% by mass or less, or 6.0 of the monomer component. It may be mass% or less.
  • a submonomer having copolymerizability with the main monomer, alkyl (meth) acrylate, can be useful for introducing a cross-linking point into the acrylic polymer and enhancing the cohesive force of the acrylic polymer.
  • the submonomer for example, the following functional group-containing monomers (however, the above-mentioned carboxy group-containing monomer is not included) can be used alone or in combination of two or more.
  • Hydroxyl-containing monomers Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono (meth) acrylate.
  • Amide group-containing monomers For example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (Meta) acrylamide, N-butoxymethyl (meth) acrylamide.
  • Amino group-containing monomer For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
  • Monomer having an epoxy group For example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
  • Cyan group-containing monomer For example, acrylonitrile and methacrylonitrile.
  • Keto group-containing monomer For example, diacetone (meth) acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, vinyl ethyl ketone, allyl acetoacetate, vinyl acetoacetate.
  • Monomers having a nitrogen atom-containing ring for example, N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazin, N-vinyl. Pyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholin, N-vinylcaprolactam, N- (meth) acryloylmorpholin.
  • Alkoxysilyl group-containing monomers for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy.
  • 3- (meth) acryloxypropyltrimethoxysilane for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy.
  • Propylmethyldiethoxysilane for example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy.
  • the content of the functional group-containing monomer in the monomer component is not particularly limited. From the viewpoint of appropriately exerting the effect of using the functional group-containing monomer, the content of the functional group-containing monomer in the monomer component can be, for example, 0.1% by mass or more, and usually 0.5% by mass or more. It is appropriate to do so, and it may be 1% by mass or more.
  • the content of the functional group-containing monomer in the monomer component is 40% by mass or less. It is preferably 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the technique disclosed herein can be preferably carried out even in a mode in which the monomer component does not substantially contain a functional group-containing monomer.
  • the monomer component is substantially composed of only an alkyl (meth) acrylate and a carboxy group-containing monomer.
  • the fact that the monomer component does not substantially contain the functional group-containing monomer means that the functional group-containing monomer is not used at least intentionally. For example, it is permissible to unintentionally contain functional group-containing monomers of 0.05% by mass or less, or 0.01% by mass or less.
  • the acrylic polymer having such a monomer composition may be one in which a black color material (particularly, a black pigment) described later is easily dispersed.
  • the monomer component constituting the acrylic polymer may contain a copolymerization component other than the above-mentioned submonomer for the purpose of improving cohesive force and the like.
  • Examples of other copolymerization components include vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), vinyl toluene; cyclohexyl (cyclohexyl).
  • vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl laurate
  • aromatic vinyl compounds such as styrene, substituted styrene ( ⁇ -methylstyrene, etc.), vinyl toluene; cyclohexyl (cyclohexyl).
  • Cycloalkyl (meth) acrylates such as meta) acrylates, cyclopentyl (meth) acrylates, isobornyl (meth) acrylates; aryl (meth) acrylates (eg, phenyl (meth) acrylates), aryloxyalkyl (meth) acrylates (eg, phenoxyethyl (eg, phenoxyethyl) Aromatic ring-containing (meth) acrylates such as meth) acrylates) and arylalkyl (meth) acrylates (eg, benzyl (meth) acrylates); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl chloride, chloride.
  • Chlorine-containing monomer such as vinylidene; isocyanate group-containing monomer such as 2- (meth) acryloyloxyethyl isocyanate; alkoxy group-containing monomer such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; methyl vinyl ether, ethyl vinyl ether and the like Vinyl ether-based monomer; 2 or more (for example, 3 or more) polymerizable functional groups (for example, (meth) acryloyl group) in one molecule such as 1,6-hexanediol di (meth) acrylate and trimethylpropantri (meth) acrylate. ), And the like.
  • the amount of the other copolymerization component may be appropriately selected depending on the purpose and application, and is not particularly limited, and is usually preferably 0.05% by mass or more from the viewpoint of appropriately exerting the effect of use. It may be 0.5% by mass or more.
  • the content of other copolymerization components in the monomer component is usually preferably 20% by mass or less, and may be 10% by mass or less, and 5% by mass. It may be less than or equal to%. In the present embodiment, it can also be preferably carried out in an embodiment in which the monomer component does not substantially contain other copolymerization components.
  • the fact that the monomer component does not substantially contain other copolymerization component means that the other copolymerization component is not used at least intentionally, and the other copolymerization component is, for example, 0.01% by mass or less. , It can be tolerated to be included unintentionally.
  • the acrylic polymer having such a monomer composition may be one in which a black color material (particularly, a black pigment) described later is easily dispersed.
  • the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for the acrylic polymer, such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Can be adopted as appropriate.
  • a solution polymerization method can be preferably adopted.
  • the polymerization temperature at the time of solution polymerization can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator, etc., for example, 20 ° C. to 170 ° C., typically 40 ° C. to 140 ° C. Can be.
  • the solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents.
  • aromatic compounds such as toluene (typically aromatic hydrocarbons); acetate esters such as ethyl acetate; aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane; 1,2-dichloroethane and the like.
  • the initiator used for polymerization can be appropriately selected from conventionally known polymerization initiators according to the type of polymerization method.
  • one or more azo-based polymerization initiators such as 2,2'-azobisisobutyronitrile (AIBN) can be preferably used.
  • polymerization initiators include persulfates such as potassium persulfate; peroxide-based initiators such as benzoyl peroxide and hydrogen peroxide; substituted ethane-based initiators such as phenyl-substituted ethane; aromatic carbonyl compounds. ; Etc. can be mentioned.
  • polymerization initiator is a redox-based initiator that is a combination of a peroxide and a reducing agent.
  • a polymerization initiator can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be a normal amount, and is selected from, for example, 0.005 to 1 part by mass, typically 0.01 to 1 part by mass with respect to 100 parts by mass of the monomer component. can do.
  • a polymerization reaction solution in which an acrylic polymer is dissolved in an organic solvent can be obtained.
  • the pressure-sensitive adhesive composition in the present embodiment may contain the above-mentioned polymerization reaction solution or an acrylic polymer solution obtained by subjecting the reaction solution to an appropriate post-treatment.
  • acrylic polymer solution a solution prepared by preparing the polymerization reaction solution to an appropriate viscosity (concentration) can be used.
  • an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization, for example, emulsion polymerization, photopolymerization, bulk polymerization, etc., and dissolving the acrylic polymer in an organic solvent may be used. ..
  • Base polymer preferably a weight average molecular weight of the acrylic polymer in the technology disclosed herein (Mw) of, may be particularly limited without, for example, 10 ⁇ 10 4 ⁇ 500 ⁇ 10 4 range. From the viewpoint of adhesive performance, the Mw of the base polymer is in the range of 30 ⁇ 10 4 to 200 ⁇ 10 4 , more preferably 45 ⁇ 10 4 to 150 ⁇ 10 4 , typically 65 ⁇ 10 4 to 130 ⁇ 10 4 . It is preferable to be in.
  • Mw weight average molecular weight of the acrylic polymer in the technology disclosed herein
  • Mw means a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • a model name "HLC-8320GPC” column: TSKgelGMH-H (S), manufactured by Tosoh Corporation
  • the infrared light transmitting pressure-sensitive adhesive composition in the present embodiment contains a near-infrared light transmitting black color material. By containing such a black color material, it is possible to form a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet that block visible light and transmit infrared light.
  • the near-infrared light-transmitting black color material may be a near-infrared light-transmitting black dye or a near-infrared light-transmitting black pigment.
  • a pressure-sensitive adhesive layer and a pressure-sensitive adhesive sheet having a uniform or almost uniform coloring concentration can be formed. It is preferable in that respect. It is also preferable in that it is excellent in transparency and haze.
  • the type of the black color material used in the present embodiment is selected so as to block visible light and transmit infrared light in the pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive composition of the present embodiment. Will be done.
  • the near-infrared light transmitting black color material may be not only a color material that exhibits black color by itself (a black color material in a narrow sense) but also a mixture that exhibits black color by mixing two or more types.
  • the mixture may be a mixture of a black color material in a narrow sense and a color material of another color.
  • the blending amount of the near-infrared light transmitting black color material in the pressure-sensitive adhesive composition of the present embodiment is set so as to form a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that block visible light and transmit infrared light.
  • NS Usually, it is suitable to be 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more.
  • the upper limit of the blending amount of the near-infrared light transmitting black coloring material is 20 with respect to 100 parts by mass of the base polymer.
  • the content is preferably parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less.
  • the dyes constituting the near-infrared light-transmitting black dye include natural dyes and synthetic dyes (for example, monoazo dyes, disazo dyes, metal complex salt dyes, acidic dyes, and reactions. Any form of dye (dye, direct dye, disperse dye, cationic dye, etc.) can be used.
  • the dye may be a water-soluble dye or an oil-soluble dye, and may be appropriately selected depending on the pressure-sensitive adhesive composition to be colored.
  • an oil-soluble dye may be used, or a water-containing pressure-sensitive adhesive containing a polymer obtained by emulsion polymerization.
  • a water-soluble dye may be used.
  • a solvent-type pressure-sensitive adhesive composition is preferably used as the pressure-sensitive adhesive composition in the present embodiment, an oil-soluble dye that is soluble in a solvent or a monomer is preferable as the dye constituting the black dye.
  • oil-soluble dyes examples include oil black, varifast black (black), oil yellow, varifast yellow, nickel titanium yellow (yellow), oil red, varifast red, congo red (red), and malakite green (blue-green).
  • Etc. can be mentioned. It is preferable to disperse these in a solvent, a monomer, or the like and use them as a coloring liquid.
  • Examples of the dyes constituting the black dye include the following azo-based, anthraquinone-based, perylene-based, perylene-based, methine-based, quinoline-based, and azine-based dyes.
  • azo dyes examples include C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 16, C.I. I. Solvent Yellow 21, C.I. I. Solvent Yellow 61, C.I. I. Solvent Yellow 81, C.I. I. Solvent Red 1, C.I. I. Solvent Red 2, C.I. I. Solvent Red 8, C.I. I. Solvent Red 19, C.I. I. Solvent Red 23, C.I. I. Solvent Red 24, C.I. I. Solvent Red 27, C.I. I. Solvent Red 31, C.I. I. Solvent Red 83, C.I. I. Solvent Red 84, C.I. I. Solvent Red 121, C.I. I.
  • Solvent Red 132 C.I. I. Solvent Violet 21, C.I. I. Solvent Black 3, C.I. I. Solvent Black 4, C.I. I. Solvent Black 21, C.I. I. Solvent Black 23, C.I. I. Solvent Black 27, C.I. I. Solvent Black 28, C.I. I. Solvent Black 31, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 9, C.I. I. Solvent Orange 37, C.I. I. Solvent Orange 40, C.I. I. Examples include Solvent Orange 45 and the like.
  • anthraquinone dyes examples include C.I. I. Solvent Red 52, C.I. I. Solvent Red 111, C.I. I. Solvent Red 149, C.I. I. Solvent Red 150, C.I. I. Solvent Red 151, C.I. I. Solvent Red 168, C.I. I. Solvent Red 191 and C.I. I. Solvent Red 207, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94, C.I.
  • perinone dyes examples include C.I. I. Solvent Orange 60, C.I. I. Solvent Orange 78, C.I. I. Solvent Orange 90, C.I. I. Solvent Violet 29, C.I. I. Solvent Red 135, C.I. I. Solvent Red 162, C.I. I. Examples include Solvent Orange 179 and the like.
  • perylene dye examples include C.I. I. Solvent Green 5, C.I. I. Solvent Orange 55, C.I. I. Bat Red 15, C.I. I. Bat orange 7 and the like can be mentioned.
  • methine dyes include C.I. I. Solvent Orange 80, C.I. I. Examples include Solvent Yellow 93 and the like.
  • quinoline dyes examples include C.I. I. Solvent Yellow 33, C.I. I. Solvent Yellow 98, C.I. I. Examples thereof include Solvent Yellow 157.
  • Examples of azine dyes include C.I. I. Solvent Black 5, C.I. I. Examples include Solvent Black 7.
  • the blending amount of the near-infrared light transmitting black dye in the pressure-sensitive adhesive composition of the present embodiment is set so that a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that block visible light and transmit infrared light are formed. Can be done, and is not particularly limited. Usually, it is suitable to be 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more.
  • the upper limit of the blending amount of the near-infrared light transmitting black dye is 20 parts by mass with respect to 100 parts by mass of the base polymer. It is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less.
  • the pigment constituting the near-infrared light-transmitting black pigment (hereinafter, may be simply referred to as a black pigment), either an organic pigment or an inorganic pigment can be used.
  • organic pigments examples include azo pigments such as azo lake pigments, insoluble mono azo pigments, insoluble disazo pigments, condensed azo pigments, and chelate azo pigments; Polycyclic pigments such as indolinone pigments and quinophthalone pigments; chelates such as basic dye type chelates and acidic dye type chelates; nitro pigments; nitroso pigments and the like. These can be used alone or in admixture of two or more.
  • azo pigments such as azo lake pigments, insoluble mono azo pigments, insoluble disazo pigments, condensed azo pigments, and chelate azo pigments
  • Polycyclic pigments such as indolinone pigments and quinophthalone pigments
  • chelates such as basic dye type chelates and acidic dye type chelates
  • nitro pigments nitroso pigments and the like.
  • inorganic pigments include titanium oxide, iron oxide, red iron oxide, chromium oxide, prussian blue, ultramarine blue, molybdenum red, iron black, and chrome yellow. These can be used alone or in admixture of two or more.
  • isoindolenone pigments quinacridone pigments, condensed azo pigments, phthalocyanine pigments, quinophthalone pigments, and anthraquinone pigments are preferably used in consideration of light resistance.
  • organic pigment examples include Pigment Yellow 1 (color index (hereinafter referred to as CI) 11680), Pigment Yellow 3 (CI 11710), and Pigment Yellow 14 (CI). 21095), Pigment Yellow 17 (CI21105), Pigment Yellow 42 (CI77492), Pigment Yellow 74 (CI11741), Pigment Yellow 83 (CI21108). , Pigment Yellow 93 (CI 20710), Pigment Yellow 98 (CI 11727), Pigment Yellow 109 (CI 56284), Pigment Yellow 110 (CI 56280), Pigment -Yellow 128 (CI 200737), Pigment Yellow 129 (CI 48042), Pigment Yellow 138 (CI 56300), Pigment Yellow 139 (CI 56298), Pigment Yellow.
  • CI color index
  • CI 11680 Pigment Yellow 3
  • Pigment Yellow 14 21095
  • Pigment Yellow 17 CI21105
  • Pigment Yellow 42 CI77492
  • Pigment Yellow 74 CI11741
  • Pigment Yellow 83 CI21108
  • Pigment Orange 71 (CI 561200), Pigment Red 5 (CI 12490), Pigment Red 8 (CI 12335), Pigment Red 17 (CI 12390) , Pigment Red 22 (CI 12315), Pigment Red 48: 2 (CI 15865: 2), Pigment Red 112 (CI 12370), Pigment Red 122 (CI 12370). 73915), Pigment Red 170 (CI12475), Pigment Red 176 (CI12515), Pigment Red 177 (CI65300), Pigment Red 178 (CI71). 155), Pigment Red 179 (C.I. I.
  • Pigment Red 185 (CI 12516), Pigment Red 202 (CI 73907), Pigment Red 208 (CI 12514), Pigment Red 254 (CI 56110).
  • Pigment Red 255 (CI 561050), Pigment Red 264, Pigment Red 272 (CI 561150), Pigment Violet 19 (CI 73900), Pigment Violet 23 (CI) .51319)
  • Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Blue 15: 4 (CI 74160), Pigment Blue 60 (CI 69800), Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265) and the like, and one kind or a mixture of two or more kinds is preferable.
  • the inorganic pigments include Pigment Yellow 42 (CI 77492), Pigment White 6 (CI 77891), Pigment Blue 27 (CI 77510), and Pigment Blue 29 (CI) CI 77007), Pigment Black 7 (CI 77266) and the like, and one kind or a mixture of two or more kinds is preferable.
  • Pigment Yellow 74 (CI 11741), Pigment Yellow 109 (CI 56284), Pigment Yellow 110 (CI 56280), Pigment Yellow 128 (CI 200737), Pigment Yellow 138 (CI 56300), Pigment Yellow 150 (CI 12764), Pigment Yellow 155 (CI 200310), Pigment Yellow 180 (C) I. 21290), Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265), Pigment Red 122 (CI 73915), Pigment Red 177 (CI) .65300), Pigment Red 202 (CI 73907), Pigment Red 254 (CI 56110), Pigment Violet 19 (CI 73900), Pigment Violet 23 (CI 51319).
  • Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Blue 15: 4 (CI 74160), Pigment Blue 15: 6.
  • Pigment Blue 60 (CI 69800), Pigment Black 7 (CI 77266) and the like are preferred.
  • the shape of the pigment is not particularly limited, and may be, for example, powdery, granular, wet cake, or slurry.
  • the group consisting of Pigment Red 177 (CI 65300), Pigment Red 254 (CI 56110), and Pigment Yellow 150 (CI 12764) is particularly used as a red pigment.
  • One or more pigments selected from the above can be preferably used.
  • a combination of 56110) and Pigment Yellow 150 (CI12764) can be preferably used.
  • the contrast ratio which is one of the color performances, can be further improved.
  • the mixing ratio of Pigment Yellow 150 is preferably in the range of 5 to 40% by mass in the pigment content because it is important to match the desired chromaticity.
  • the green inks include Pigment Green 7 (CI 74260), Pigment Green 36 (CI 74265), Pigment Yellow 138 (CI 56300), and Pigment Yellow 150 (C.I. 56300).
  • One or more pigments selected from the group consisting of CI 12764) can be preferably used.
  • pigments of Pigment Blue 15: 6 (CI 74160) and / or Pigment Violet 23 (CI 51319) can be preferably used.
  • the blending amount of the near-infrared light transmitting black pigment in the pressure-sensitive adhesive composition of the present embodiment is set so that a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet that block visible light and transmit infrared light are formed. Can be done, and is not particularly limited.
  • 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more.
  • the upper limit of the blending amount of the near-infrared light transmitting black pigment is 20 parts by mass with respect to 100 parts by mass of the base polymer. It is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 6 parts by mass or less.
  • the average particle size of the near-infrared light transmitting black pigment can be set so that the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet are formed so as to block visible light and transmit infrared light.
  • the pressure-sensitive adhesive and the pressure-sensitive adhesive sheet are formed so as to block visible light and transmit infrared light.
  • the lower limit of the average particle size of the near-infrared light transmitting black pigment can be, for example, 10 nm or more, 50 nm or more, or 100 nm or more. It may be 150 nm or more.
  • the upper limit of the average particle size of the near-infrared light transmitting black pigment is, for example, 500 nm or less, 300 nm or less, 250 nm or less, or 200 nm or less. May be good.
  • the average particle size of the above-mentioned near-infrared light transmitting black pigment refers to a volume average particle size, and specifically, an integrated value 50 in a particle size distribution measured based on a particle size distribution measuring device based on a laser scattering / diffraction method.
  • particle size in% (50% volume-average particle size,. the following, sometimes abbreviated as D 50) means.
  • the measuring device for example, the product name “Microtrack MT3000II” manufactured by Microtrack Bell Co., Ltd. or an equivalent product thereof can be used.
  • the form of adding the near-infrared light transmitting black pigment to the pressure-sensitive adhesive composition is not particularly limited.
  • the near-infrared light-transmitting black pigment can be added to the pressure-sensitive adhesive composition in the form of a dispersion liquid in which the particles are dispersed in a dispersion medium.
  • the dispersion medium constituting the dispersion is not particularly limited, and water (ion exchange water, back-penetration water, distilled water, etc.) and various organic solvents (alcohols such as ethanol; ketones such as acetone; butyl cellosolve, propylene glycol monomethyl) are not particularly limited. Examples include ethers such as ether acetate; esters such as ethyl acetate; aromatic hydrocarbons such as toluene; mixed solvents thereof), and aqueous mixed solvents of water and the above organic solvent.
  • the dispersion liquid may contain a dispersant described later.
  • the pressure-sensitive adhesive composition contains a near-infrared light-transmitting black pigment, and may further contain a dispersant described later.
  • the pressure-sensitive adhesive composition of the present embodiment may contain a component that contributes to improving the dispersibility of the black color material, particularly the black pigment.
  • the dispersibility improving component may be, for example, a polymer, an oligomer, a liquid resin, a surfactant, or the like.
  • the dispersibility improving component is preferably dissolved in the pressure-sensitive adhesive composition.
  • the oligomer is, for example, one or a low molecular weight polymer of a monomer component containing two or more acrylic monomers as exemplified above (e.g., Mw of less than 10 ⁇ 10 4, preferably less than 5 ⁇ 10 4 It can be an acrylic oligomer).
  • the liquid resin is, for example, a tackifier resin having a softening point of 50 ° C. or lower, more preferably 40 ° C. or lower (typically, a rosin-based, terpene-based, hydrocarbon-based, or other tackifier resin, for example, a hydrogenated rosin methyl ester. Etc.).
  • dispersibility improving component it is possible to suppress the uneven dispersion of the black color material and, by extension, the color unevenness of the pressure-sensitive adhesive layer. Therefore, it is possible to form the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet having better appearance quality.
  • the content of the dispersibility improving component is not particularly limited, and from the viewpoint of suppressing the influence on the adhesive properties (for example, decrease in cohesiveness), it is usually appropriate and preferably 20% by mass or less of the entire adhesive layer. Is 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less.
  • the content of the dispersibility improving component can be, for example, 10 times or less, preferably 5 times or less, and more preferably 3 times or less the mass of the black color material.
  • the content thereof is usually 0.2% by mass or more, preferably 0.5% by mass or more, and more preferably 1 of the entire pressure-sensitive adhesive layer. It is appropriate to make it by mass% or more.
  • the content of the dispersibility improving component can be 0.2 times or more, preferably 0.5 times or more, more preferably 1 time or more the mass of the black color material.
  • the pressure-sensitive adhesive composition of the present embodiment may contain a pressure-imparting resin. Thereby, the peel strength of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive sheet can be increased.
  • tackifying resin examples include phenol-based tack-imparting resin, terpene-based tackifier resin, modified terpene-based tackifier resin, rosin-based tackifier resin, hydrocarbon-based tackifier resin, epoxy-based tackifier resin, polyamide-based tackifier resin, and the like.
  • One or more selected from various known pressure-sensitive adhesive resins such as an elastomer-based pressure-sensitive adhesive resin and a ketone-based pressure-sensitive adhesive resin can be used.
  • phenol-based tackifier resins examples include terpene phenol resins, hydrogenated terpene phenol resins, alkylphenol resins and rosinphenol resins.
  • the terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, and is a copolymer of terpenes and a phenol compound (terpene-phenol copolymer resin) and a homopolymer or copolymer of terpenes. Is a concept that includes both phenol-modified products (phenol-modified terpene resin).
  • terpenes constituting such a terpene phenol resin are monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-form, l-form, and d / l-form (dipentene)). Can be mentioned.
  • the hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure in which such a terpene phenol resin is hydrogenated. It is also called hydrogenated terpene phenol resin.
  • the alkylphenol resin is a resin (oil-based phenol resin) obtained from alkylphenol and formaldehyde.
  • alkylphenol resins include novolak type and resol type.
  • the rosin phenol resin is typically a phenolic product of rosins or the various rosin derivatives described above (including rosin esters, unsaturated fatty acid modified rosins and unsaturated fatty acid modified rosin esters).
  • the rosin phenol resin include a rosin phenol resin obtained by adding phenol to rosins or the above-mentioned various rosin derivatives with an acid catalyst and thermally polymerizing the resin.
  • terpene-based tackifier resins include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene, and dipentene. It may be a homopolymer of one kind of terpenes or a copolymer of two or more kinds of terpenes.
  • Examples of the homopolymer of one kind of terpenes include ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer and the like.
  • modified terpene resin examples include those modified from the above terpene resin. Specific examples thereof include styrene-modified terpene resin and hydrogenated terpene resin.
  • rosin-based tackifier resin here includes both rosins and rosin derivative resins.
  • rosins include unmodified rosins (raw rosins) such as gum rosins, wood rosins, and tall oil rosins; modified rosins obtained by modifying these unmodified rosins by hydrogenation, disproportionation, polymerization, etc. (hydrogenated rosins, non-modified rosins) Normalized rosin, polymerized rosin, other chemically modified rosins, etc.);
  • the rosin derivative resin is typically a derivative of rosins as described above.
  • the concept of a rosin-based resin as used herein includes derivatives of unmodified rosins and derivatives of modified rosins (including hydrogenated rosins, disproportionated rosins and polymerized rosins).
  • rosin esters such as unmodified rosin esters, which are esters of unmodified rosins and alcohols, and modified rosin esters, which are esters of modified rosins and alcohols; for example, unmodified rosins modified with unsaturated fatty acids.
  • Saturated fatty acid-modified rosins for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; for example, rosins or various rosin derivatives described above (rosin esters, unsaturated fatty acid-modified rosins and unsaturated fatty acids).
  • examples thereof include rosin alcohols obtained by reducing the carboxy group of fatty acid-modified rosin esters; for example, metal salts of rosins or various rosin derivatives described above.
  • rosin esters include methyl esters of unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, etc.), triethylene glycol esters, glycerin esters, pentaerythritol esters, and the like.
  • hydrocarbon-based tackifier resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (styrene-olefin copolymers, etc.) ), Various hydrocarbon-based resins such as aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, kumaron-based resins, and kumaron-inden-based resins.
  • the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving the cohesive force, in one embodiment, a tackifier resin having a softening point (softening temperature) of 80 ° C. or higher, preferably 100 ° C. or higher can be preferably adopted.
  • the total amount of the tackifier resin contained in the pressure-sensitive adhesive composition is 100% by mass, of which more than 50% by mass, more preferably more than 70% by mass, still more preferably more than 90% by mass is softened. It can be preferably carried out in the embodiment of a tackifier resin having dots.
  • a phenol-based tackifier resin (terpene phenol resin or the like) having such a softening point can be preferably used.
  • the tackifier resin may contain, for example, a terpene phenol resin having a softening point of 135 ° C. or higher or 140 ° C. or higher.
  • the upper limit of the softening point of the tackifying resin is not particularly limited. From the viewpoint of improving the adhesion to the adherend, in one embodiment, a tackifier resin having a softening point of 200 ° C. or lower, more preferably 180 ° C. or lower can be preferably used. In a preferred embodiment, the tackifier resin (typically a terpene phenolic resin) has a softening point of less than 130 ° C, for example 120 ° C or less.
  • the dispersibility of the black color material can be improved.
  • the softening point of the tackifier resin can be measured based on the softening point test method (ring ball method) specified in JIS K2207.
  • the tackifier resin contains one or more types of phenol-based tackifier resin (typically, a terpene phenol resin).
  • the technique disclosed herein can be preferably carried out, for example, in a manner in which the total amount of the tackifier resin is 100% by mass, of which 25% by mass or more, more preferably 30% by mass or more is a terpene phenol resin.
  • 50% by mass or more of the total amount of the tackifier resin may be a terpene phenol resin, 80% by mass or more may be a terpene phenol resin, and 90% by mass or more may be a terpene phenol resin. Further, 95 to 100% by mass, further 99 to 100% by mass, of the total amount of the tackifier resin may be terpenephenol resin, and substantially all of the tackifier resin may be terpenephenol resin.
  • the pressure-sensitive adhesive resin may include a pressure-sensitive adhesive resin having a hydroxyl value higher than 20 mgKOH / g.
  • a tackifier resin having a hydroxyl value of 30 mgKOH / g or more is preferable.
  • a tackifier resin having a hydroxyl value of 30 mgKOH / g or more may be referred to as a “high hydroxyl value resin”.
  • the tackifier resin containing such a high hydroxyl value resin, a pressure-sensitive adhesive layer having excellent adhesion to an adherend and high cohesive force can be obtained.
  • the tackifier resin may contain a high hydroxyl value resin having a hydroxyl value of 50 mgKOH / g or more, more preferably 70 mgKOH / g or more.
  • a value measured by the potentiometric titration method specified in JIS K0070: 1992 can be adopted.
  • the high hydroxyl value resin among the various tackifier resins described above, those having a hydroxyl value equal to or higher than a predetermined value can be used.
  • the high hydroxyl value resin one type can be used alone or two or more types can be used in combination.
  • a phenolic tackifier resin having a hydroxyl value of 30 mgKOH / g or more can be preferably adopted.
  • a terpene phenol resin having a hydroxyl value of at least 30 mgKOH / g is used as the tackifier resin.
  • the terpene phenol resin is convenient because the hydroxyl value can be arbitrarily controlled by the copolymerization ratio of phenol.
  • the upper limit of the hydroxyl value of the high hydroxyl value resin is not particularly limited. From the viewpoint of compatibility with the base polymer and the like, the hydroxyl value of the high hydroxyl value resin is usually 200 mgKOH / g or less, preferably 180 mgKOH / g or less, more preferably 160 mgKOH / g or less, still more preferably 140 mgKOH or less. It is less than / g.
  • the tackifier resin contains a high hydroxyl value resin having a hydroxyl value of 30 to 160 mgKOH / g (for example, a phenol-based tackifier resin, preferably a terpene phenol resin).
  • a high hydroxyl value resin having a hydroxyl value of 30 to 80 mgKOH / g can be preferably adopted, and a high hydroxyl value resin having a hydroxyl value of 30 to 65 mgKOH / g can be preferably adopted.
  • a high hydroxyl value resin having a hydroxyl value of 70 to 140 mgKOH / g can be preferably adopted.
  • the ratio of the high hydroxyl value resin (for example, terpene phenol resin) to the entire tackifier resin contained in the pressure-sensitive adhesive composition is, for example, 25% by mass or more. can do. It is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Further, substantially all of the tackifier resin may be a high hydroxyl value resin, for example, 95 to 100% by mass, and further 99 to 100% by mass may be a high hydroxyl value resin.
  • the amount of the pressure-sensitive adhesive resin used is not particularly limited, and can be appropriately set in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the base polymer, for example.
  • the amount of the tackifier resin used with respect to 100 parts by mass of the base polymer is usually 5 parts by mass or more, and 10 parts by mass. It is preferably 10 parts or more, and may be 15 parts by mass or more.
  • the amount of the tackifier resin used with respect to 100 parts by mass of the base polymer is usually 50 parts by mass or less, and may be 40 parts by mass or less. , 30 parts by mass or less may be used.
  • the pressure-sensitive adhesive composition of the present embodiment may contain a cross-linking agent, if necessary.
  • the type of the cross-linking agent is not particularly limited, and a conventionally known cross-linking agent can be appropriately selected and used.
  • cross-linking agents examples include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, peroxide-based cross-linking agents, urea-based cross-linking agents, and metal alkoxide-based cross-linking agents.
  • examples thereof include a cross-linking agent, a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, a hydrazine-based cross-linking agent, an amine-based cross-linking agent, and a silane coupling agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • an isocyanate-based cross-linking agent and at least one kind of cross-linking agent having a different type of cross-linking functional group from the isocyanate-based cross-linking agent are used in combination.
  • a cross-linking agent other than the isocyanate-based cross-linking agent that is, a cross-linking agent having a different type of cross-linking reactive group from the isocyanate-based cross-linking agent; hereinafter also referred to as "non-isocyanate-based cross-linking agent").
  • non-isocyanate-based cross-linking agent By using it in combination with an isocyanate-based cross-linking agent, it is possible to suitably achieve both high heat-resistant coagulation power and excellent metal corrosion prevention property in a configuration containing a rust preventive agent such as an azole-based rust preventive agent.
  • the above-mentioned cross-linking agent is subjected to a form after the cross-linking reaction, a form before the cross-linking reaction, a form in which the cross-linking reaction is partially carried out, an intermediate or complex form thereof, and the like. Can be contained in.
  • the cross-linking agent is typically contained in the pressure-sensitive adhesive composition exclusively in the form after the cross-linking reaction.
  • polyfunctional isocyanate (a compound having an average of two or more isocyanate groups per molecule, including one having an isocyanurate structure) can be preferably used.
  • the isocyanate-based cross-linking agent may be used alone or in combination of two or more.
  • polyfunctional isocyanates examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and the like.
  • aliphatic polyisocyanes include 1,2-ethylene diisocyanate; 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,4-tetramethylene diisocyanate and other tetramethylene diisocyanates; 1,2.
  • -Hexamethylene diisocyanate such as 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate;
  • Examples thereof include 2-methyl-1,5-pentanediisocyanate, 3-methyl-1,5-pentanediisocyanate and lysine diisocyanate.
  • alicyclic polyisocyanates include isophorone diisocyanates; 1,2-cyclohexyldiisocyanates, 1,3-cyclohexyldiisocyanates, cyclohexyldiisocyanates such as 1,4-cyclohexyldiisocyanates; 1,2-cyclopentyldiisocyanates, 1,3.
  • -Cyclopentyl diisocyanate such as cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.
  • aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate.
  • polyfunctional isocyanate As a preferable polyfunctional isocyanate, a polyfunctional isocyanate having an average of 3 or more isocyanate groups per molecule is exemplified.
  • trifunctional or higher functional isocyanates are bifunctional or trifunctional or higher functional isocyanate multimers (typically dimers or trimers), derivatives (eg, polyhydric alcohols and two or more molecules of polyfunctional isocyanates). It can be an addition reaction product), a polymer, or the like.
  • examples thereof include reaction products with methylene diisocyanate, polyfunctional isocyanates such as polymethylene polyphenyl isocyanate, polyether polyisocyanate, and polyester polyisocyanate.
  • the amount of the isocyanate-based cross-linking agent used is not particularly limited. For example, it can be 0.5 parts by mass or more with respect to 100 parts by mass of the base polymer.
  • the amount of the isocyanate-based cross-linking agent used with respect to 100 parts by mass of the base polymer can be, for example, 1.0 part by mass or more, preferably 1.5 parts by mass. As mentioned above, it may be more preferably 2.0 parts by mass or more, and further preferably 2.5 parts by mass or more.
  • the amount of the isocyanate-based cross-linking agent used is 10 parts by mass or less with respect to 100 parts by mass of the base polymer, and 8 parts by mass or less. It may be 5 parts by mass or less.
  • non-isocyanate-based cross-linking agent used in combination with the isocyanate-based cross-linking agent is not particularly limited, and can be appropriately selected and used from the above-mentioned cross-linking agents.
  • the non-isocyanate cross-linking agent may be used alone or in combination of two or more.
  • an epoxy-based cross-linking agent can be adopted as the non-isocyanate-based cross-linking agent.
  • the epoxy-based cross-linking agent a compound having two or more epoxy groups in one molecule can be used without particular limitation.
  • An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferable.
  • the epoxy-based cross-linking agent may be used alone or in combination of two or more.
  • epoxy-based cross-linking agent examples include, for example, N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidyl aminomethyl).
  • Cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether and the like can be mentioned.
  • epoxy-based cross-linking agents include Mitsubishi Gas Chemical Company's product name “TETRAD-C” and product name “TETRAD-X”, DIC Corporation's product name “Epicron CR-5L”, and Nagase ChemteX Corporation.
  • the product name "Denacol EX-512”, the product name "TEPIC-G” manufactured by Nissan Chemical Industries, Ltd., and the like can be mentioned.
  • the amount of epoxy cross-linking agent used is not particularly limited.
  • the amount of the epoxy-based cross-linking agent used can be, for example, more than 0 parts by mass and 1 part by mass or less, typically 0.001 to 0.5 parts by mass, with respect to 100 parts by mass of the base polymer.
  • the amount of the epoxy-based cross-linking agent used is 0.002 parts by mass or more with respect to 100 parts by mass of the base polymer, and 0.005 parts by mass. More than parts are preferable, and 0.008 parts by mass or more is more preferable.
  • the amount of the epoxy-based cross-linking agent used is 0.2 parts by mass or less with respect to 100 parts by mass of the base polymer, and 0.1 mass by mass.
  • the amount is preferably less than 0.05 parts by mass, more preferably less than 0.05 parts by mass, further preferably less than 0.03 parts by mass, and particularly preferably 0.025 parts by mass or less.
  • the relationship between the content of the isocyanate-based cross-linking agent and the content of the non-isocyanate-based cross-linking agent is not particularly limited.
  • the content of the non-isocyanate cross-linking agent can be, for example, 1/50 or less of the content of the isocyanate-based cross-linking agent.
  • the content of the non-isocyanate cross-linking agent is 1/75 or less of the content of the isocyanate-based cross-linking agent on a mass basis. It is preferably 1/100 or less, and more preferably 1/150 or less.
  • the content of the non-isocyanate-based cross-linking agent is usually set to the isocyanate-based cross-linking. It is appropriate that the content of the agent is 1/1000 or more, for example, 1/500 or more.
  • the total amount of cross-linking agent used is not particularly limited. For example, it can be 10 parts by mass or less with respect to 100 parts by mass of the base polymer (preferably an acrylic polymer), preferably in the range of 0.005 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass. You can choose from.
  • the pressure-sensitive adhesive composition may be used as a leveling agent, a cross-linking aid, a plasticizer, a softening agent, an antistatic agent, an antioxidant, an ultraviolet absorber, an antioxidant, a light stabilizer and the like, if necessary. It may contain various additives that are common in the field of agents.
  • the pressure-sensitive adhesive composition of the present embodiment may be a water-based pressure-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, a hot-melt type pressure-sensitive adhesive composition, or an active energy ray-curable pressure-sensitive adhesive composition.
  • the water-based pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which a pressure-sensitive adhesive (sticking agent layer-forming component) is contained in a solvent containing water as a main component (water-based solvent), and is typically water-dispersed.
  • a type pressure-sensitive adhesive composition (a composition in which at least a part of the pressure-sensitive adhesive is dispersed in water) and the like are included.
  • the solvent-type pressure-sensitive adhesive composition refers to a pressure-sensitive adhesive composition in which a pressure-sensitive adhesive is contained in an organic solvent.
  • a solvent-based pressure-sensitive adhesive composition can be preferably implemented from the viewpoint of pressure-sensitive adhesive properties and the like.
  • the infrared light transmitting pressure-sensitive adhesive layer of the present embodiment is formed by using the above-mentioned pressure-sensitive adhesive composition.
  • the forming method is not particularly limited, and a known method can be adopted, but it can be performed according to the method for producing an adhesive sheet described later.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer has a multi-layer structure of two or more layers, it can be produced by laminating the pressure-sensitive adhesive layers formed in advance. Alternatively, the pressure-sensitive adhesive composition may be applied onto the first pressure-sensitive adhesive layer formed in advance, and the pressure-sensitive adhesive composition may be cured to form a second pressure-sensitive adhesive layer.
  • the photo-curing pressure-sensitive adhesive layer is a part of the multi-layer structure. It may be a layer (for example, one layer) or all layers.
  • a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater is used. Can be carried out.
  • a direct method of directly applying the pressure-sensitive adhesive composition to the base material to form the pressure-sensitive adhesive layer may be used.
  • a transfer method may be used in which the pressure-sensitive adhesive layer formed on the peeled surface is transferred to the base material.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, 3 ⁇ m to 2000 ⁇ m. From the viewpoint of adhesion to the adherend such as step followability, in some embodiments, the thickness of the pressure-sensitive adhesive layer may be, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, preferably 20 ⁇ m or more, and more. It is preferably 30 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer may be 50 ⁇ m or more, more than 50 ⁇ m, 70 ⁇ m or more, 100 ⁇ m or more, or 120 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer may be, for example, 1000 ⁇ m or less, 700 ⁇ m or less, or 500 ⁇ m or less in some embodiments. , 300 ⁇ m or less, 200 ⁇ m or less, 170 ⁇ m or less.
  • the technique according to this aspect can also be preferably carried out in the form of a pressure-sensitive adhesive sheet described below in which the thickness of the pressure-sensitive adhesive layer is 130 ⁇ m or less, 90 ⁇ m or less, 60 ⁇ m or less, or 40 ⁇ m or less.
  • the thickness of the adhesive layer is from the adhesive surface attached to the adherend to the surface opposite to the adhesive surface. The thickness of.
  • the infrared light transmitting pressure-sensitive adhesive sheet according to the embodiment of the present invention includes the above-mentioned pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present embodiment may be a pressure-sensitive adhesive sheet with a base material having a pressure-sensitive adhesive layer on one side (FIG. 2) or both sides (FIG. 3) of the sheet-like base material (support), and the pressure-sensitive adhesive layer. May be a base material-less adhesive sheet (FIG. 1) such as a form held on a release sheet (12a, 12b).
  • an adhesive sheet here may include what is called an adhesive tape, an adhesive label, an adhesive film, or the like.
  • the pressure-sensitive adhesive layer is typically formed continuously, but is not limited to such a form.
  • the pressure-sensitive adhesive layer is formed in a regular or random pattern such as a dot shape or a stripe shape. It may be.
  • the adhesive sheet of the present embodiment may be in the form of a roll or in the form of a single leaf. Alternatively, it may be an adhesive sheet in a form further processed into various shapes.
  • the pressure-sensitive adhesive sheet of the present embodiment preferably has no base material and does not have a base material as shown in FIG.
  • the adhesive sheet has a step-following property, so that the adhesive sheet can be attached along the step and the waterproofness of the object can be improved.
  • the adhesive sheet of the present embodiment may include a supporting base material as shown in FIG.
  • the adhesive sheet can be accurately processed by punching or the like.
  • Such an adhesive sheet is preferable for applications where it is processed into a specific shape or narrowed and used.
  • the thickness of the supporting base material in the present embodiment is, for example, less than 75 ⁇ m.
  • the support base material having a limited thickness is preferably used in applications requiring thinning and weight reduction.
  • the thickness of the supporting base material is preferably 60 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably less than 50 ⁇ m, still more preferably 40 ⁇ m or less, still more preferably 30 ⁇ m or less, still more preferably less than 30 ⁇ m, in particular. It is preferably 25 ⁇ m or less.
  • the thickness of the supporting base material may be 20 ⁇ m or less, 12 ⁇ m or less, 7 ⁇ m or less, or 3 ⁇ m or less.
  • the lower limit of the thickness of the supporting base material is not particularly limited. From the viewpoint of handleability (handleability), processability, and the like of the pressure-sensitive adhesive sheet, the thickness of the supporting base material is usually 0.5 ⁇ m or more (for example, 1 ⁇ m or more).
  • the thickness of the supporting base material may be 3 ⁇ m or more. In another aspect, the thickness of the supporting substrate can be 8 ⁇ m or more, 13 ⁇ m or more, or 16 ⁇ m or more.
  • the structure and material of the supporting base material are not particularly limited, and are typically a film-like base material (also referred to as "base material film").
  • base film a base film containing a resin film can be preferably used.
  • the base film is typically an independently shape-maintainable (independent) member.
  • the base film in the present embodiment may be substantially composed of such a base film.
  • the base film may include an auxiliary layer in addition to the base film.
  • the auxiliary layer include a colored layer, a reflective layer, an undercoat layer, an antistatic layer and the like provided on the surface of the base film.
  • the resin film is a film containing a resin material as a main component (for example, a component contained in the resin film in an amount of more than 50% by mass).
  • resin films examples include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene / propylene copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like.
  • the resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film.
  • a polyester film is preferable from the viewpoint of handleability and processability, and a PET film is particularly preferable.
  • the "resin film” is typically a non-porous sheet, and is a concept that is distinguished from so-called non-woven fabrics and woven fabrics (in other words, a concept excluding non-woven fabrics and woven fabrics). be.
  • the base film (typically a resin film) can also contain the above black color material. Thereby, the light transmission property and the light blocking property of the base film can be adjusted.
  • the amount of the black color material used in the base film is not particularly limited, and can be appropriately adjusted so as to impart desired optical characteristics.
  • the dose of the black color material is usually preferably 0.1 to 30% by mass, for example 0.1 to 25% by mass, typically 0.1 to 20% by mass, based on the total mass of the base film. Can be%.
  • the base film may contain, if necessary, fillers (inorganic fillers, organic fillers, etc.), dispersants (surfactants, etc.), antioxidants, antioxidants, ultraviolet absorbers, antistatic agents, etc.
  • Various additives such as lubricants and plasticizers may be blended.
  • the blending ratio of the various additives is usually less than 30% by mass, less than 20% by mass, and typically less than 10% by mass.
  • the base film may have a single-layer structure, or may have a multi-layer structure of two layers, three layers or more.
  • the base film preferably has a single-layer structure.
  • At least one layer is a layer having a continuous structure of the above resin (for example, a polyester resin, typically a black colorant-containing resin).
  • the method for producing the base film is not particularly limited as long as a conventionally known method may be appropriately adopted.
  • conventionally known general film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calendar roll molding can be appropriately adopted.
  • the base film may be colored by a colored layer arranged on the surface of the base film (preferably a resin film).
  • the base film may or may not contain a colorant.
  • the colored layer may be arranged on one surface of the base film, or may be arranged on both surfaces. In the configuration in which the colored layers are arranged on both surfaces of the base film, the configurations of the colored layers may be the same or different.
  • Such a colored layer can typically be formed by applying a colored layer forming composition containing a colorant and a binder to a base film.
  • colorant conventionally known pigments and dyes can be used as well as the colorants that can be contained in the pressure-sensitive adhesive layer and the base film.
  • binder materials known in the field of paint or printing can be used without particular limitation.
  • materials known in the field of paint or printing can be used without particular limitation.
  • polyurethane, phenol resin, epoxy resin, urea melamine resin, polymethyl methacrylate and the like are exemplified.
  • the composition for forming a colored layer may be, for example, a solvent type, an ultraviolet curable type, a thermosetting type, or the like.
  • the colored layer can be formed by using the means conventionally used for forming the colored layer without particular limitation.
  • a method of forming a colored layer (printing layer) by printing such as gravure printing, flexographic printing, and offset printing can be preferably adopted.
  • the colored layer may have a single-layer structure in which the whole is composed of one layer, or may have a multi-layer structure including two layers, three layers or more sub-colored layers.
  • a colored layer having a multi-layer structure including two or more sub-colored layers can be formed, for example, by repeatedly applying (for example, printing) a composition for forming a colored layer.
  • the color and blending amount of the colorant contained in each sub-colored layer may be the same or different.
  • the colored layer for imparting light-shielding property it is particularly meaningful to have a multi-layer structure from the viewpoint of preventing the occurrence of pinholes and increasing the reliability of light leakage prevention.
  • the thickness of the entire colored layer is usually 1 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 7 ⁇ m, and can be, for example, 1 ⁇ m to 5 ⁇ m.
  • the thickness of each sub-colored layer is usually preferably 1 ⁇ m to 2 ⁇ m.
  • the surface of the base film may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of an undercoat agent.
  • Such a surface treatment can be a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer on the base film. Twice
  • the back surface of the base material film may be peeled off, if necessary.
  • a general silicone-based, long-chain alkyl-based, fluorine-based or other peeling treatment agent is applied in the form of a thin film typically of 0.01 ⁇ m to 1 ⁇ m (for example, 0.01 ⁇ m to 0.1 ⁇ m). It can be a process to do.
  • a release liner can be used when forming the pressure-sensitive adhesive layer, producing the pressure-sensitive adhesive sheet, storing the pressure-sensitive adhesive sheet before use, distributing it, processing the shape, and the like.
  • the release liner is not particularly limited, and for example, a release liner having a release treatment layer on the surface of a liner base material such as a resin film or paper, a fluoropolymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, etc.)
  • a release liner or the like made of a low adhesive material can be used.
  • the peeling treatment layer may be formed by surface-treating the liner base material with a peeling treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • a peeling treatment agent such as silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide.
  • the infrared light transmitting adhesive sheet of the present embodiment may further include an antireflection layer.
  • the antireflection layer refers to a layer that exhibits antireflection (antireflection function) by canceling the reversed phases of incident light and reflected light with each other by utilizing, for example, the interference effect of light, and transmits infrared light. It has a function of suppressing the reflection of light incident from the antireflection layer side of the adhesive sheet and improving the display quality of the display portion of the optical product.
  • the antireflection layer may be provided, for example, on the surface of the base material opposite to the pressure-sensitive adhesive layer provided on the base material (adhesive layer-base material-antireflection layer), or the adhesive layer may be adhered. It may be provided directly on the surface (adhesive layer-antireflection layer-base material, antireflection layer-adhesive layer-base material), or may not have a base material (adhesive layer-antireflection layer). ), The mode of lamination is not particularly limited.
  • the antireflection layer a known or conventional antireflection layer by a wet or dry coating can be applied, and the antireflection layer is not particularly limited.
  • the method of forming (depositing) the antireflection layer known and commonly used methods can be applied and are not particularly limited.
  • the antireflection layer basically has a refractive index smaller than the refractive index of the transparent base material (in the case of having an anchor coat layer or a hard coat layer, the refractive index of the transparent base material including these layers).
  • a layer of a transparent compound (preferably a metal oxide) having a layer and a layer of a compound (preferably a metal oxide) having a refractive index larger than the refractive index of the transparent substrate have an overall reflectance close to the minimum. It is composed of an optical film thickness (product of refractive index n and absolute thickness d) designed to be a value.
  • the structure of the antireflection layer varies depending on the purpose of use, cost, film forming method, etc., and is not particularly limited, and may be a single layer structure or a multi-layer (multilayer) structure. Among them, an antireflection layer composed of a plurality of layers (antireflection layer having a multi-layer structure) is particularly preferable because it has extremely low reflectance and high antireflection property (antireflection performance).
  • the antireflection film is formed by a vapor deposition method based on an electron beam heating method. More specifically, as the antireflection layer, for example, Japanese Patent Application Laid-Open No. 9-314038 (antireflection layer by wet coating) and Japanese Patent Application Laid-Open No. 2010-92003 (antireflection layer by dry coating). The disclosed antireflection layer and the like can be preferably used.
  • the total thickness of the pressure-sensitive adhesive sheet of the present embodiment is not particularly limited.
  • the total thickness of the adhesive sheet is usually 200 ⁇ m or less from the viewpoint of thinning.
  • the lower limit of the thickness of the pressure-sensitive adhesive sheet is not particularly limited and can be usually 1 ⁇ m or more, for example, 3 ⁇ m or more is suitable, preferably 6 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 15 ⁇ m or more. Is.
  • the total thickness of the pressure-sensitive adhesive sheet is 150 ⁇ m or less, more preferably 120 ⁇ m or less, still more preferably 70 ⁇ m or less, still more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less, still more preferably 35 ⁇ m or less, still more preferably. It is 25 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, still more preferably 7 ⁇ m or less.
  • the light-shielding effect according to the present embodiment can be preferably exhibited.
  • the ratio of the total thickness of the pressure-sensitive adhesive layer contained in the pressure-sensitive adhesive sheet to the total thickness of the pressure-sensitive adhesive sheet is not particularly limited.
  • the total thickness of the pressure-sensitive adhesive layer contained in the pressure-sensitive adhesive sheet is the total thickness of the pressure-sensitive adhesive layer provided on one surface of the base film and the pressure-sensitive adhesive layer provided on the other surface. say.
  • the thickness of the pressure-sensitive adhesive layer provided on the other surface is zero, and the thickness of the pressure-sensitive adhesive layer is zero.
  • the thickness of the provided pressure-sensitive adhesive layer matches the total thickness of the pressure-sensitive adhesive layer.
  • the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet is 40% or more, preferably 50% or more, more preferably more than 50%, and even more preferably. It can be carried out in an embodiment of 60% or more, particularly preferably 70% or more. With such a configuration, a higher level of impact resistance tends to be exhibited even in a narrow width as compared with the total thickness of the pressure-sensitive adhesive sheet.
  • the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet may be 75% or more, and further 80% or more.
  • the upper limit of the ratio of the total thickness of the pressure-sensitive adhesive layer to the total thickness of the pressure-sensitive adhesive sheet is not particularly limited, but usually 95% or less is appropriate, and 90% or less is preferable.
  • the pressure-sensitive adhesive sheet of the present embodiment is excellent in processing accuracy, it is suitable for applications that can be processed into a specific shape or narrowed and used, for example, for fixing a member in a portable electronic device.
  • the adhesive sheet may be required to have a light-shielding property.
  • some devices use infrared light, and it may be required to have a light-shielding property with respect to visible light and to selectively transmit infrared light.
  • the adhesive sheet of the present embodiment has wavelength selectivity of blocking visible light and transmitting infrared light, it may meet the needs of the above equipment.
  • Non-limiting examples of the above-mentioned portable electronic devices include mobile phones, smartphones, tablet computers, laptop computers, various wearable devices (for example, wristwear type worn on the wrist like a wristwatch, clips, straps, etc.).
  • Modular type to be attached to a part of eyewear type including glasses type (monocular type and binocular type, including head mount type), clothes type to be attached to shirts, socks, hats, etc. in the form of accessories, earphones (Earwear type, etc.
  • digital camera digital video camera
  • audio equipment portable music player, IC recorder, etc.
  • computer computer, etc.
  • portable game equipment electronic dictionary, electronic notebook, electronic book
  • in-vehicle Includes information devices, mobile radios, mobile TVs, mobile printers, mobile scanners, mobile modems, etc.
  • portable means that it is not enough to be portable, but to have a level of portability that an individual (standard adult) can carry relatively easily. It shall mean.
  • the adhesive sheet of the present embodiment can be preferably used for the purpose of fixing the pressure sensor and other members in the portable electronic device including the pressure sensor among such portable electronic devices.
  • the adhesive sheet comprises a device for indicating a position on the screen (typically a pen-type or mouse-type device) and a device for detecting the position, and a plate corresponding to the screen (typically). It is used to fix the pressure sensor and other members in an electronic device (typically a portable electronic device) that has a function that allows the absolute position to be specified on the touch panel). obtain.
  • the adhesive sheet of the present embodiment is arranged on the back surface of a display screen (display unit) of a touch panel display or the like in a portable electronic device, and is also suitable for an application of preventing reflection of light through the display screen.
  • the adhesive sheet of the present embodiment By arranging the adhesive sheet of the present embodiment on the back surface of the display screen (display unit), it is possible to prevent deterioration of the visibility of the display screen regardless of the usage mode of the portable electronic device.
  • the above-mentioned reflection may occur due to a metal member arranged on the back surface side of the display screen, but by using the adhesive sheet disclosed here for joining the metal member and the display portion, for example, the member And the addition of light-shielding property can be realized at the same time.
  • the material constituting the fixed object for example, the back surface member such as the electromagnetic wave shield or the reinforcing plate
  • the pressure sensitive sensor and the display unit is not particularly limited.
  • metal materials such as copper, silver, gold, iron, tin, palladium, aluminum, nickel, titanium, chromium, zinc, etc., or alloys containing two or more of these, for example, polyimide resins, acrylic resins, polys, etc.
  • Ethernitrile resin polyether sulfone resin
  • polyester resin polyethylene terephthalate resin, polyethylene naphthalate resin, etc.
  • polyvinyl chloride resin polyphenylene sulfide resin
  • polyether ether ketone resin polyamide resin
  • resin materials typically plastic materials
  • polyarylate resin polycarbonate resin
  • liquid crystal polymer liquid crystal polymer
  • inorganic materials such as alumina, zirconia, soda glass, quartz glass, and carbon. ..
  • metal materials such as copper, aluminum, and stainless steel
  • resin materials typically plastic materials
  • polyimide resins such as polyimide resins, aramid resins, and polyphenylene sulfide resins are widely used.
  • the object to be fixed may be in either a single-layer structure or a multi-layer structure, and the surface to which the adhesive sheet is attached (attachment surface) may be subjected to various surface treatments.
  • an example of the object to be fixed includes a back surface member having a thickness of 1 ⁇ m or more, 5 ⁇ m or more, 60 ⁇ m or more, or 120 ⁇ m or more. Further, examples of the object to be fixed include a back surface member having a thickness of 1500 ⁇ m or less or 800 ⁇ m or less.
  • the adhesive strength of the adhesive sheets of Examples and Comparative Examples was evaluated by performing a peeling adhesive strength test according to JIS Z 0237: 2009. That is, in an environment of 23 ° C. and 50% RH, a PET film having a thickness of 25 ⁇ m was attached to one of the adhesive surfaces of the double-sided adhesive sheet, lined with the adhesive, and cut to a width of 20 mm to prepare a measurement sample.
  • the other adhesive surface of the measurement sample was attached to a glass plate as an adherend by reciprocating a 2 kg roller once with an adhesive area of 20 mm in width and 100 mm in length.
  • the measurement sample attached to the adherend in this way was left at an ambient temperature of 40 ° C. for 3 days. Then, the force (N / 20 mm) when the measurement sample was peeled off from the adherend at a peeling angle of 180 ° and a tensile speed of 300 mm / min was measured.
  • Light transmittance The light transmittance of the adhesive sheets of Examples and Comparative Examples at wavelengths of 380 nm to 2500 nm was determined by measuring the absorption spectrum using a spectrophotometer (U-4100 type spectrophotometer, manufactured by Hitachi High-Technologies Corporation). .. Then, the average transmittance of visible light having a wavelength range of 400 to 700 nm and the average transmittance of infrared light having a wavelength range of 850 to 1500 nm were determined.
  • Example 1 (Preparation of adhesive composition) A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a reflux condenser and a dropping funnel is charged with 95 parts of n-butyl acrylate (BA) and 5 parts of acrylic acid (AA) as monomer components, and nitrogen gas is charged. Was stirred for 2 hours while introducing. After removing oxygen in the polymerization system in this way, 0.2 parts of 2,2'-azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and solution polymerization was carried out at 60 ° C. for 8 hours to carry out acrylic. A solution of the system polymer 1 was obtained. The Mw of this acrylic polymer 1 was about 600,000.
  • the glass transition temperature was ⁇ 49 ° C.
  • 2 parts of Oilblack HBB manufactured by Orient Chemical Industries Co., Ltd.
  • a black color material black dye
  • isociepoxy as a cross-linking agent
  • 0.075 parts of a cross-linking agent (trade name "Tetrad C", manufactured by Mitsubishi Gas Chemical Company, Ltd.) was added, and the mixture was stirred and mixed to prepare the pressure-sensitive adhesive composition of Example 1.
  • peeling liner As the peeling liner, two polyester peeling films (trade name "Diafoil MRF", thickness 38 ⁇ m, manufactured by Mitsubishi Polyester Co., Ltd.) having a peeled surface on one side were prepared.
  • the pressure-sensitive adhesive composition was applied to the peeled surface of these peeling liners so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes. In this way, an adhesive layer was formed on each of the peeling surfaces of the two peeling liners. In this way, a base material-less double-sided adhesive sheet having a thickness of 25 ⁇ m was obtained in which both sides were protected by the above two polyester release liners.
  • Example 2 In this example, this example is the same as the production of the pressure-sensitive adhesive sheet according to Example 1, except that 5 parts of an isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation) is used as the cross-linking agent. A substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • an isocyanate-based cross-linking agent trade name “Coronate L”, manufactured by Tosoh Corporation
  • Example 3 is the same as the production of the pressure-sensitive adhesive sheet according to Example 1, except that 10 parts of an isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation) is used as the cross-linking agent.
  • an isocyanate-based cross-linking agent trade name “Coronate L”, manufactured by Tosoh Corporation
  • a substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • Example 4 In this example, this example is the same as the production of the pressure-sensitive adhesive sheet according to Example 1, except that 20 parts of an isocyanate-based cross-linking agent (trade name "Coronate L", manufactured by Tosoh Corporation) is used as the cross-linking agent. A substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • an isocyanate-based cross-linking agent trade name "Coronate L", manufactured by Tosoh Corporation
  • the base material-less double-sided pressure-sensitive adhesive sheet according to this example is the same as the preparation of the pressure-sensitive adhesive sheet according to Example 2, except that the acrylic polymer 1 is the acrylic polymer 2 produced below.
  • the acrylic polymer 1 is the acrylic polymer 2 produced below.
  • [Acrylic polymer 2] A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a reflux condenser and a dropping funnel is charged with 67 parts of n-butyl acrylate (BA) and 33 parts of methyl methacrylate (MMA) as monomer components, and nitrogen gas is charged. Was stirred for 2 hours while introducing.
  • BA n-butyl acrylate
  • MMA methyl methacrylate
  • this example is the same as the production of the pressure-sensitive adhesive sheet according to Comparative Example 1, except that 10 parts of an isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation) was used as the cross-linking agent.
  • an isocyanate-based cross-linking agent trade name “Coronate L”, manufactured by Tosoh Corporation
  • a substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • this example is the same as the production of the pressure-sensitive adhesive sheet according to Comparative Example 1, except that 20 parts of an isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation) was used as the cross-linking agent.
  • an isocyanate-based cross-linking agent trade name “Coronate L”, manufactured by Tosoh Corporation
  • a substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • this example is the same as the production of the pressure-sensitive adhesive sheet according to Comparative Example 1, except that 30 parts of an isocyanate-based cross-linking agent (trade name “Coronate L”, manufactured by Tosoh Corporation) was used as the cross-linking agent.
  • an isocyanate-based cross-linking agent trade name “Coronate L”, manufactured by Tosoh Corporation
  • a substrate-less double-sided pressure-sensitive adhesive sheet according to the above was prepared.
  • Table 1 shows the component composition and various evaluation results for Examples 1 to 4 and Comparative Examples 1 to 4.
  • the pressure-sensitive adhesive sheets of Examples 1 to 4 have an average transmittance of 30% or less at a wavelength of 400 to 700 nm, a light transmittance of 80% or more at a wavelength of 850 to 1500 nm, and visible light. The effects of absorption and infrared light transmission were obtained.
  • the adhesive strength was 3N / 20 mm or more, which was a high value.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
PCT/JP2021/011524 2020-03-31 2021-03-19 赤外光透過粘着剤組成物 WO2021200293A1 (ja)

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