WO2023176023A1 - Feuille adhésive et procédé de fabrication d'une feuille adhésive - Google Patents

Feuille adhésive et procédé de fabrication d'une feuille adhésive Download PDF

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Publication number
WO2023176023A1
WO2023176023A1 PCT/JP2022/037117 JP2022037117W WO2023176023A1 WO 2023176023 A1 WO2023176023 A1 WO 2023176023A1 JP 2022037117 W JP2022037117 W JP 2022037117W WO 2023176023 A1 WO2023176023 A1 WO 2023176023A1
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WIPO (PCT)
Prior art keywords
adhesive sheet
adhesive
base material
pressure
sensitive adhesive
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PCT/JP2022/037117
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English (en)
Japanese (ja)
Inventor
翔 小鯖
隆行 荒井
幹広 樫尾
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リンテック株式会社
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Publication of WO2023176023A1 publication Critical patent/WO2023176023A1/fr

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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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]

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet and a method of manufacturing the pressure-sensitive adhesive sheet, and particularly relates to a recyclable pressure-sensitive adhesive sheet and a method of manufacturing the pressure-sensitive adhesive sheet.
  • Patent Document 1 describes a polymer material containing a crosslinked polymer crosslinked by interaction between a host group and a guest group, in which the host group removes one hydrogen atom or one hydroxyl group from cyclodextrin.
  • a polymer material has been proposed in which the crosslinked polymer contains a predetermined repeating structural unit.
  • Patent Document 2 discloses that a cyclodextrin monomer derivative is formed from a host group of a host group-containing monomer and a guest group of a guest group-containing monomer, and the host group-containing monomer has a (meth)acryloyl group; Inclusion complexes have been proposed in which the containing monomer is a predetermined monomer having a vinyl group.
  • Patent Documents 1 and 2 do not include any description regarding the adhesive of the adhesive sheet, and do not mention recyclability at all.
  • Adhesive sheets are used to fix various types of adherends, and the shape of the surface of the adherend varies depending on the adherend, such as flat surfaces and curved surfaces. Adhesive sheets are required to be able to fix well regardless of whether the surface is flat or curved.
  • the present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a pressure-sensitive adhesive sheet that can exhibit good fixation to an adherend and whose pressure-sensitive adhesive layer can be recycled, and a method for manufacturing the same. With the goal.
  • the present invention firstly provides an adhesive sheet comprising a base material made of a paper-based material and an adhesive layer laminated on at least one side of the base material, the adhesive sheet comprising: a base material made of a paper-based material;
  • a pressure-sensitive adhesive sheet characterized in that a pressure-sensitive adhesive constituting a layer contains a cyclodextrin derivative (Invention 1).
  • the adhesive constituting the adhesive layer contains a cyclodextrin derivative, it can exhibit good fixation to the adherend and the adhesive (layer) can be recycled. Become something.
  • the total light transmittance is 50% or less (invention 2).
  • the gel fraction of the adhesive is preferably 10% or less (Invention 3).
  • the total light rays obtained by subtracting the total light transmittance (%) of only the base material from the total light transmittance (%) of the laminate consisting of the base material and the adhesive layer. It is preferable that the amount of change in transmittance (points) is 0 points or more and 20 points or less (Invention 4).
  • the mass per unit area of the base material is N1 (mg), and the base material of the unit area is immersed for 72 hours in a solvent that dissolves the adhesive layer during recycling.
  • the holding force in accordance with JIS Z0237:2009 is determined by applying a pasting area to soda lime glass of 25 mm x 25 mm, a test temperature of 23°C, and a standing time of 24 hours.
  • the amount of deviation measured by applying a load of 40 g is preferably 20 mm or less (Invention 6).
  • the adhesive force to soda lime glass is preferably 1 N/25 mm or more (Invention 7).
  • the mass per unit area of the adhesive sheet is M1 (mg), and the unit area of the adhesive sheet is immersed for 72 hours in a solvent that dissolves the adhesive layer during recycling. , the mass of the adhesive sheet that is then dried is M2 (mg), the mass per unit area of the base material is N1 (mg), and the base material of the unit area is added to the solvent that dissolves the adhesive layer during recycling.
  • the adhesive mass reduction rate (%) calculated by the following formula (II) is 80% or more. is preferable (Invention 8).
  • Adhesive mass reduction rate (%) ⁇ 1-(N1-N2)/(M1-M2) ⁇ 100...(II)
  • the adhesive contains a polymer having a main chain obtained by copolymerizing an acrylic monomer and a cyclodextrin derivative having a polymerizable group (Invention 9). .
  • the polymerizable group of the cyclodextrin derivative is a group containing a polymerizable unsaturated double bond (invention 10).
  • the weight average molecular weight of the sol portion of the adhesive determined by gel permeation chromatography is 50,000 or more and 1,400,000 or less (Invention 11).
  • the present invention forms a coating film by applying an adhesive composition containing an acrylic monomer and a cyclodextrin derivative having a polymerizable group to at least one side of a base material made of a paper-based material.
  • an adhesive composition containing an acrylic monomer and a cyclodextrin derivative having a polymerizable group
  • a method for producing a pressure-sensitive adhesive sheet characterized in that the coating film is irradiated with active energy rays, and the acrylic monomer and the cyclodextrin derivative are copolymerized to form a pressure-sensitive adhesive layer.
  • Invention 12 ).
  • the pressure-sensitive adhesive sheet according to the present invention can exhibit good fixation to an adherend, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet can be recycled. Furthermore, according to the method for producing a pressure-sensitive adhesive sheet according to the present invention, a pressure-sensitive adhesive sheet can be produced that exhibits good fixability to an adherend and allows for recycling of the pressure-sensitive adhesive layer.
  • FIG. 1 is a cross-sectional view of a pressure-sensitive adhesive sheet according to an embodiment of the present invention.
  • An adhesive sheet according to an embodiment of the present invention includes a base material made of a paper-based material and an adhesive layer laminated on at least one side of the base material, wherein the adhesive constituting the adhesive layer is , containing cyclodextrin derivatives.
  • the adhesive constituting the adhesive layer contains a cyclodextrin derivative, so that the adhesive can be recycled. That is, by immersing the adhesive sheet according to this embodiment in a predetermined solvent, the adhesive dissolves in the solvent and falls off from the base material. The adhesive dissolved in the solvent can be reused by volatilizing the solvent. Moreover, when the base material is made of a material with low solubility in the above-mentioned solvent, the base material can also be reused.
  • the solvent for dissolving the adhesive (layer) during recycling is not particularly limited, but includes, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, methylene chloride, ethylene chloride, etc.
  • Halogenated hydrocarbons alcohols such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, esters such as ethyl acetate, butyl acetate, ethyl cellosolve Cellosolve-based solvents such as these are used.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a cyclodextrin derivative, it is possible to exhibit good fixability to an adherend. That is, the adhesive sheet according to the present embodiment exhibits good adhesion and holding power, and thus exhibits good lamination properties not only for flat surfaces but also for adherends having curved surfaces. I can do it.
  • the adhesive sheet according to the present embodiment can exhibit good fixation to the adherend and can also be recycled because the adhesive constituting the adhesive layer contains a cyclodextrin derivative. It becomes possible.
  • the adhesive sheet 1 includes a base material 11, an adhesive layer 12 laminated on one side of the base material 11, and an adhesive layer 12 on the opposite side of the base material 11. It is composed of a laminated release sheet 13.
  • the release sheet 13 is laminated on the adhesive layer 12 such that its release surface is in contact with the adhesive layer 12.
  • the release surface of the release sheet in this specification refers to the surface of the release sheet that has releasability, and includes both the surface that has been subjected to release treatment and the surface that exhibits releasability even without release treatment. .
  • the base material 11 in this embodiment is made of a paper-based material.
  • paper-based materials include high-quality paper, glassine paper, kraft paper, art paper, coated paper, and laminated paper. Among these, from the viewpoint of recyclability of the base material 11 itself, paper that does not use synthetic resin, such as wood-free paper and kraft paper, is preferable, and wood-free paper that has strength suitable for recycling is particularly preferable.
  • the mass per unit area of the base material 11 is N1 (mg), and the base material of the above unit area is soaked in a solvent (methyl ethyl ketone is used in the test example) that dissolves the adhesive layer during recycling for 72 hours.
  • N2 (mg) When the mass of the substrate soaked and then dried is N2 (mg), it is preferable that the following relational expression (I) is satisfied. 0 ⁇ (N1-N2)/N1 ⁇ 0.1...(I)
  • the value on the right side of the above relational expression (I) is preferably ⁇ 0.05, more preferably ⁇ 0.03, particularly preferably ⁇ 0.02, and furthermore ⁇ 0.01. It is preferable that
  • the thickness of the base material 11 is preferably 0.1 to 500 ⁇ m, more preferably 1 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and even more preferably 30 to 100 ⁇ m. Most preferably it is 50-80 ⁇ m. When the thickness of the base material 11 is within the above range, it becomes recyclable and has excellent handling properties.
  • the total light transmittance of the base material 11 is preferably 90% or less, more preferably 80% or less, and particularly 60% or less. is preferable, more preferably 40% or less, and most preferably 30% or less. This makes it possible to exhibit concealment properties, making it suitable for use in labels and the like that require concealment properties.
  • the lower limit of the total light transmittance may be 0%, but is usually preferably 5% or more, more preferably 10% or more, particularly preferably 15% or more. , more preferably 20% or more.
  • the total light transmittance (%) of the laminate consisting of the base material and the adhesive layer from the total light transmittance (%) of the laminate consisting of the base material and the adhesive layer, the total light transmittance of only the base material (the base material before laminating the adhesive layer) It is preferable that the total light transmittance change amount (points) after subtracting (%) is 0 points or more and 20 points or less. This allows the base material 11 to sufficiently exhibit its concealing properties, making it suitable for use in labels and the like that require concealing properties. Note that the total light transmittance in this specification is a value measured in accordance with JIS K7361-1:1997.
  • the amount of change in total light transmittance is more preferably 15 points or less, particularly preferably 7 points or less, and even more preferably 3 points or less.
  • the adhesive constituting the adhesive layer 12 contains a cyclodextrin derivative, and preferably contains a polymer having a cyclodextrin derivative as a constituent monomer.
  • the gel fraction of the adhesive is preferably 10% or less, more preferably 8% or less, particularly preferably 5% or less, and even more preferably 3% or less. . Due to the low gel fraction of the adhesive, when the adhesive sheet 1 is immersed in a solvent, the adhesive is easily eluted into the solvent, and the adhesive layer 12 is therefore easy to dissolve and fall off, making it easy to recycle. It becomes superior due to its characteristics.
  • the lower limit of the gel fraction is most preferably 0%, but in reality it is preferably 0.01% or more, more preferably 0.05% or more, particularly 0.1%. % or more, more preferably 0.2% or more. Note that the method for measuring the gel fraction in this specification is as shown in the test example described below.
  • the above-mentioned pressure-sensitive adhesive contains a polymer having a main chain obtained by copolymerizing an acrylic monomer and a cyclodextrin derivative having a polymerizable group. This makes it possible to exhibit the desired adhesive strength and holding power, and the adhesive eluted into the solvent during recycling can be easily reused, resulting in better recyclability of the adhesive.
  • the adhesive does not contain a guest molecule that can be included in the cyclodextrin derivative.
  • inclusion refers to a phenomenon in which a guest molecule is incorporated into a cavity of a host molecule (cyclodextrin derivative).
  • guest molecule refers to a molecule that can be included in a cyclodextrin derivative, and includes molecules that are not yet included.
  • Such guest molecules include n-butyl acrylate, styrene, octyl acrylate and dodecyl acrylate for ⁇ -cyclodextrin derivatives, and n-butyl acrylate, t-acrylate for ⁇ -cyclodextrin derivatives.
  • -butyl, styrene, adamantyl acrylate and isobornyl acrylate and for ⁇ -cyclodextrin derivatives, octyl acrylate and dodecyl acrylate.
  • the expression that the adhesive "does not contain guest molecules that can be included in a cyclodextrin derivative” means that the adhesive does not substantially contain any guest molecules that can be included in a cyclodextrin derivative.
  • the adhesive contains guest molecules in an amount of 1 mol or less, preferably 0.1 mol or less, particularly preferably 0.01 mol or less, and even more preferably 0.001 mol or less, per 100 mol of the total amount of the acrylic monomer. It is permitted to do so.
  • the monomers listed above may be used as acrylic monomers, but these monomers basically become polymers through polymerization and do not become guest molecules that can be included, but even after polymerization, a slight amount of Since some may remain, the above provisions are made.
  • the polymer having a main chain obtained by copolymerizing the above acrylic monomer and a cyclodextrin derivative having a polymerizable group preferably does not have a branched structure. As a result, the obtained adhesive does not become too dense, and the above-mentioned gel fraction is easily satisfied.
  • the adhesive layer is made of an adhesive composition (hereinafter referred to as "adhesive It may be referred to as "Composition P").
  • Adhesive It may be referred to as "Composition P”
  • a polymer having a main chain obtained by copolymerizing an acrylic monomer (A) and a cyclodextrin derivative (B) may be hereinafter referred to as "polymer Q”.
  • Acrylic monomer (A) is preferably a monofunctional acrylic monomer.
  • the polymer Q of the acrylic monomer (A) and the cyclodextrin derivative (B) can be made to have no branched structure, and the above-mentioned gel fraction can be easily satisfied.
  • acrylic monomer (A) in this embodiment examples include (meth)acrylic ester, (meth)acrylic acid, (meth)acrylamide, vinyl acetate, styrene, etc. Among them, (meth)acrylic ester is preferable.
  • the acrylic monomers (A) may be used alone or in combination of two or more.
  • (meth)acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • (Meth)acrylic acid esters include, for example, (meth)acrylic acid alkyl esters in which the alkyl group is linear or branched, (meth)acrylic acid esters having a cyclic structure such as an alicyclic structure, hydroxyl groups, etc. Examples include (meth)acrylic acid esters having a functional group. Among these, (meth)acrylic acid alkyl esters in which the alkyl group is linear or branched are preferred.
  • the above (meth)acrylic acid alkyl ester is preferably a (meth)acrylic acid alkyl ester in which the alkyl group has 1 to 20 carbon atoms.
  • Examples of (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-(meth)acrylate.
  • Examples include n-dodecyl, myristyl (meth)acrylate, palmityl (meth)acrylate, and stearyl (meth)acrylate.
  • (meth)acrylic acid esters in which the alkyl group has 1 to 8 carbon atoms from the viewpoint of good adhesiveness, such as methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. More preferred are n-butyl acid, 2-ethylhexyl (meth)acrylate, and the like. From the viewpoint of recyclability, methyl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc. are particularly preferred, and ethyl acrylate, n-butyl acrylate, etc. are more preferred.
  • ethyl acrylate and n-butyl acrylate in combination, and in that case, it is preferable to use them at a mass ratio of 0.01:0.99 to 0.99:0.01, and 1:99 to 99. :1 mass ratio is more preferable, particularly 5:95 to 95:5 mass ratio is preferred, and even more preferably 10:90 to 90:10 mass ratio, Most preferably, a weight ratio of 20:80 to 80:20 is used.
  • Cyclodextrin derivative (B) The cyclodextrin moiety of the cyclodextrin derivative (B) having a polymerizable group in this embodiment is preferably ⁇ -cyclodextrin, ⁇ -cyclodextrin or ⁇ -cyclodextrin, and in particular, from the viewpoint of solvent solubility, Preferably it is ⁇ -cyclodextrin or ⁇ -cyclodextrin.
  • the polymerizable group possessed by the cyclodextrin derivative (B) is not particularly limited as long as it can be polymerized with the acryloyl group of the acrylic monomer (A), but it may be a group containing a polymerizable unsaturated double bond. It is preferably an ethylenically unsaturated group, more preferably an ethylenically unsaturated group, specifically a (meth)acryloyl group, a vinyl group, an allyl group, etc., and particularly preferably a (meth)acryloyl group.
  • the cyclodextrin derivative (B) has one polymerizable group per cyclodextrin molecule.
  • the polymer Q of the acrylic monomer (A) and the cyclodextrin derivative (B) can be made to have no branched structure, and the above-mentioned gel fraction can be easily satisfied.
  • the content of the cyclodextrin derivative having two or more polymerizable groups per molecule in the adhesive composition P is preferably as small as possible. Specifically, it is preferably at most 0.1% by mass, particularly preferably at most 0.01% by mass, and even more preferably at most 0.001% by mass.
  • the cyclodextrin derivative (B) in this embodiment is preferably a compound represented by the following formula (1).
  • R 1 in the above formula (1) represents a hydrogen atom or a methyl group.
  • R 2 represents O, NH, a hydrocarbon containing O, a hydrocarbon containing NH, or a hydrocarbon containing O and NH.
  • .CD indicates ⁇ -cyclodextrin, ⁇ -cyclodextrin or ⁇ -cyclodextrin.
  • hydrocarbons containing NH examples include -CH 2 -NH-CH 2 -, -O-CH 2 -NH-CH 2 -, -CH 2 -NH-CH 2 -O-, -O -CH 2 -NH-CH 2 -O-, -CH 2 -O-CO-NH-CH 2 -O-, -CH 2 -O-CO-NH-C 2 H 4 -O-, and the like.
  • the content of the cyclodextrin derivative (B) in the adhesive composition P is preferably such that the molar ratio is 0.01 to 10, and 0.1 to 10 when the total amount of the acrylic monomer (A) is 100 mol. It is more preferably 7, particularly preferably 0.5 to 4, and even more preferably 0.8 to 2. When the content of the cyclodextrin derivative (B) is within the above range, it is possible to obtain better recyclability and good adhesiveness.
  • Photopolymerization initiator (C) When ultraviolet rays are used as active energy rays for copolymerizing the acrylic monomer (A) and the cyclodextrin derivative (B) having a polymerizable group, the adhesive composition P is further used to initiate photopolymerization. It is preferable to contain agent (C). By containing the photopolymerization initiator (C) in this way, the acrylic monomer (A) can be efficiently copolymerized without remaining in the adhesive, and the polymerization curing time and active energy rays can be reduced. The amount of irradiation can be reduced.
  • photopolymerization initiators (C) examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy -2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylamino Benzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-e
  • the content of the photopolymerization initiator (C) in the adhesive composition P has a molar ratio of 0.001 to 10 when the total amount of the acrylic monomer (A) and the cyclodextrin derivative (B) is 100 mol. It is preferably 0.01 to 1, more preferably 0.02 to 0.5, particularly preferably 0.05 to 0.3, and even more preferably 0.01 to 1. It is preferably 1 to 0.2. Thereby, the resulting adhesive layer easily satisfies the above-mentioned physical properties and exhibits good recyclability.
  • the adhesive composition P may optionally contain various additives commonly used in acrylic adhesives, such as silane coupling agents, rust preventives, ultraviolet absorbers, and antistatic agents. , a tackifier, an antioxidant, a light stabilizer, a softener, a refractive index modifier, a filler, etc. can be added.
  • Weight average molecular weight of the sol component The weight average molecular weight of the sol component of the above adhesive measured by gel permeation chromatography is preferably 1.4 million or less, and preferably 1.2 million or less. More preferably, it is particularly preferably 1,000,000 or less, further preferably 800,000 or less, and most preferably 600,000 or less. As a result, when the pressure-sensitive adhesive sheet is immersed in a solvent, the pressure-sensitive adhesive is easily eluted into the solvent, and the recyclability of the pressure-sensitive adhesive is improved. Further, the weight average molecular weight is preferably 50,000 or more, more preferably 100,000 or more, particularly preferably 150,000 or more, and even more preferably 200,000 or more. This makes it easier to reuse the adhesive eluted into the solvent. Note that a specific method for measuring the weight average molecular weight of the sol content is as shown in the test example described below.
  • the haze value of the adhesive layer 12 in the adhesive sheet 1 according to the present embodiment is preferably 5% or less, more preferably 3% or less, particularly 1 % or less, more preferably 0.5% or less.
  • the adhesive layer 12 has excellent transparency, which tends to make it easier to satisfy the preferable total light transmittance of the adhesive layer 12 and the adhesive sheet 1, and to easily satisfy the above-mentioned amount of change in total light transmittance.
  • the lower limit value of the haze value may be 0%, but from the viewpoint of making it easier to satisfy the amount of change in total light transmittance described above, it is preferably 0.01% or more, and preferably 0.1% or more. is more preferable, particularly preferably 0.2% or more, and even more preferably more than 0.2%. Note that a specific method for measuring the haze value is as shown in the test example described below.
  • Total light transmittance of adhesive layer The total light transmittance of the adhesive layer 12 in the adhesive sheet 1 according to the present embodiment is determined from the viewpoint of easily satisfying the value of the amount of change in total light transmittance described above. It is preferably 40 to 100%, more preferably 60 to 99%, particularly preferably 80 to 96%, and even more preferably 90 to 94%.
  • the thickness of the adhesive layer 12 in the adhesive sheet 1 according to the present embodiment is preferably 1 ⁇ m or more, and preferably 3 ⁇ m or more. It is more preferably at least 5 ⁇ m, particularly preferably at least 5 ⁇ m, further preferably at least 10 ⁇ m, and most preferably at least 15 ⁇ m. Thereby, desired adhesive force and holding force can be exhibited. Further, the thickness of the adhesive layer 12 is preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less, particularly preferably 50 ⁇ m or less, further preferably 40 ⁇ m or less, and even more preferably 30 ⁇ m or less. Most preferably.
  • the adhesive layer 12 easily falls off from the base material 11, and the recyclability of the adhesive and the base material 11 becomes more excellent.
  • the adhesive sheet 1 can easily satisfy the above-mentioned total light transmittance change amount.
  • the adhesive layer 12 may be formed as a single layer, or may be formed by laminating multiple layers.
  • the release sheet 13 protects the adhesive layer 12 until the adhesive sheet 1 is used, and is peeled off when the adhesive sheet 1 (adhesive layer 12) is used. In the adhesive sheet 1 according to this embodiment, the release sheet 13 is not necessarily necessary.
  • Examples of the release sheet 13 include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and polybutylene terephthalate film. , polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film Plastic films such as the following are preferably used. Moreover, these crosslinked films are also used. Furthermore, a laminated film of these may be used.
  • the release surface of the release sheet 13 (particularly the surface in contact with the adhesive layer 12) is subjected to a release treatment.
  • the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
  • the thickness of the release sheet 13 is not particularly limited, but is usually about 20 to 200 ⁇ m.
  • an adhesive composition P is prepared. Specifically, an acrylic monomer (A), a cyclodextrin derivative (B), and if desired a photopolymerization initiator (C), additives, etc. are mixed. In addition, it is preferable that the adhesive composition P does not contain a solvent (water, organic solvent, etc.).
  • the adhesive composition P is applied to one side of the base material 11 to form a coating layer.
  • a method for applying the adhesive composition P for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, etc. can be used.
  • a release sheet 13 is laminated on the coating layer so that the release surface thereof is in contact with the coating layer. Then, the coating layer is irradiated with active energy rays to copolymerize the acrylic monomer (A) and the cyclodextrin derivative (B) to form an adhesive layer.
  • Active energy rays refer to electromagnetic waves or charged particle beams that have energy quanta, and specifically include ultraviolet rays and electron beams. Among active energy rays, ultraviolet rays are particularly preferred because they are easy to handle.
  • Irradiation of ultraviolet rays can be performed using a high-pressure mercury lamp, a Heraeus H lamp, a xenon lamp, etc., and the amount of irradiation of ultraviolet rays preferably has an illuminance of 50 to 1000 mW/ cm2 , and 100 to 500 mW/cm2. It is preferable that it is 2 . Further, the amount of light is preferably 50 to 10,000 mJ/cm 2 , more preferably 200 to 7,000 mJ/cm 2 , and particularly preferably 500 to 3,000 mJ/cm 2 .
  • the electron beam irradiation can be performed using an electron beam accelerator or the like, and the amount of electron beam irradiation is preferably about 10 to 1000 krad.
  • the active energy rays are ultraviolet rays
  • the adhesive composition P may be applied to the release surface of the release sheet 13, and then the base material 11 may be laminated on the coating layer.
  • Adhesive mass reduction rate In the adhesive sheet 1 according to the present embodiment (excluding the release sheet 13), the mass per unit area of the adhesive sheet 1 is M1 (mg), and the adhesive layer 12 is removed during recycling. A unit area of the adhesive sheet 1 is immersed in a solvent to be dissolved (methyl ethyl ketone is used in the test example) for 72 hours, and then the mass of the adhesive sheet 1 that is dried is defined as M2 (mg), and the mass of the adhesive sheet 1 per unit area of the base material 11 is When the mass is N1 (mg), the base material 11 of the above unit area is immersed for 72 hours in a solvent that dissolves the adhesive layer 12 during recycling, and then the mass of the base material 11 that is dried is N2 (mg).
  • the adhesive mass reduction rate (%) calculated by the following formula (II) is 80% or more.
  • the adhesive mass reduction rate is more preferably 85% or more, particularly preferably 90% or more, further preferably 95% or more, and preferably 99% or more. Most preferred. Note that the upper limit of the adhesive mass reduction rate is 100%.
  • the total light transmittance of the adhesive sheet 1 (excluding the release sheet 13) according to the present embodiment is preferably 50% or less, more preferably 45% or less, particularly 41% or less. % or less, more preferably 37% or less. This results in excellent hiding properties, making it suitable for use in labels and the like that require hiding properties.
  • the lower limit of the total light transmittance may be 0%, but is usually preferably 1% or more, more preferably 5% or more, and particularly preferably 10% or more. , more preferably 20% or more, most preferably 28% or more.
  • the adhesive sheet 1 according to the present embodiment has a holding power in accordance with JIS Z0237:2009 when the pasting area to soda lime glass is 25 mm x 25 mm, the temperature during the test is 23°C, and the standing time is 25 mm x 25 mm.
  • the amount of deviation measured under a load of 40 g for 24 hours is preferably 20 mm or less, more preferably 18 mm or less, particularly preferably 15 mm or less, and even more preferably 10 mm or less. is preferable, particularly preferably 5 mm or less, and most preferably 1 mm or less.
  • the adhesive sheet 1 exhibits better fixing properties to the adherend, and even when the adherend has a shape that is not flat, such as a curved surface, it can exhibit better bonding properties. can.
  • the lower limit of the amount of deviation is 0 mm.
  • the adhesive force of the adhesive sheet 1 according to the present embodiment to soda lime glass is preferably 1 N/25 mm or more, more preferably 3 N/25 mm or more, and particularly 5 N/25 mm or more. It is preferably 7 N/25 mm or more, and most preferably 10 N/25 mm or more.
  • the adhesive sheet 1 exhibits better fixing properties to the adherend, and even when the adherend has a shape that is not flat, such as a curved surface, it can exhibit better bonding properties. can.
  • the adhesive force is preferably 100 N/25 mm or less, more preferably 75 N/25 mm or less, particularly preferably 50 N/25 mm or less, and even more preferably 40 N/25 mm or less. . This makes it possible to obtain reworkability that allows the adhesive to be peeled off from the adherend and reattached to the adherend.
  • the adhesive strength in this specification basically refers to the adhesive strength measured by the 180 degree peeling method according to JIS Z0237:2009, but the measurement sample was 25 mm wide and 100 mm long. Affix it to the adherend, apply pressure at 0.5 MPa and 50°C for 20 minutes, leave it for 24 hours under normal pressure, 23°C, and 50% RH, and then measure at a peeling rate of 300 mm/min. shall be taken as a thing.
  • the adhesive sheet 1 according to the present embodiment has a size of 15 mm width and 50 mm length, and the adhesive sheet 1 is applied so as to be wrapped around an adherend having a curved surface (for example, a glass screw bottle with a diameter of 35 mm). After applying the layer and allowing it to stand for 24 hours in an environment of 23°C and 50% RH, when the adhesive sheet 1 was visually checked to see if it had lifted from the adherend, it was found that there was no lifting at the longitudinal ends. It is preferably less than 5 mm, particularly preferably the lift at the longitudinal end is 3 mm or less, and even more preferably 1 mm or less at the longitudinal end.
  • the adhesive sheet 1 has a size of 15 mm width and 50 mm length, and is attached so as to wrap the adhesive layer around an adherend having a curved surface (for example, a glass screw bottle with a diameter of 35 mm). °C and 50% RH for 24 hours, and when the peeling of the adhesive sheet 1 from the adherend was visually confirmed, it was found that both the longitudinal end and the transverse end It is preferable that substantially no peeling is observed, and it is particularly preferable that no peeling is observed at either the longitudinal ends or the transverse ends. As a result, the adhesive sheet 1 exhibits good fixing properties even to adherends having curved surfaces.
  • the adhesive sheet 1 exhibits the following properties when immersed in a solvent (such as methyl ethyl ketone) for 72 hours after the adhesive layer is attached to a soda lime glass plate (thickness: 1.1 mm). It is preferable that the pressure-sensitive adhesive sheet falls off from the soda lime glass plate, and the time until the pressure-sensitive adhesive sheet falls off is preferably within 72 hours, and particularly preferably within 24 hours. Thereby, the adhesive sheet 1 can be separated from the adherend in a short time, and efficient recyclability can be realized. Moreover, from the viewpoint of recyclability, it is preferable that substantially no adhesive layer 12 (adhesive) remains on the base material of the adhesive sheet 1 after falling off.
  • a solvent such as methyl ethyl ketone
  • the pressure-sensitive adhesive sheet according to this embodiment can be preferably used for applications that allow recycling.
  • Such uses include, but are not particularly limited to, labels (paper labels), fixing tapes (gum tape, etc.), process tapes (temporary fixing curing tape, etc.), and the like.
  • the objects to which labels are attached include, but are not particularly limited to, various containers such as glass bottles, PET bottles, and cans, and packaging materials such as wrapping paper and cardboard.
  • the release sheet 13 in the adhesive sheet 1 may be omitted.
  • Example 1 Preparation of coating liquid of adhesive composition n-butyl acrylate as the acrylic monomer (A), 6-acrylamide- ⁇ -cyclodextrin (B1) as the cyclodextrin derivative (B), and a photopolymerization initiator ( C) and 1-hydroxycyclohexylphenyl ketone were mixed at the molar ratio shown in Table 1 and sufficiently stirred to obtain an adhesive composition.
  • the molar ratios shown in Table 1 are the molar ratios for each acrylic monomer (A) when the total amount of the acrylic monomer (A) is 100 mol, and the cyclodextrin derivative (B), photopolymerization initiator Regarding (C), other components, and crosslinking agents, the molar ratio is based on the total amount of 100 mol of the acrylic monomer (A).
  • UV illuminance/light meter uses “UVPF-A1” manufactured by Eye Graphics.
  • the thickness of the adhesive layer is a value measured using a constant pressure thickness measuring device (manufactured by Techlock Co., Ltd., product name "PG-02") in accordance with JIS K7130 (the same applies hereinafter).
  • Examples 2-3, Comparative Examples 1-3 The type and amount of acrylic monomer (A), the type and amount of cyclodextrin derivative (B), the amount of photopolymerization initiator (C), and the thickness of the adhesive layer were changed as shown in Table 1.
  • a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except for the following.
  • Comparative Example 1 0.1 mol of "TETRAD C” manufactured by Mitsubishi Gas Chemical Co., Ltd. was blended as an epoxy crosslinking agent.
  • Comparative Example 2 1 mol of "EtAdA” (EtAD) manufactured by Osaka Organic Chemical Industry Co., Ltd. was blended.
  • the adhesive wrapped in the polyester mesh was immersed in ethyl acetate at room temperature (23°C) for 24 hours. Thereafter, the adhesive was taken out and air-dried for 24 hours at a temperature of 23°C and a relative humidity of 50%, and further dried in an oven at 80°C for 12 hours. After drying, the mass was weighed using a precision balance, and the mass of the adhesive alone was calculated by subtracting the mass of the mesh alone. Let the mass at this time be M2. Gel fraction (%) is expressed as (M2/M1) ⁇ 100. From this, the gel fraction of the adhesive was derived. The results are shown in Table 2.
  • the above weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured using gel permeation chromatography (GPC) under the following conditions (GPC measurement).
  • GPC measurement gel permeation chromatography
  • ⁇ Measurement conditions> ⁇ GPC measurement device: Tosoh Corporation, HLC-8020 ⁇ GPC column (passed in the following order): TSK guard column HXL-H manufactured by Tosoh Corporation TSK gel GMHXL (x2) TSK gel G2000HXL ⁇ Measurement solvent: Tetrahydrofuran ⁇ Measurement temperature: 40°C
  • the coated layer on the heavy release type release sheet obtained above and a light release type release sheet (manufactured by Lintec, product name "SP-PET381031") in which one side of the polyethylene terephthalate film was treated with a silicone release agent. were bonded together so that the release-treated surface of the easy-release release sheet was in contact with the coating layer.
  • active energy rays (ultraviolet light; UV) were irradiated through the light release type release sheet under the same conditions as in the Examples and Comparative Examples to harden the coating layer, and the adhesive was made to the same thickness as in the Examples and Comparative Examples. formed a layer.
  • the light release type release sheet was peeled off from the adhesive layer, the adhesive layer was bonded to glass, the heavy release type release sheet was then peeled off, and this was used as a sample for measurement. After background measurement was performed on the glass, the haze value of the adhesive layer was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH5000") in accordance with JIS K7136:2000. (%) was measured. The results are shown in Table 2.
  • Test Example 4 Measurement of total light transmittance
  • background measurement was performed using glass, and a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH7000") was used in accordance with JIS K7361-1:1997.
  • the total light transmittance (%) of the adhesive layer was measured. The results are shown in Table 2.
  • the substrates used in the Examples and Comparative Examples were measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH7000") in accordance with JIS K7361-1:1997.
  • the total light transmittance (%) of the base material was measured. The results are shown in Table 2.
  • the release sheet was peeled off from the adhesive sheets obtained in Examples and Comparative Examples, and the adhesive layer was bonded to glass, which was used as a sample for measurement. After background measurement was performed on the glass, the above measurement sample was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SH7000") in accordance with JIS K7361-1:1997. The total light transmittance (%) of the material + adhesive layer) was measured. The results are shown in Table 2.
  • the holding force of the adhesive sheet was measured according to JIS Z0237:2009 except for the operations shown below.
  • the adhesive sheets obtained in Examples and Comparative Examples were cut into pieces of 25 mm width and 125 mm length, and the release sheet was peeled off. Only the 25 mm x 25 mm exposed adhesive layer of the adhesive sheet was cut into pieces, and the other parts were covered with soda lime.
  • the adhesive sheet was attached to the soda lime glass so as not to touch the glass (the adhesive sheet was attached so that the non-attached part of the adhesive sheet protruded from the soda lime glass). Thereafter, the soda lime glass was placed perpendicular to the ground so that the adhesive sheet was suspended from the soda lime glass, and left at 23° C.
  • the adhesive sheets of Examples had excellent recyclability for both the base material and the adhesive layer. Moreover, the pressure-sensitive adhesive sheets of Examples were also excellent in curved surface bonding properties and hiding properties.
  • the adhesive sheet according to the present invention can be suitably used as a paper label that is desired to be recycled.
  • Adhesive sheet 11 Base material 12
  • Adhesive layer 13 Adhesive layer 13

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille adhésive (1) comprenant : un matériau de base (11) formé à partir d'un matériau à base de papier ; et une couche adhésive (12) contrecollée sur au moins une surface du matériau de base (11), l'adhésif constituant la couche adhésive (12) contenant un dérivé de cyclodextrine. Le facteur de transmission lumineuse total de la feuille adhésive (1) est de préférence de 50 % ou moins. De plus, la fraction gel de l'adhésif est de préférence de 10 % ou moins. En outre, la quantité de changements de facteur de transmission lumineuse total (points) obtenue par soustraction du facteur de transmission lumineuse total (%) seulement du matériau de base du facteur de transmission lumineuse total (%) d'un stratifié comprenant le matériau de base (11) et la couche adhésive (12), est de préférence de 0 point à 20 points, limites comprises. Grâce à la feuille adhésive (1), la pièce à coller peut présenter une bonne aptitude à la fixation, et la couche adhésive peut être recyclée.
PCT/JP2022/037117 2022-03-16 2022-10-04 Feuille adhésive et procédé de fabrication d'une feuille adhésive WO2023176023A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6253662A (ja) * 1985-08-31 1987-03-09 日東電工株式会社 粘着性ゲル組成物
JPH01153601A (ja) * 1987-12-11 1989-06-15 Unie Kogyo Kk 野菜、果実等の防黴、防菌、防虫用粘着テープ或いはシート
JPH09241598A (ja) * 1996-03-13 1997-09-16 Mitsubishi Paper Mills Ltd 包接型可塑剤、該包接型可塑剤を含有する粘着剤および粘着シート
WO2007097365A1 (fr) * 2006-02-23 2007-08-30 Lintec Corporation Composition adhesive sensible a la pression et feuille adhesive sensible a la pression l'utilisant
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2014162834A (ja) * 2013-02-25 2014-09-08 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2017014153A (ja) * 2015-07-01 2017-01-19 日本化薬株式会社 ペメトレキセドを含有する注射用溶液製剤

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6253662A (ja) * 1985-08-31 1987-03-09 日東電工株式会社 粘着性ゲル組成物
JPH01153601A (ja) * 1987-12-11 1989-06-15 Unie Kogyo Kk 野菜、果実等の防黴、防菌、防虫用粘着テープ或いはシート
JPH09241598A (ja) * 1996-03-13 1997-09-16 Mitsubishi Paper Mills Ltd 包接型可塑剤、該包接型可塑剤を含有する粘着剤および粘着シート
WO2007097365A1 (fr) * 2006-02-23 2007-08-30 Lintec Corporation Composition adhesive sensible a la pression et feuille adhesive sensible a la pression l'utilisant
JP2013209586A (ja) * 2012-03-30 2013-10-10 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2014162834A (ja) * 2013-02-25 2014-09-08 Lintec Corp 粘着性組成物、粘着剤および粘着シート
JP2017014153A (ja) * 2015-07-01 2017-01-19 日本化薬株式会社 ペメトレキセドを含有する注射用溶液製剤

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