WO2020170448A1 - 真贋判定方法および粘着シート - Google Patents
真贋判定方法および粘着シート Download PDFInfo
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- WO2020170448A1 WO2020170448A1 PCT/JP2019/006888 JP2019006888W WO2020170448A1 WO 2020170448 A1 WO2020170448 A1 WO 2020170448A1 JP 2019006888 W JP2019006888 W JP 2019006888W WO 2020170448 A1 WO2020170448 A1 WO 2020170448A1
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- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- base material
- release liner
- Prior art date
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2458/00—Labels used in chemical analysis of biological material
- G01N2458/15—Non-radioactive isotope labels, e.g. for detection by mass spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/44—Resins; Plastics; Rubber; Leather
- G01N33/442—Resins; Plastics
Definitions
- the present invention relates to an authenticity determination method and an adhesive sheet.
- counterfeit products are specified by utilizing component analysis such as IR (infrared absorption spectroscopy) and NMR (nuclear magnetic resonance) for authenticity determination.
- component analysis such as IR (infrared absorption spectroscopy) and NMR (nuclear magnetic resonance)
- IR infrared absorption spectroscopy
- NMR nuclear magnetic resonance
- adhesive materials such as adhesive sheets are often available only in the state in which they are installed in the product, unlike products in which the appearance, display, and product information can be used. The previous properties may not be evaluated. In such a case, it is not easy to determine whether or not the product is a patent infringing product and whether or not it is an in-house product, and it is unavoidable to rely on component analysis.
- identification of counterfeit products by component analysis requires specialized knowledge and analysis technology.
- an object of the present invention is to provide a method for determining authenticity of a product or a member.
- Another object of the present invention is to provide a pressure-sensitive adhesive sheet that can be suitably used in the above method.
- a method for determining the authenticity of a product or a component includes the step of measuring the concentration ratio of radioactive carbon 14 based on ASTM D6866 for one or more constituent elements of the obtained product or member to be judged.
- the one or more constituent elements of the genuine product or the genuine member, and the constituent elements corresponding to the constituent elements of the product or the member to be judged are resin containing radioactive carbon 14 at a predetermined concentration ratio. contains.
- the 14 C concentration ratio of the constituent elements of the product or member to be judged corresponds to the corresponding genuine product or genuine member (hereinafter also referred to as “genuine product”). It is possible to judge whether the object to be judged is a genuine product or not by comparing it with the 14 C concentration ratio of the constituent elements in ( 4 ). According to this method, quick and highly reliable determination can be performed.
- Patent Document 1 describes a method for discriminating glycol derived from biomass resources, its use for discriminating imitation products is not considered.
- the biomass carbon ratio in the constituent element of the determination target product or member is ⁇ 5% of the biomass carbon ratio in the genuine product or the constituent element of the authentic member. If it is within the range, it may be a method including a step of determining the product or member to be determined as authentic, and if outside the range of ⁇ 5%, determining the product or member to be determined as not authentic. .. According to this method, the authenticity can be determined with an accuracy of ⁇ 5% or less based on the biomass carbon as described above.
- the method disclosed herein preferably includes the step of obtaining the product or member to be judged from the market in which the genuine product or the product including the genuine member is distributed. According to the method disclosed herein, it is possible to quickly and accurately perform the authenticity determination by using the determination target object obtained from the market, and thus it is possible to efficiently identify the counterfeit product or trace the genuine product. ..
- the biomass carbon ratio of the constituent elements of the genuine product or genuine member is preferably 5% or more.
- highly reliable authenticity determination can be performed based on the measurement result of the biomass carbon ratio.
- the product or member is an adhesive sheet.
- the pressure-sensitive adhesive sheet comprises: (A) a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer; (B) a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer; A pressure-sensitive adhesive sheet with a release liner, which further comprises a release liner for protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer; and (C) a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer, and a release liner for further protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- the release liner-provided pressure-sensitive adhesive sheet comprising; In the pressure-sensitive adhesive sheet, at least one of the base material layer, the pressure-sensitive adhesive layer, and the release liner base material layer is a constituent element containing a resin containing radioactive carbon 14 at a predetermined concentration ratio.
- the determination target is a pressure-sensitive adhesive sheet
- the predetermined 14 The authenticity of the pressure-sensitive adhesive sheet can be efficiently determined by setting the C concentration ratio and measuring the 14 C concentration ratio of only this component.
- the base material layer may be formed using a biomass material so as to have a predetermined 14 C concentration ratio
- the pressure-sensitive adhesive layer may be formed only from a fossil resource-based material, or a predetermined 14 C concentration ratio using a biomass material.
- the pressure-sensitive adhesive sheet includes the pressure-sensitive adhesive layer, the base material layer, and the release liner base material layer as the constituent elements.
- the pressure-sensitive adhesive layer, the base material layer, and the release liner base material layer each contain a resin containing radioactive carbon 14 in the same or different concentration ratio. Confidence in authenticity judgment is achieved by using a resin containing 14 C at a predetermined concentration ratio (same concentration ratio or different concentration ratios) for all of the pressure-sensitive adhesive layer, base material layer and release liner constituting the pressure-sensitive adhesive sheet. The sex can be enhanced.
- the pressure-sensitive adhesive sheet includes a polyester resin film layer as the base material layer and/or the release liner base material layer.
- the polyester resin film layer is a constituent element containing radioactive carbon 14 in a predetermined concentration ratio.
- pressure-sensitive adhesives that may contain plant components such as natural rubber and rosin
- Patent Documents 2 and 3 since the practical use of pressure-sensitive adhesive sheets provided with a biomass carbon-containing polyester resin film has not been reported (for example, Patent Documents 2 and 3), it is included in the pressure-sensitive adhesive sheets.
- the polyester resin film used has a high probability of being able to determine authenticity based only on the presence or absence of biomass carbon, and is suitable for identifying counterfeit products by measuring 14 C concentration ratio.
- the polyester resin film has high heat resistance and rigidity, and is suitable for authenticity judgment in that it is incorporated into products and members, and that it is easy to collect the required amount in a state that can be analyzed even after use. ..
- the polyester resin film contained in the pressure-sensitive adhesive sheet unlike the pressure-sensitive adhesive that determines the pressure-sensitive adhesive properties, is used as a supporting substrate, release liner, etc., so even if it is replaced with a biomass material, it will affect the performance change as a pressure-sensitive adhesive sheet. There are few, if any. In the field of pressure-sensitive adhesive sheets, by using a polyester resin film containing 14 C at a predetermined concentration ratio, rapid and highly reliable authentication can be preferably performed.
- the pressure-sensitive adhesive sheet is a double-sided adhesive pressure-sensitive adhesive sheet, and is a fixing member for components constituting an electronic device.
- the pressure-sensitive adhesive sheet By taking out specific constituent elements from the pressure-sensitive adhesive sheet incorporated in the electronic device, it is possible to make a quick and highly reliable authenticity judgment from the 14 C concentration ratio measurement.
- Imitation sheets for fixing electronic device parts are imitated because they are available only in the form of being built into the product, are as thin as several tens of microns, and are often firmly adhered to the adherend. There is a high degree of difficulty in determining whether a product or the like.
- the advantage of applying the highly accurate authenticity determination method disclosed herein to a pressure-sensitive adhesive sheet used for such an application is great.
- a polyester resin film layer is preferably adopted as the above-mentioned constituent element.
- This pressure-sensitive adhesive sheet comprises: (A) a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer; (B) a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer; A pressure-sensitive adhesive sheet with a release liner, which further comprises a release liner for protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer; and (C) a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer, and a release liner for further protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- a release liner-attached pressure-sensitive adhesive sheet Further, at least one of the base material layer, the pressure-sensitive adhesive layer, and the release liner base material layer contains a resin containing radioactive carbon 14 at a predetermined concentration ratio.
- the pressure-sensitive adhesive sheet having the above structure is particularly suitable for authenticity determination disclosed herein, and can be preferably used in the above method.
- a release liner comprising (A) a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is disposed on at least one surface of a base material layer, and a release liner that further protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive sheet having any one of a pressure-sensitive adhesive sheet; and (B) a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, and a release liner having a release liner for protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- each of the base material layer, the pressure-sensitive adhesive layer, and the release liner base material layer contains a resin containing radioactive carbon 14.
- the pressure-sensitive adhesive sheet having the above structure can be preferably used for authenticity determination disclosed herein. By using the pressure-sensitive adhesive sheet, it is possible to further enhance the reliability of authenticity determination.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer (B) a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of a base material layer.
- C a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer, and release for further protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive sheet having a release liner which comprises a liner;
- This pressure-sensitive adhesive sheet includes a polyester resin film layer as the base material layer and/or the release liner base material layer.
- the biomass carbon ratio of the polyester resin film is 5% or more.
- the pressure-sensitive adhesive sheet having the above structure can be preferably used for authenticity determination disclosed herein.
- the authenticity determination method disclosed herein is a method of determining authenticity of a product or a member.
- FIG. 1 shows a flow chart of the authenticity determination method according to one embodiment.
- the authenticity determination method disclosed herein will be described in detail with reference to FIG.
- the object (product or member) of authenticity determination disclosed herein is obtained by an appropriate method (S10).
- the acquisition method is not particularly limited, and it can be obtained by, for example, purchasing a commercial product from a market in which genuine products and non-genuine products are distributed.
- a product incorporating the member can be obtained and disassembled to obtain the target member.
- the determination target disclosed herein may include a genuine product and a non-genuine product (which may be a counterfeit product). Usually, when they are available, it is difficult to judge the authenticity only from the appearance, display, and product information.
- the authenticity determination method disclosed herein can be preferably applied to such products and members (hereinafter also referred to as “products and the like”).
- ⁇ Products to be judged are not particularly limited.
- Various electrical products such as home electric appliances, electronic devices, electronic parts, precision equipment, interior and exterior materials for automobiles, furniture, clothing, decorations, sports equipment, medical parts, cookware, tableware, various containers, miscellaneous goods, musical instruments, building materials, etc.
- Products used in various fields and members thereof can be targeted for judgment.
- a product or the like is composed of one or more (for example, two or three or more) components.
- the product or the like comprises one or more components (resin part) made of a resin such as a synthetic resin.
- the type of resin (for example, synthetic resin) forming the resin portion is not particularly limited, and polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene naphthalate (PBN), polyethylene furanoate.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PBN polybutylene naphthalate
- Polyester resin such as (PEF) and polybutylene succinate (PBS); Polyolefin resin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-butene copolymer; polycarbonate (PC); urethane Resin; Polyether; Acrylic resin; Natural rubber, modified natural rubber, synthetic rubber (chloroprene rubber, styrene-butadiene rubber, nitrile rubber, etc.) rubber; vinyl chloride resin; vinylidene chloride resin; vinyl acetate resin; polyvinyl alcohol; polystyrene Polyacetal; Polyimide; Polyamide; Fluorine resin; Silicone resin; Phenolic resin; Melamine resin, urea resin; Epoxy resin; Polylactic acid; Cellophane; These may be used alone or in combination of two or more.
- PBS polybutylene succinate
- Polyolefin resin such as polyethylene (PE), polypropylene (PP), ethylene-propylene copo
- a typical example of a product or the like to be judged is a pressure sensitive adhesive sheet.
- the form of the pressure-sensitive adhesive sheet is not particularly limited, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer arranged on at least one surface of the base material layer can be used.
- the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer disposed on at least one surface of the base material layer, and a release liner that further protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- a release liner is mentioned as another example of the product or the like which is the object of judgment.
- the release liner can be a release liner typically used for protecting the adhesive surface of an adhesive sheet.
- the product or the like is a polyester resin-containing product or the like.
- Non-limiting examples include polyester resin film-containing products and members such as packaging films, various optical films, protective films and adhesive sheets; polyester resin molded products such as containers (typically bottles); textiles such as clothing. , Knitted fabrics, non-woven fabrics and the like containing polyester resin cloth; and the like.
- the polyester resin has high heat resistance and rigidity, and it is easy to collect the required amount in a form incorporated in products and members or in a state where it can be analyzed even after use.
- a suitable example of the determination target disclosed herein is a pressure-sensitive adhesive sheet containing a polyester resin film.
- the electronic device is disassembled, and the polyester resin part of the pressure-sensitive adhesive sheet that is the object of determination is taken out from the joint between the parts, and the 14 C concentration ratio described below is used. A measurement can be made.
- One or more constituent elements of the genuine product or genuine member in authenticity determination contain a resin (for example, synthetic resin), and the resin contains 14 C at a predetermined concentration ratio. Other than that, it is not particularly limited.
- the genuine product has the same or similar configuration as that of the determination target object, and when the genuine product includes two or more (for example, three or more) constituent elements, those two are used from the viewpoint of improving the reliability of the authenticity determination. It is preferable that three or more (for example, three or more) constituent elements each contain a resin containing 14 C at a predetermined concentration ratio.
- the above constituent elements are preferably constituent elements made of resin.
- a resin part made of a synthetic resin or the like can easily set the 14 C concentration ratio within a stable specific range depending on the biomass material type and its usage ratio. Therefore, the component of the genuine product or the genuine member must be the resin part. Is preferred. In many cases, 14 C is usually uniformly distributed in the resin portion at almost the same concentration ratio. With respect to such a resin portion, a stable 14 C concentration ratio can be measured regardless of which portion is sampled. Examples of the types of genuine products or genuine members and the materials (specifically, resin materials) of the constituent elements thereof include the types and materials described in the determination target object.
- acrylic resins, rubbers, polyester resins, polyolefin resins, and urethane resins which are easy to obtain a predetermined 14 C concentration ratio using a biomass material, are preferable.
- the resin of one or more constituent elements (either the base material layer, the pressure-sensitive adhesive layer or the release liner base material layer) of the genuine pressure-sensitive adhesive sheet is 14 C at a predetermined concentration ratio.
- the 14 C concentration ratio in the genuine component may be a specific amount selected from the range obtained by the measuring method described below.
- the biomass carbon ratio of the genuine constituents is appropriately about 1% or more, and preferably 5% or more.
- the 14 C concentration ratio can be accurately measured by setting the biomass carbon ratio to a specific amount selected from the above range.
- the biomass carbon ratio of the above components is selected from the range of approximately 8% or more (eg approximately 12% or more, typically approximately 15% or more) 100% or less (typically 50% or less, eg 30% or less). It is more preferable to set the specific amount. By using a predetermined amount of biomass material, it is possible to adjust to a specific biomass carbon ratio.
- the genuine product eg, pressure-sensitive adhesive sheet
- the polyester resin part has a predetermined concentration ratio of 14 C.
- a component polyethylene resin part, eg, polyester resin film
- the polyester resin part has a predetermined concentration ratio of 14 C.
- a specific amount of 14 C can be introduced into the polyester resin part.
- 14 C is usually uniformly distributed at almost the same concentration ratio, and even if any part of the polyester resin part is sampled, a stable 14 C concentration can be obtained. The ratio can be measured.
- the polyester resin film is often possible to determine the authenticity only by the presence or absence of biomass carbon, advantageous is there.
- the biomass carbon ratio of the polyester resin portion is appropriately about 1% or more, for example, and preferably about 5% or more.
- the 14 C concentration ratio can be accurately measured by setting the biomass carbon ratio of the polyester resin to a specific amount selected from the above range.
- the biomass carbon ratio of the polyester resin is selected from the range of approximately 8% or more (eg approximately 12% or more, typically approximately 15% or more) 100% or less (typically 50% or less, eg 30% or less). It is more preferable to set the specific amount.
- biomass carbon means carbon (renewable carbon) contained in a biomass material, that is, a material derived from a renewable organic resource.
- the biomass material is typically a material derived from a biological resource (typically, a plant that performs photosynthesis) capable of continuous reproduction in the presence of sunlight, water, and carbon dioxide.
- biomass carbon ratio refers to the content ratio of biomass carbon in the total carbon in the measurement target (sample), and is measured based on ASTM D6866. It Among the methods described in ASTM D6866, the highly accurate B method is preferable. The same applies to the bio-based degree of the pressure-sensitive adhesive layer, the base material layer, the release liner, and the pressure-sensitive adhesive sheet described below, and the bio-based degree of the biomass polyester resin film.
- the biomass carbon ratio in the present specification is a value obtained from a 14 C concentration ratio (unit: pMC (percent Modern Carbon)) with respect to a standard value (Modern Reference Standard) defined by a standard substance. Specifically, the biomass carbon ratio [%] in the present specification can be obtained by dividing the measured value [pMC] of the 14 C concentration ratio by 1.005.
- the 14 C concentration ratio is measured for the constituent elements of the product or the like to be determined obtained as described above (S20).
- This measurement can be a measure of biobasedness.
- 14 C concentration ratio and degree of biobased are measured according to ASTM D6866. A bio-based degree is preferably used as a measurement value because of ease of comparison.
- the sample used for the measurement (a component included in the product to be determined, such as a polyester resin portion) is subjected to treatment such as washing as necessary in order to avoid mixing in other portions. For example, in a pressure-sensitive adhesive sheet including a polyester resin film as a base material layer, the measurement is performed on the polyester resin film from which the pressure-sensitive adhesive has been removed with water, a solvent, or the like.
- the release liner may be separated from the pressure-sensitive adhesive and the release-treated layer such as a silicone resin layer may be removed from the polyester resin film layer with a solvent or the like to make a measurement.
- the measurement may be carried out in the state where a release treatment layer such as a silicone resin layer is provided.
- the judgment object By comparing the measured value (A1) of the 14 C concentration ratio of the constituent element of the judgment object obtained above with the 14 C concentration ratio (A0) of the corresponding constituent element of the genuine product, the judgment object is It is possible to determine whether or not it is a product (S40).
- the measurement value A0 a value measured in advance may be used, or a value measured at the same time as the 14 C concentration ratio measurement of the constituent elements of the determination object may be used (S30).
- authenticity judgment is performed based on the degree of biobase.
- the bio-based degree in the constituent element (for example, polyester resin portion) of the determination target is within ⁇ 5% of the bio-based degree in the corresponding constituent element (for example, polyester resin portion) of the genuine product
- the determination target object is “ It is determined to be “authentic” (S50), and if it is outside the range of ⁇ 5%, the determination target is determined to be “non-authentic” (S60).
- ASTM D6866 B method instead of the range of ⁇ 5% of biobase as a criterion of authenticity, the range of ⁇ 3% or ⁇ 1% (even ⁇ 0.5%, for example ⁇ 0 The range of 0.2%) can be adopted.
- the technique disclosed here is not limited to this.
- the authenticity can be determined by measuring the 14 C concentration ratio of the products and the like exemplified above and the constituent elements made of the various materials exemplified above.
- the determination object is the pressure-sensitive adhesive sheet, per adhesive layer of the adhesive sheet (which may be an acrylic or rubber-based.), Was performed 14 C-concentration ratio measurement, compared with 14 C concentration ratio of authentic By doing so, it is possible to perform authenticity determination and tracing of genuine products.
- the authenticity of a product or the like can be efficiently determined by measuring the 14 C concentration ratio of only one constituent element of the product or the like.
- the reliability of the authenticity determination can be improved by measuring the 14 C concentration ratio and making the determination for two or more (for example, three or more) constituent elements of the product or the like.
- only one of the plurality of constituent elements that the genuine product may have is configured to have a predetermined 14 C concentration ratio by using the biomass resin material, and the other one of the constituent elements is configured. It can be formed from only fossil resource materials, and the 14 C concentration ratio can be measured for these two constituent elements.
- two or more (for example, three or more) constituent elements of the genuine product are made into a predetermined 14 C concentration ratio (the same 14 C concentration ratio or different 14 C concentration ratio) by using a biomass resin material, and Highly reliable determination can be performed by measuring the 14 C concentration ratio for each constituent element.
- the determination target is an adhesive sheet in which both the base material layer and the release liner base material layer are polyester resin film layers.
- Another example is a pressure-sensitive adhesive sheet in which two release liner base material layers that protect both pressure-sensitive adhesive surfaces are polyester resin film layers.
- the 14 C concentration ratio measurement is additionally performed for one or more constituent elements, such as constituent elements formed of a material other than polyester resin (for example, an acrylic or rubber adhesive layer). It can be done and contrasted with the genuine product.
- the determination target is a pressure-sensitive adhesive sheet, the comparison of the bio-based degree between the genuine product and the pressure-sensitive adhesive of the determination target can be added to the determination step.
- the pressure-sensitive adhesive sheet disclosed herein is a traceable pressure-sensitive adhesive sheet capable of determining whether it is a genuine product or a non-genuine product based on the biobased degree of its constituent elements (pressure-sensitive adhesive layer, base material layer, release liner base material layer, etc.). possible.
- the pressure-sensitive adhesive sheet according to some embodiments may be a pressure-sensitive adhesive sheet having a form in which the pressure-sensitive adhesive layer is provided on one surface or both surfaces of a non-peelable base material (supporting base material).
- Such a PSA sheet may be in the form of a PSA sheet with a release liner in which the surface of the PSA layer is protected by a release liner.
- the pressure-sensitive adhesive sheet may be a pressure-sensitive adhesive sheet without a base material (that is, a pressure-sensitive adhesive sheet having no non-releasable base material) such as a form in which the pressure-sensitive adhesive layer is held by a release liner.
- the concept of the pressure-sensitive adhesive sheet here may include what is called a pressure-sensitive adhesive tape, a pressure-sensitive adhesive label, a pressure-sensitive adhesive film, or the like.
- the pressure-sensitive adhesive layer is typically formed continuously, but the pressure-sensitive adhesive layer is not limited to such a form, and may be a pressure-sensitive adhesive layer formed in a regular or random pattern such as dots or stripes. May be.
- the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a sheet. Alternatively, it may be a pressure-sensitive adhesive sheet further processed into various shapes.
- the "adhesive” is a material having a property of being a soft solid (viscoelastic body) in a temperature range near room temperature and easily adhering to an adherend by pressure, as described above.
- the adhesive used herein generally has a complex tensile modulus E * (1 Hz) as defined in “C. A. Dahlquist, “Adhesion: Fundamental and Practice”, McLaren & Sons, (1966) P. 143”. It may be a material having a property satisfying ⁇ 10 7 dyne/cm 2 (typically, a material having the above property at 25° C.).
- the pressure-sensitive adhesive sheet disclosed herein may have, for example, a cross-sectional structure schematically shown in FIGS. 2 to 7.
- FIG. 2 and FIG. 3 are examples of the configuration of a pressure-sensitive adhesive sheet with a base material having one-sided adhesiveness.
- the pressure-sensitive adhesive layer 21 is provided on one surface 10A (non-peeling property) of the base material layer 10.
- the surface (adhesion surface) 21A of the pressure-sensitive adhesive layer 21 is protected by a release liner 31 having a release surface on at least the pressure-sensitive adhesive layer side. It has a different configuration.
- the pressure-sensitive adhesive sheet 2 shown in FIG. 3 has a structure in which the pressure-sensitive adhesive layer 21 is provided on one surface 10A (non-peeling property) of the base material layer 10.
- the other surface 10B of the base material layer 10 is a release surface, and before use, when the pressure-sensitive adhesive sheet 2 is wound, the pressure-sensitive adhesive layer 21 comes into contact with the other surface 10B, The surface (adhesion surface) 21B of the layer is protected by the other surface 10B of the base material layer 10.
- FIG. 4 and 5 show an example of the structure of a double-sided adhesive type adhesive sheet with a base material.
- pressure-sensitive adhesive layers 21 and 22 are provided on the respective surfaces of the base material layer 10 (both of which are non-peeling).
- the pressure-sensitive adhesive sheet 3 before use has a structure in which the pressure-sensitive adhesive layers 21 and 22 are protected by release liners 31 and 32 having a release surface on at least the pressure-sensitive adhesive layer side.
- the pressure-sensitive adhesive sheet 4 shown in FIG. 5 is provided with pressure-sensitive adhesive layers 21 and 22 on each surface of the base material layer 10 (both of which are non-peelable), and before use, one of the pressure-sensitive adhesive layers 21 is used.
- the pressure-sensitive adhesive sheet 4 may be configured such that the pressure-sensitive adhesive layer 22 is also protected by the release liner 31 by winding the pressure-sensitive adhesive sheet 4 and bringing the other pressure-sensitive adhesive layer 22 into contact with the back surface of the release liner 31. it can.
- the pressure-sensitive adhesive sheet 5 shown in FIG. 6 has both surfaces 21A and 21B of the substrateless pressure-sensitive adhesive layer 21 protected by release liners 31 and 32 having release surfaces on at least the pressure-sensitive adhesive layer side. Have a configuration.
- the pressure-sensitive adhesive sheet 6 shown in FIG. 7 has a configuration in which one surface (adhesion surface) 21A of the substrate-less pressure-sensitive adhesive layer 21 is protected by a release liner 31 having both surfaces as release surfaces. Then, when this is wound, the other surface (adhesion surface) 21B of the pressure-sensitive adhesive layer 21 comes into contact with the back surface of the release liner 31, so that the other surface 21B can also be protected by the release liner 31. Has become.
- the type of the adhesive forming the adhesive layer is not particularly limited.
- the pressure-sensitive adhesive (which may also be a pressure-sensitive adhesive composition) is an acrylic polymer, rubber-based polymer, polyester-based polymer, urethane-based polymer, polyether-based polymer, silicone-based polymer, polyamide-based polymer known in the field of pressure-sensitive adhesives. , One type or two or more types of various rubber-like polymers such as fluoropolymers. From the viewpoint of adhesive performance and cost, an adhesive containing an acrylic polymer as a main component (acrylic adhesive) or an adhesive containing a rubber polymer as a main component (rubber adhesive) is preferable.
- the rubber-based adhesive examples include natural rubber-based adhesives and synthetic rubber-based adhesives, and modified rubber-based adhesives such as acrylic modified natural rubber can also be preferably used.
- the biobased degree of the pressure-sensitive adhesive layer can be adjusted by the polymer species constituting the pressure-sensitive adhesive and the content ratio thereof.
- the pressure-sensitive adhesive layer is, if necessary, various rosin-based or terpene-based tackifying resins, various crosslinking agents such as isocyanate-based or epoxy-based, crosslinking aids, leveling agents, plasticizers, fillers, colorants (pigments, dyes). Etc.), antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and the like, and various additives generally used in the field of pressure-sensitive adhesive compositions may be included. As such various additives, conventionally known ones can be used by a conventional method. The biobased degree of the pressure-sensitive adhesive layer can be adjusted by the kind and amount of the additive used.
- the form of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a water-based pressure-sensitive adhesive composition, a solvent-based pressure-sensitive adhesive composition, a hot-melt pressure-sensitive adhesive composition, and an active energy ray-curable pressure-sensitive adhesive. It may be a composition or the like.
- the pressure-sensitive adhesive layer can be formed from the pressure-sensitive adhesive composition by a conventionally known method.
- the pressure-sensitive adhesive composition for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, die coater, bar coater, knife coater, spray coater, etc., using a known or common coater
- the pressure-sensitive adhesive composition may be applied by impregnation, curtain coating, or the like.
- the drying temperature may be, for example, about 40 to 150°C, preferably about 60 to 130°C.
- the bio-based degree of the adhesive layer is not particularly limited.
- the biobased degree of the pressure-sensitive adhesive layer can be set to, for example, about 1% or more from the usage ratio of the biomass resource-derived material such as natural rubber or rosin, may be about 10% or more, may be about 30% or more, and may be about 30% or more. It may be 50% or more, or about 70% or more (for example, about 80% or more).
- the degree of biobased of the adhesive layer may be about 90% or less, about 60% or less, about 40% or less, about 20% or less (for example, 1% or less), or substantially 0%. ..
- the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately selected according to the purpose.
- the thickness of the pressure-sensitive adhesive layer can be set to, for example, about 2 ⁇ m to 500 ⁇ m in consideration of the balance between the adhesiveness to the adherend and the cohesiveness. From the viewpoint of adhesiveness to an adherend, the thickness of the pressure-sensitive adhesive layer is appropriately 3 ⁇ m or more, and preferably 5 ⁇ m or more. From the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive layer may be, for example, 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less.
- the thickness of the pressure-sensitive adhesive layer may be, for example, 20 ⁇ m or less, 15 ⁇ m or less, or 12 ⁇ m or less.
- the thickness of each PSA layer may be the same or different.
- the pressure-sensitive adhesive sheet disclosed herein may be in the form of a pressure-sensitive adhesive sheet with a substrate, which has a pressure-sensitive adhesive layer on one side or both sides of the substrate (layer).
- the base material (layer) various base material films can be used, and for example, a resin film, paper, cloth, a rubber sheet, a foam sheet, a metal foil, a composite of these, or the like can be used.
- a resin film, a rubber sheet, a foam sheet, a metal foil, a composite of these or the like which is unlikely to be a source of dust (fine fibers or particles such as paper dust), can be preferably used. ..
- the resin film is more preferable from the viewpoint of dimensional stability, thickness accuracy, economic efficiency (cost), workability, tensile strength and the like.
- the resin film may have a single-layer structure, or may have a multilayer structure of two layers, three layers or more (for example, at least one layer thereof has a biomass resin film layer described later). From the viewpoint of shape stability, the resin film preferably has a single layer structure.
- the "resin film” is typically a non-porous film and is a concept distinguished from so-called non-woven fabrics and woven fabrics.
- the resin film examples include a polyester resin film formed from polyester such as PET, PEN, PBT, PBN, PEF, and PBS; formed from PE, PP, ethylene-propylene copolymer, ethylene-butene copolymer, and the like.
- a polyester resin film can be preferably used as the base material layer from the viewpoint of strength and workability.
- the PET resin film is more preferable.
- biomass material can be used as a material for forming the base material layer.
- the base material layer contains biomass carbon, for example, the authenticity can be preferably determined from the biobase degree of the base material layer of the adhesive sheet.
- the biomass material typically a biomass resin material
- the biomass material that can form the base material layer is not particularly limited, and examples thereof include biomass PET resin, biomass PEN resin, biomass PBT resin, biomass PBN resin, biomass PEF resin, and biomass PBS resin.
- Biomass polyester resin such as biomass polytrimethylene terephthalate resin; biomass high density polyethylene (biomass HDPE) resin, biomass low density polyethylene (biomass LDPE) resin, biomass linear low density polyethylene (biomass LLDPE) resin, and other biomass polyethylene resins , Biomass polypropylene resin such as biomass polypropylene (biomass PP) resin; polylactic acid; biomass poly(3-hydroxybutyrate-co-3-hydroxyhexanoate); polyhexamethylene sebacamide, poly(xylylene sebacamide) ) And other biomass polyamide resins; biomass polyester ether urethane resins, biomass polyether urethane resins and other biomass polyurethane resins; cellulosic resins; and the like.
- biomass polytrimethylene terephthalate resin biomass high density polyethylene (biomass HDPE) resin, biomass low density polyethylene (biomass LDPE) resin, biomass linear low density polyethylene (biomass LLDPE) resin, and other biomass poly
- biomass polyester resin and biomass polyolefin resin are preferable, and biomass PET resin is particularly preferable.
- biomass polyester resin and biomass polyolefin resin are preferable, and biomass PET resin is particularly preferable.
- the above biomass material is a resin material, it can be preferably applied to a constitution in which the base material layer is a resin film. By using the biomass resin film material formed from the above biomass material, it is possible to reliably carry out the authenticity determination based on the degree of biobase.
- the base layer of the pressure-sensitive adhesive sheet is composed of a polyester resin film.
- a polyester resin film base material layer contains biomass carbon, and the authenticity can be reliably determined from the 14 C concentration ratio thereof.
- the polyester resin forming the polyester resin film typically, a polyester resin containing a polyester obtained by polycondensing a dicarboxylic acid and a diol as a main component is used.
- a biomass-derived compound as at least one (for example, both) of the dicarboxylic acid and the diol used in the synthesis, the polyester resin can be made into biomass.
- dicarboxylic acid constituting the polyester examples include phthalic acid, isophthalic acid, terephthalic acid, 2-methylterephthalic acid, 5-sulfoisophthalic acid, 4, 4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylketone dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 1,4 -Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid
- the dicarboxylic acid that constitutes the polyester may be mainly composed of terephthalic acid.
- the polyester resin of this aspect include PET resin and PBT resin.
- the proportion of terephthalic acid in the entire dicarboxylic acid constituting the polyester is appropriately about 50% by weight or more, and from the viewpoint of sufficiently exerting the effect of using terephthalic acid, preferably about 90% by weight. Or more (typically 95% by weight or more, for example 99 to 100% by weight).
- Terephthalic acid can be used in polyester synthesis, for example, in the form of derivatives such as lower alkyl esters of terephthalic acid.
- a biomass-derived dicarboxylic acid can be preferably used. This allows the polyester resin film to contain a predetermined amount of biomass carbon.
- biomass-derived terephthalic acid and its derivatives can be used as the dicarboxylic acid.
- the method for obtaining a biomass-derived dicarboxylic acid is not particularly limited, and for example, biomass-derived terephthalic acid is corn, sugars, or isobutanol obtained from wood, which is then converted to isobutylene and dimerized to obtain isooctene.
- Examples thereof include a method (International Publication No. 2009/079213).
- the proportion of the biomass-derived dicarboxylic acid (eg, terephthalic acid) in the dicarboxylic acid (eg, terephthalic acid) constituting the polyester is not particularly limited. From the viewpoint of analysis accuracy, the proportion of the biomass-derived dicarboxylic acid in the entire dicarboxylic acid constituting the polyester is approximately 1% by weight or more (eg 1 to 100% by weight), and approximately 10% by weight or more is appropriate. For example, it may be about 50% by weight or more, about 80% by weight or more, about 90% by weight or more, or about 99% by weight or more. Substantially all of the above dicarboxylic acids may be biomass-derived dicarboxylic acids.
- the proportion of the biomass-derived dicarboxylic acid in the entire dicarboxylic acid may be less than 1% by weight. It may be substantially free of biomass-derived diols.
- diol constituting the polyester examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,2-propanediol, 1,3- Propanediol, 1,5-pentanediol, neopentyl glycol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, poly Aliphatic diols such as oxytetramethylene glycol; alicyclic diols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, and 1,4-cyclohexanedimethylol; xylylene glycol, Aroma
- aliphatic diols are preferable, and ethylene glycol is particularly preferable.
- the proportion of the aliphatic diol (preferably ethylene glycol) in the diol constituting the polyester is preferably 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more).
- the diol may be composed essentially of ethylene glycol.
- the diol constituting the polyester may be mainly composed of ethylene glycol.
- Specific examples of the polyester resin of this aspect include biomass PET resin and biomass PEN resin.
- the proportion of ethylene glycol in the entire diol constituting the polyester is appropriately about 50% by weight or more, and preferably about 90% by weight or more from the viewpoint of sufficiently exerting the effect of using ethylene glycol. (Typically 95% by weight or more, eg 99-100% by weight).
- a biomass-derived diol (typically, a biomass diol obtained by using biomass ethanol as a raw material) can be preferably used. This allows the polyester resin film to contain a predetermined amount of biomass carbon.
- biomass-derived ethylene glycol (typically, biomass ethylene glycol obtained by using biomass ethanol as a raw material) can be used as the diol.
- the proportion of the biomass-derived diol (preferably ethylene glycol) in the diol (preferably ethylene glycol) constituting the polyester is not particularly limited. From the viewpoint of analytical accuracy, the proportion of diol derived from biomass in the whole diol constituting the polyester is about 1% by weight or more (eg 1 to 100% by weight), and about 10% by weight or more is appropriate. For example, it may be about 50% by weight or more, about 80% by weight or more, about 90% by weight or more, or about 99% by weight or more. Substantially all of the above diols may be biomass-derived diols.
- the proportion of the biomass-derived diol in the entire diol may be less than 1% by weight. It may be substantially free of the derived diol.
- the polyester may be substantially composed of a dicarboxylic acid and a diol, but for the purpose of introducing a desired functional group, adjusting the molecular weight, or the like, a trivalent polyester may be used as long as the effect of the technique disclosed herein is not impaired.
- the above polyvalent carboxylic acid, trivalent or higher valent polyol, monocarboxylic acid or monoalcohol, hydroxycarboxylic acid, lactone and the like may be copolymerized.
- These other copolymerization components may or may not be derived from biomass. It is suitable that the ratio of the other copolymerization component is, for example, less than 30 mol %, typically less than 10 mol% (further less than 1 mol %).
- the technique disclosed herein can be preferably carried out even in a mode in which the monomer component of the polyester does not substantially contain the other copolymerization component.
- the method for obtaining the polyester disclosed herein is not particularly limited, and a polymerization method known as a polyester synthesis method can be appropriately adopted.
- the monomer raw material used for synthesizing the polyester can be obtained by polycondensing dicarboxylic acid and diol at an appropriate molar ratio from the viewpoint of polymerization efficiency, molecular weight adjustment and the like. More specifically, the reaction of the carboxy group of the dicarboxylic acid with the hydroxyl group of the diol is carried out while removing water (produced water) typically produced by the above reaction to the outside of the reaction system to give a polyester. Can be synthesized.
- a method for removing the produced water to the outside of the reaction system a method of blowing an inert gas into the reaction system and taking out the produced water together with the inert gas to the outside of the reaction system, distilling the produced water from the reaction system under reduced pressure
- the method (pressure reduction method) or the like can be used.
- the above decompression method can be preferably adopted because it is easy to shorten the synthesis time and is suitable for improving the productivity.
- the reaction may be batch polymerization, semi-continuous polymerization, or continuous polymerization.
- the reaction temperature at the time of carrying out the above reaction (including esterification and polycondensation) and the degree of reduced pressure (pressure in the reaction system) when the reduced pressure method is adopted are determined by the polymer having the desired characteristics (for example, molecular weight). It can be appropriately set so as to obtain efficiently.
- a known or conventional catalyst can be used in an appropriate amount for esterification and condensation, as in general polyester synthesis.
- the transesterification catalyst include magnesium-based compounds, manganese-based compounds, calcium-based compounds, cobalt-based compounds, lithium-based compounds, titanium-based compounds, zinc-based compounds, and barium-based compounds.
- the polymerization catalyst include titanium-based compounds, aluminum-based compounds, and germanium-based compounds.
- Various metal compounds such as antimony-based, tin-based and zinc-based compounds; strong acids such as p-toluenesulfonic acid and sulfuric acid; A solvent may or may not be used in the above synthesis.
- the above-mentioned synthesis can be carried out substantially without using an organic solvent (for example, it is meant to exclude a mode in which an organic solvent is intentionally used as a reaction solvent in the above reaction).
- an additive component such as a stabilizer (phosphorus compound etc.) may be optionally mixed.
- the biomass polyester resin film used in the technology disclosed herein may contain a polymer other than the above polyester in addition to the polyester.
- the polymer other than polyester among various polymer materials exemplified as the resin film capable of forming the above-mentioned base material layer, those other than polyester are preferable examples.
- the polymer other than polyester may be a biomass resource-derived polymer or a fossil resource-derived polymer.
- the content of the polymer other than polyester is appropriately less than 100 parts by weight with respect to 100 parts by weight of polyester, and is about 50.
- the amount is preferably not more than 30 parts by weight, more preferably not more than about 30 parts by weight, even more preferably not more than about 10 parts by weight.
- the content of the polymer other than polyester may be about 5 parts by weight or less, or about 1 part by weight or less, relative to 100 parts by weight of polyester.
- the technique disclosed herein can be preferably carried out, for example, in a mode in which 99.5 to 100% by weight of the polymer contained in the polyester resin film layer is polyester.
- the biobased degree of the biomass polyester resin film disclosed herein is not particularly limited and is about 1% by weight or more, and about 5% by weight or more is suitable.
- the biobased degree of the biomass polyester resin film is preferably about 8% or more, more preferably about 12% or more (for example, about 15% or more), about 30% or more, and about 60%.
- the above may be sufficient, and it may be a specific ratio selected from the range of about 90% or more.
- the upper limit of the bio-based degree of the biomass polyester resin film is 100%, and from the viewpoint of cost-effectiveness and authenticity determination, it may be less than 50%, less than 40%, less than 30% (for example, less than 20%). It can be a specific proportion selected from a range.
- the method for producing the biomass polyester resin film disclosed herein is not particularly limited as long as a conventionally known method is appropriately adopted except that the biomass polyester resin is used.
- a biomass polyester resin prepared by a known polyester synthesis method using the above-mentioned materials or a polyester derived from a commercially available biomass resource (for example, product name “Plant Pet” manufactured by Teijin Ltd.)
- various A biomass polyester resin film can be produced by appropriately incorporating a film forming method such as extrusion molding, inflation molding, T die cast molding, or calender roll molding by mixing an appropriate amount of additives.
- the thickness of the biomass polyester resin film layer is not particularly limited and can be appropriately selected according to the purpose.
- the thickness of the biomass polyester resin film layer is appropriately about 1 ⁇ m or more, and from the viewpoint of handleability and processability, it may be, for example, 1.5 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more, It may be 4 ⁇ m or more, or 4.5 ⁇ m or more.
- the thickness of the biomass polyester resin film layer may be, for example, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, or 25 ⁇ m or less, It may be 20 ⁇ m or less, 10 ⁇ m or less, 7 ⁇ m or less, less than 5 ⁇ m, or less than 4 ⁇ m.
- the base material layer may include a filler (inorganic filler, organic filler, etc.), an antioxidant, an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a plasticizer, if necessary.
- Various additives such as colorants (pigments, dyes, etc.) may be blended.
- the mixing ratio of various additives is usually about 30% by weight or less (for example, 20% by weight or less, typically 10% by weight or less).
- a pigment eg, white pigment
- the content ratio should be about 0.1 to 10% by weight (eg, 1 to 8% by weight, typically 1 to 5% by weight). Is appropriate.
- the surface (adhesive layer side surface) of the base material layer (for example, resin film, rubber sheet, foam sheet, etc.) on which the adhesive layer is arranged is corona discharge treated, plasma treated, ultraviolet irradiation treated, acid treated, alkali-treated.
- a known or common surface treatment such as treatment or formation of an undercoat layer may be applied.
- Such a surface treatment may be a treatment for improving the adhesion between the base material layer and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material layer.
- the base material layer may be one in which the surface treatment for improving the anchoring property has not been applied to the pressure-sensitive adhesive layer side surface.
- the undercoat agent (primer) used for the formation is not particularly limited and can be appropriately selected from known ones.
- the thickness of the undercoat layer is not particularly limited and may be, for example, more than 0.01 ⁇ m, suitably 0.1 ⁇ m or more, and may be 0.2 ⁇ m or more from the viewpoint of enhancing the effect.
- the thickness of the undercoat layer is preferably less than 1.0 ⁇ m, and may be 0.7 ⁇ m or less, or 0.5 ⁇ m or less.
- the surface of the base material layer on which the pressure-sensitive adhesive layer is not formed is subjected to release treatment with a release treatment agent (back treatment agent).
- back treatment agent that can be used to form the back treatment layer is not particularly limited, and a silicone-based back treatment agent, a fluorine-based back treatment agent, a long-chain alkyl-based back treatment agent, and other known or commonly used treatment agents can be used. It can be used depending on the application.
- the backside treating agent may be used alone or in combination of two or more kinds.
- the biobase degree of the base material layer is not particularly limited.
- the degree of biobase of the base material layer is, for example, about 1% by weight or more, and about 5% by weight or more is suitable.
- the bio-based degree of the base material layer is preferably about 8% or more, more preferably about 12% or more (for example, about 15% or more), about 30% or more, and about 60% or more.
- it may be a specific ratio selected from the range of about 90% or more.
- the upper limit of the bio-based degree of the base material layer is 100%, and from the viewpoint of cost-effectiveness and authenticity determination, it may be less than 50%, less than 40%, less than 30% (eg less than 20%). Can be a specific proportion selected from The biobased degree of the base material layer may be about 10% or less (for example, 1% or less), or may be substantially 0%.
- the thickness of the base material layer is not particularly limited and can be appropriately selected according to the purpose, and is in the range of, for example, about 1 ⁇ m to 500 ⁇ m. From the viewpoint of handleability and workability of the base material layer, the thickness of the base material layer may be, for example, 1.5 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, 4.5 ⁇ m. Or more. From the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet, in some embodiments, the thickness of the base material layer may be, for example, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less, and 20 ⁇ m or less. It may be 10 ⁇ m or less, 7 ⁇ m or less, less than 5 ⁇ m, or less than 4 ⁇ m.
- the pressure-sensitive adhesive sheet disclosed herein is a form in which a release liner is bonded to the pressure-sensitive adhesive surface for the purpose of protecting the pressure-sensitive adhesive surface (the surface of the pressure-sensitive adhesive layer that is attached to the adherend). (In the form of a pressure-sensitive adhesive sheet with a release liner).
- the release liner is not particularly limited.
- a release liner in which the surface of a liner substrate such as a resin film or paper is subjected to a release treatment, a fluoropolymer (polytetrafluoroethylene, etc.), a polyolefin resin (PE, PP, etc.) It is possible to use a release liner or the like made of the low-adhesion material of ).
- a polyester resin film such as a PET resin film
- a polyolefin resin film such as PP or ethylene-propylene copolymer
- a thermoplastic resin film such as polyvinyl chloride film
- a polyester resin film is more preferable.
- a silicone-based, fluorine-based, long-chain alkyl-based, fatty acid amide-based, molybdenum sulfide-based peeling treatment agent, silica powder, or the like can be used.
- a release-treated resin film (for example, a polyester resin film) can be preferably used as the release liner.
- the release treatment layer may be provided on at least one surface (for example, both surfaces) of the resin film.
- the release liner base material layer can be formed using a biomass material.
- the release liner base material layer contains biomass carbon.
- the biomass material typically, the biomass resin material
- one or more suitable materials can be selected and used from the materials exemplified as the biomass material of the biomass base material layer.
- the authenticity can be reliably determined from the biobased degree of the release liner base material layer.
- a biomass polyester resin film is used as a preferable biomass release liner base material layer. Since the details of the biomass polyester resin film are as described above, the duplicate description will not be repeated.
- the biobase degree of the release liner substrate layer is not particularly limited.
- the biobased degree of the release liner base material layer is, for example, about 1% by weight or more, and about 5% by weight or more is suitable.
- the release liner base material layer has a bio-based degree of preferably about 8% or more, more preferably about 12% or more (for example, about 15% or more), and may be about 30% or more, about 60%.
- the upper limit of the bio-based degree of the release liner substrate layer is 100%, and from the viewpoint of cost-effectiveness and authenticity determination, it may be less than 50%, less than 40%, less than 30% (eg less than 20%). Can be a specific ratio selected from the range.
- the biobased degree of the base material layer may be about 10% or less (for example, 1% or less), or may be substantially 0%. In a double-sided adhesive pressure-sensitive adhesive sheet with a substrate or without a substrate (double-sided pressure-sensitive adhesive sheet), when each side is protected by two release liners, each release liner substrate layer has the same biobase degree. Well, it may be different.
- the thickness of the release liner is not particularly limited, and may be, for example, about 5 ⁇ m to 200 ⁇ m, and preferably about 10 ⁇ m to 100 ⁇ m, from the viewpoint of conformability to the adhesive surface and peeling workability.
- the thickness of each release liner be different from the viewpoint of release workability of the release liner.
- the thickness of the first release liner can be about 10 to 200 ⁇ m (typically about 30 to 100 ⁇ m, for example about 50 to 80 ⁇ m)
- the thickness of the second release liner is about 5 ⁇ m or more and 100 ⁇ m or less.
- the thickness of the first release liner is preferably about 1.5 to 5 times (for example, 2 to 3 times) the thickness of the second release liner.
- the technique disclosed herein is carried out in an embodiment using a pressure-sensitive adhesive sheet with a release liner, which comprises a pressure-sensitive adhesive layer, a base material layer supporting the pressure-sensitive adhesive layer, and a release liner protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive sheet with a release liner which comprises a pressure-sensitive adhesive layer, a base material layer supporting the pressure-sensitive adhesive layer, and a release liner protecting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
- the biomass polyester resin film for both the base material layer and the release liner
- the reliability of authenticity determination can be further improved from the comparison of the 14 C concentration ratios of a plurality of biomass polyester resin films.
- the technology disclosed herein is carried out using a double-sided pressure-sensitive adhesive sheet in which each pressure-sensitive adhesive surface is protected by two release liners, by using a biomass polyester resin film for the two release liners, it is possible to determine the authenticity. The reliability of can be improved.
- the reliability of authenticity determination can be further improved by using the biomass polyester resin film for the base material layer in addition to the two release liners.
- the 14 C concentration ratio in the biomass polyester resin film of the base material layer and the biomass polyester resin film of the two release liners can be the same or different depending on the assumed imitation product and the authenticity determination property. it can.
- the thickness (total thickness) of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited and may be, for example, about the same. It can be in the range of 2 ⁇ m to 1000 ⁇ m. In some aspects, the thickness of the pressure-sensitive adhesive sheet is preferably about 5 ⁇ m to 500 ⁇ m (for example, 10 ⁇ m to 300 ⁇ m, typically 15 ⁇ m to 200 ⁇ m) in consideration of the pressure-sensitive adhesive property and the like.
- the thickness of the pressure-sensitive adhesive sheet may be 100 ⁇ m or less (eg 5 ⁇ m to 100 ⁇ m), 70 ⁇ m or less (eg 5 ⁇ m to 70 ⁇ m), or 45 ⁇ m or less (eg 5 ⁇ m to 45 ⁇ m).
- the biobased degree of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and more than 40% of the total carbon contained in the pressure-sensitive adhesive sheet may be biomass-derived carbon.
- the biobased degree of the adhesive sheet may be 50% or more, 60% or more, 70% or more, 75% or more, or 80% or more.
- the upper limit of the bio-based degree is 100% by definition, and in some embodiments, the bio-based degree of the pressure-sensitive adhesive sheet may be, for example, 95% or less, and even if 90% or less when the adhesive performance is more important. Well, it may be 85% or less.
- the authenticity determination method disclosed herein can be preferably applied to such an adhesive sheet.
- the application of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and a pressure-sensitive adhesive sheet used for various purposes in which a counterfeit product or the like may appear can be targeted. Typical applications include applications such as being attached to a component that constitutes an electronic device and fixing, joining, reinforcing, etc. the component.
- the pressure-sensitive adhesive sheet used for this purpose is difficult to obtain before use, and it is often necessary to determine whether or not it is a counterfeit product from the state of being incorporated in an electronic device. Further, since it is often firmly adhered to the adherend, it may be deformed or damaged when it is separated from the main body of the electronic device.
- the authenticity determination method disclosed herein can be preferably applied to a pressure-sensitive adhesive sheet used for such an application.
- the pressure-sensitive adhesive sheet used for the above-mentioned applications is typically in the form of a double-sided pressure-sensitive adhesive sheet, and can be preferably used for the purpose of fixing or joining parts.
- a double-sided pressure-sensitive adhesive sheet with a substrate using a thin substrate can be adopted.
- a pressure-sensitive adhesive sheet having a base material layer having a thickness of 10 ⁇ m or less (for example, less than 5 ⁇ m) can be used.
- the pressure-sensitive adhesive sheet for fixing or joining may have a shear adhesive force of a predetermined value or more. Since such a pressure-sensitive adhesive sheet has a strong resistance to a force (that is, a shearing force) for shifting the adhesive interface, it is excellent in the performance of holding an adherend.
- a pressure-sensitive adhesive sheet having a shear adhesive strength of 1.8 MPa or more preferably 2.0 MPa or more, more preferably 2.2 MPa or more, for example 20 MPa or less
- 1.8 MPa or more preferably 2.0 MPa or more, more preferably 2.2 MPa or more, for example 20 MPa or less
- the shear adhesive strength can be measured by the method described below. That is, a pressure-sensitive adhesive sheet (typically a double-sided pressure-sensitive adhesive sheet) is cut into a size of 10 mm ⁇ 10 mm to prepare a measurement sample. Under an environment of 23° C. and 50% RH, each adhesive surface of the measurement sample is superposed on the surface of two stainless steel plates (SUS304BA plate), and a 2 kg roller is reciprocated once to perform pressure bonding. After leaving this for 2 days in the same environment, the shear adhesive strength [MPa] is measured using a tensile tester under the conditions of a tensile speed of 10 mm/min and a peeling angle of 0 degree.
- the non-adhesive surface of the sheet may be fixed to a stainless steel plate with an adhesive or the like, and other measurements may be performed in the same manner as above.
- a universal tensile compression tester product name “TG-1kN”, manufactured by Minebea
- the pressure-sensitive adhesive sheet disclosed herein is suitable for parts fixing applications in portable electronic devices, for example.
- portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, and various wearable devices (for example, wristwear type worn on wrist like wristwatch, clip or strap, etc.).
- Modular type to be attached to a part of eyeglasses eyewear type including glasses type (monocular type and binocular type, including head mount type), clothes type to be attached to shirts, socks, hats, etc.
- the pressure-sensitive adhesive sheet disclosed herein can be preferably used for the purpose of fixing the pressure-sensitive sensor and other members in, for example, a portable electronic device including the pressure-sensitive sensor among such portable electronic devices.
- the pressure-sensitive adhesive sheet includes a device (typically a pen-type device or a mouse-type device) for indicating a position on the screen and a device for detecting the position, which corresponds to the screen (typically It is used to fix the pressure-sensitive sensor and other members in an electronic device (typically a portable electronic device) that has a function of allowing the absolute position to be specified on the touch panel. obtain.
- a device typically a pen-type device or a mouse-type device
- portable does not mean that it is simply portable, and that it has a level of portability that an individual (standard adult) can carry relatively easily. Shall mean.
- a second release liner was prepared.
- one side of the PET resin film is the release surface with the silicone release treatment agent.
- a PET resin film base material having a thickness of 4.5 ⁇ m formed by using a commercially available biomass PET resin was prepared.
- the above-mentioned biomass PET resin is a biomass PET resin synthesized by using terephthalic acid or a derivative thereof and plant-derived ethylene glycol as a biomass resource-derived raw material.
- the degree of biobase of each of the PET resin films of the first and second release liners and the PET resin film of the base material was 15% when measured based on ASTM D6866.
- a pressure-sensitive adhesive composition containing a modified rubber as a main component is applied to each release surface of the first release liner and the second release liner and dried at 100° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 13 ⁇ m. did.
- the pressure-sensitive adhesive layers formed on the first and second release liners were bonded to the respective surfaces of the PET resin film base material having a thickness of 4.5 ⁇ m to prepare a pressure-sensitive adhesive sheet (transfer method).
- the release liner was left as it was on the pressure-sensitive adhesive layer and used for protecting the surface (pressure-sensitive surface) of the pressure-sensitive adhesive layer.
- the biobased degree of the entire pressure-sensitive adhesive sheet (excluding the release liner) was 76%.
- An authenticity-determining pressure-sensitive adhesive sheet A was obtained in the same manner using the same material as the genuine pressure-sensitive adhesive sheet.
- An authenticity-determining pressure-sensitive adhesive sheet B having the same structure as the above genuine pressure-sensitive adhesive sheet was prepared except that a commercially available fossil resource-derived PET resin film was used as the PET resin film of the release liner.
- an authenticity-determining pressure-sensitive adhesive sheet C having the same structure as the above-mentioned genuine pressure-sensitive adhesive sheet was prepared, except that a commercially available fossil resource-derived PET resin film was used as the base PET resin film.
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Abstract
Description
ここに開示される真贋判定方法は、製品または部材の真贋を判定する方法である。一実施形態に係る真贋判定方法のフローチャートを図1に示す。以下、図1を参照して、ここに開示される真贋判定方法について詳述する。
ここに開示される真贋判定の対象物(製品や部材)は適当な方法で入手される(S10)。入手方法は特に制限されず、例えば、真正品や非真正品が流通する市場から市販品を購入するなどして入手することができる。判定対象物が部材の場合、当該部材が組み込まれた製品を入手し、分解して目的とする部材を得ることができる。ここに開示される判定対象物は、真正品と非真正品(模倣品であり得る。)とを含み得る。通常、それらは入手可能な状態において、外観や表示、製品情報のみからでは、真贋判定が難しい。このような製品や部材(以下「製品等」ともいう。)に対して、ここに開示される真贋判定方法が好ましく適用され得る。
真贋判定における真正製品または真正部材は、その1つ以上の構成要素が樹脂(例えば合成樹脂)を含有しており、その樹脂は所定の濃度比で14Cを含む。そのこと以外は特に限定されない。真正品は、上記判定対象物と同じか類似した構成を有し、真正品が2つ以上(例えば3つ以上)の構成要素を含む場合は、真贋判定の信頼性向上の観点から、それら2つ以上(例えば3つ以上)の構成要素が、それぞれ所定の濃度比で14Cを含む樹脂を含有することが好ましい。上記構成要素は、樹脂からなる構成要素であることが好ましい。例えば、合成樹脂等からなる樹脂部は、バイオマス材料種、その使用割合によって14C濃度比を、安定した特定範囲に設定しやすいので、真正製品または真正部材の構成要素は、樹脂部であることが好ましい。多くの場合、樹脂部内は、通常、ほぼ同じ濃度比で14Cが均一に分布している。そのような樹脂部については、どの部分をサンプリングしても、安定した14C濃度比が測定され得る。真正製品または真正部材の種類や、その構成要素の材料(具体的には樹脂材料)としては、判定対象物において記載した種類や材料が挙げられる。なかでも、バイオマス材料を用いて所定の14C濃度比としやすいアクリル樹脂、ゴム類、ポリエステル樹脂、ポリオレフィン樹脂、ウレタン樹脂が好ましい。製品等の一例である粘着シートにおいては、真正粘着シートの1つ以上の構成要素(基材層、粘着剤層および剥離ライナー基材層のいずれか)の樹脂が所定の濃度比で14Cを含む。判定の信頼性向上の観点からは、真正粘着シートの粘着剤層、基材層および剥離ライナーのすべてが、それぞれ同じか異なる濃度比で14Cを含む樹脂を含有することが好ましい。
次に、上記のようにして入手した判定対象の製品等が有する構成要素につき、14C濃度比を測定する(S20)。この測定はバイオベース度の測定であり得る。14C濃度比およびバイオベース度はASTM D6866に基づいて測定される。対比のしやすさから、測定値としてバイオベース度が好ましく用いられる。測定に用いるサンプル(判定対象の製品等が有する構成要素。例えばポリエステル樹脂部)については、他の部位の混入を避けるため、必要に応じて洗浄等の処置がとられる。例えば、ポリエステル樹脂フィルムを基材層として備える粘着シートでは、水や溶剤等で粘着剤を除去したポリエステル樹脂フィルムについて測定を行う。また、ポリエステル樹脂フィルム層を有する剥離ライナー付き粘着シートでは、粘着剤から剥離ライナーを分離し、シリコーン樹脂層等の剥離処理層をポリエステル樹脂フィルム層から溶剤等で除去したものにつき測定を行ってもよく、シリコーン樹脂層等の剥離処理層を有する状態で測定してもよい。
上記で得られた判定対象物の構成要素の14C濃度比の測定値(A1)を、真正品の対応する構成要素の14C濃度比(A0)と対比することにより、判定対象物が真正品か否かの判定を行うことができる(S40)。測定値A0は、予め測定した値を用いてもよく、判定対象物の構成要素の14C濃度比測定と同時に測定した値を用いてもよい(S30)。
次に、ここに開示される真贋判定方法に好ましく用いられる粘着シートについて説明する。ここに開示される粘着シートは、その構成要素(粘着剤層、基材層、剥離ライナー基材層等)のバイオベース度から、真正品か非真正品かの判断が可能なトレーサブル粘着シートであり得る。いくつかの態様に係る粘着シートは、非剥離性の基材(支持基材)の片面または両面に上記粘着剤層を有する形態の粘着シートであり得る。そのような粘着シートは、上記粘着剤層の表面が剥離ライナーで保護された剥離ライナー付き粘着シートの形態であり得る。他のいくつかの態様に係る粘着シートは、粘着剤層が剥離ライナーに保持された形態等の基材レスの粘着シート(すなわち、非剥離性の基材を有しない粘着シート)であり得る。
ここに開示される技術において、粘着剤層を構成する粘着剤の種類は特に限定されない。上記粘着剤(粘着剤組成物でもあり得る。)は、粘着剤の分野において公知のアクリル系ポリマー、ゴム系ポリマー、ポリエステル系ポリマー、ウレタン系ポリマー、ポリエーテル系ポリマー、シリコーン系ポリマー、ポリアミド系ポリマー、フッ素系ポリマー等の各種ゴム状ポリマーの1種または2種以上を含むものであり得る。粘着性能やコスト等の観点から、アクリル系ポリマーを主成分とする粘着剤(アクリル系粘着剤)やゴム系ポリマーを主成分とする粘着剤(ゴム系粘着剤)が好ましい。ゴム系粘着剤としては、天然ゴム系粘着剤や合成ゴム系粘着剤が挙げられ、アクリル変性天然ゴム等の変性ゴム系粘着剤も好ましく用いられ得る。粘着剤を構成するポリマー種やその含有割合によって、粘着剤層のバイオベース度は調節され得る。
ここに開示される粘着シートは、基材(層)の片面または両面に粘着剤層を備える基材付き粘着シートの形態であり得る。基材(層)としては、各種の基材フィルムを用いることができ、例えば樹脂フィルム、紙、布、ゴムシート、発泡体シート、金属箔、これらの複合体等を用いることができる。電子機器用の分野においては、塵埃(例えば紙粉等の、微小な繊維または粒子)の発生源となりにくい樹脂フィルム、ゴムシート、発泡体シート、金属箔、これらの複合体等を好ましく使用し得る。なかでも、寸法安定性、厚み精度、経済性(コスト)、加工性、引張強度等の観点から、樹脂フィルムがより好ましい。樹脂フィルムは、単層構造であってもよく、2層、3層またはそれ以上の多層構造(例えば、そのうちの少なくとも1層に、後述するバイオマス樹脂フィルム層)を有するものであってもよい。形状安定性の観点から、樹脂フィルムは単層構造であることが好ましい。なお、この明細書において「樹脂フィルム」とは、典型的には非多孔質のフィルムであって、いわゆる不織布や織布とは区別される概念である。
また、基材層を形成する材料としてバイオマス材料を用いることができる。かかる構成によると、基材層はバイオマス炭素を含むので、例えば、粘着シートの基材層のバイオベース度から真贋判定を好ましく行うことができる。上記基材層を構成し得るバイオマス材料(典型的にはバイオマス樹脂材料)は特に限定されず、例えば、バイオマスPET樹脂、バイオマスPEN樹脂、バイオマスPBT樹脂、バイオマスPBN樹脂、バイオマスPEF樹脂、バイオマスPBS樹脂、バイオマスポリトリメチレンテレフタレート樹脂等のバイオマスポリエステル樹脂;バイオマス高密度ポリエチレン(バイオマスHDPE)樹脂、バイオマス低密度ポリエチレン(バイオマスLDPE)樹脂、バイオマス直鎖状低密度ポリエチレン(バイオマスLLDPE)樹脂等のバイオマスポリエチレン樹脂、バイオマスポリプロピレン(バイオマスPP)樹脂等のバイオマスポリオレフィン樹脂;ポリ乳酸;バイオマスポリ(3-ヒドロキシブチレート-co-3-ヒドロキシヘキサノエート);ポリヘキサメチレンセバカミド、ポリ(キシリレンセバカミド)等のバイオマスポリアミド樹脂;バイオマスポリエステルエーテルウレタン樹脂、バイオマスポリエーテルウレタン樹脂等のバイオマスポリウレタン樹脂;セルロース系樹脂;等が挙げられる。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。なかでも、バイオマスポリエステル樹脂、バイオマスポリオレフィン樹脂が好ましく、バイオマスPET樹脂が特に好ましい。上記のバイオマス材料は樹脂材料であることから、基材層が樹脂フィルムである構成に好ましく適用され得る。上記のバイオマス材料から形成されたバイオマス樹脂フィルム材料を用いることによって、そのバイオベース度から真贋判定を信頼性よく実施することができる。
いくつかの好ましい態様において、粘着シートの基材層はポリエステル樹脂フィルムから構成されている。このようなポリエステル樹脂フィルム基材層はバイオマス炭素を含み、その14C濃度比から、真贋判定を信頼性よく実施することができる。ポリエステル樹脂フィルムを構成するポリエステル樹脂としては、典型的には、ジカルボン酸とジオールを重縮合して得られるポリエステルを主成分として含むポリエステル樹脂が用いられる。合成に使用するジカルボン酸とジオールの少なくとも一方(例えば両方)にバイオマス由来の化合物を使用することにより、ポリエステル樹脂をバイオマス化することができる。
ここに開示される粘着シートは、必要に応じて、粘着面(粘着剤層のうち被着体に貼り付けられる側の面)を保護する目的で、該粘着面に剥離ライナーを貼り合わせた形態(剥離ライナー付き粘着シートの形態)で提供され得る。剥離ライナーとしては、特に限定されず、例えば樹脂フィルムや紙等のライナー基材の表面が剥離処理された剥離ライナーや、フッ素系ポリマー(ポリテトラフルオロエチレン等)やポリオレフィン系樹脂(PE、PP等)の低接着性材料からなる剥離ライナー等を用いることができる。剥離ライナーの樹脂フィルム(層)としては、PET樹脂フィルム等のポリエステル樹脂フィルム;PP、エチレン-プロピレン共重合体等のポリオレフィン樹脂フィルム、ポリ塩化ビニル等フィルム等の熱可塑性樹脂フィルムが好ましく用いられ得る。強度や加工性の観点から、ポリエステル樹脂フィルムがより好ましい。また、上記剥離処理には、例えば、シリコーン系、フッ素系、長鎖アルキル系、脂肪酸アミド系、硫化モリブデン等の剥離処理剤、あるいはシリカ粉等が用いられ得る。剥離処理された樹脂フィルム(例えばポリエステル樹脂フィルム)を剥離ライナーとして好ましく採用し得る。上記剥離処理層は、樹脂フィルムの少なくとも一方の面(例えば両面)に設けられ得る。
ここに開示される粘着シート(粘着剤層を含み、基材付き粘着シートではさらに基材を含むが、剥離ライナーは含まない。)の厚さ(総厚)は、特に限定されず、例えば凡そ2μm~1000μmの範囲とすることができる。いくつかの態様において、粘着シートの厚さは、粘着特性等を考慮して、5μm~500μm(例えば10μm~300μm、典型的には15μm~200μm)程度とすることが好ましい。あるいは、薄型化を重視するいくつかの態様において、粘着シートの厚さは、100μm以下(例えば5μm~100μm)であってよく、70μm以下(例えば5μm~70μm)でもよく、45μm以下(例えば5μm~45μm)でもよい。
ここに開示される粘着シートの用途は特に限定されず、模倣品等が出現し得る各種用途に用いられる粘着シートが対象となり得る。典型的な用途としては、電子機器を構成する部品に貼り付けられて、当該部品の固定、接合、補強等する用途が挙げられる。この用途に用いられる粘着シートは、使用前の状態で入手し難く、電子機器に組み込まれた状態から、模倣品か否かの判断をしなければならないことが多い。また、被着体に強固に接着していることが多いため、電子機器本体から分離する際に変形、損壊してしまうこともある。そのような用途で用いられる粘着シートに対して、ここに開示される真贋判定方法を好ましく適用することができる。上記用途に用いられる粘着シートは、典型的には両面粘着シートの形態で、部品を固定または接合する用途に好ましく利用され得る。上記両面粘着シートは、薄型化の観点から、いくつかの態様において、薄手の基材を用いた基材付き両面粘着シートの形態が採用され得る。例えば、厚さが10μm以下(例えば5μm未満)の基材層を有する粘着シートが用いられ得る。
以下、本発明に関連する検証実験について説明するが、本発明をかかる具体例に示すものに限定することを意図したものではない。なお、以下の説明中の「部」および「%」は、特に断りがない限り重量基準である。
市販のバイオマスPET樹脂を用いて成形した厚さ25μmのPET樹脂フィルム基材層を有する第1剥離ライナーと、市販のバイオマスPET樹脂を用いて成形した厚さ75μmのPET樹脂フィルム基材層を有する第2剥離ライナーとを用意した。これら第1および第2の剥離ライナーは、PET樹脂フィルムの片面がシリコーン系剥離処理剤による剥離面となっている。また、市販のバイオマスPET樹脂を用いて成形した厚さ4.5μmのPET樹脂フィルム基材を用意した。上記バイオマスPET樹脂は、テレフタル酸またはその誘導体と、バイオマス資源由来原料として植物由来のエチレングリコールとを用いて合成したバイオマスPET樹脂である。第1および第2の剥離ライナーのPET樹脂フィルムおよび基材のPET樹脂フィルムにつき、ASTM D6866に基づいてバイオベース度を測定したところ、いずれも15%であった。
上記第1剥離ライナーおよび第2剥離ライナーの各々の剥離面に、変性ゴムを主成分とする粘着剤組成物を塗布し、100℃で2分間乾燥させて、厚さ13μmの粘着剤層を形成した。次いで、厚さ4.5μmのPET樹脂フィルム基材の各面に、上記第1および第2の剥離ライナー上に形成した粘着剤層をそれぞれ貼り合わせて、粘着シートを作製した(転写法)。上記剥離ライナーは、そのまま粘着剤層上に残し、該粘着剤層の表面(粘着面)の保護に使用した。この粘着シート全体(剥離ライナーを除く。)のバイオベース度は76%であった。
上記真正粘着シートと同じ材料を用いて同様の方法で真贋判定用粘着シートAを得た。また、剥離ライナーのPET樹脂フィルムとして市販の化石資源由来のPET樹脂フィルムを用いた他は上記の真正粘着シートと同じ構成の真贋判定用粘着シートBを用意した。また、基材のPET樹脂フィルムとして市販の化石資源由来のPET樹脂フィルムを用いた他は上記の真正粘着シートと同じ構成の真贋判定用粘着シートCを用意した。これらの粘着シートは外観からは互いに区別ができない。
上記で用意した真贋判定用粘着シートA~Cにつき、それらが有する剥離ライナーのPET樹脂フィルム、基材のPET樹脂フィルムおよび粘着シート全体(剥離ライナーを除く。)のバイオベース度をASTM D6866に基づいて測定した。結果を表1に示す。
10 基材層
21,22 粘着剤層
31,32 剥離ライナー
Claims (11)
- 製品または部材の真贋を判定する方法であって、
入手した判定対象の製品または部材が有する1つ以上の構成要素につき、ASTM D6866に基づいて放射性炭素14の濃度比を測定する工程を含み、
ここで、真正製品または真正部材が有する1つ以上の構成要素であって、前記判定対象の製品または部材の前記構成要素に対応する構成要素は、所定の濃度比で放射性炭素14を含む樹脂を含有する、方法。 - 前記判定対象の製品または部材の前記構成要素におけるバイオマス炭素比が、前記真正製品または真正部材の前記構成要素におけるバイオマス炭素比の±5%の範囲内の場合は、前記判定対象の製品または部材を真正と判定し、前記±5%の範囲外の場合は前記判定対象の製品または部材を非真正と判定する工程を含む、請求項1に記載の方法。
- 前記真正製品または前記真正部材を含む製品が流通する市場から、前記判定対象の製品または部材を入手する工程を含む、請求項1または2に記載の方法。
- 前記真正製品または真正部材が有する前記構成要素のバイオマス炭素比は5%以上である、請求項1~3のいずれか一項に記載の方法。
- 前記製品または部材は粘着シートであり、
前記粘着シートは:
(A)基材層の少なくとも一方の面に粘着剤層が配置された粘着シート;
(B)基材層の少なくとも一方の面に粘着剤層が配置された粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;および
(C)粘着剤層からなる粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;
のいずれかであり、
前記基材層、前記粘着剤層、および、前記剥離ライナー基材層の少なくとも1つが、所定の濃度比で放射性炭素14を含む樹脂を含有する構成要素である、請求項1~4のいずれか一項に記載の方法。 - 前記粘着シートは、前記構成要素として、前記粘着剤層、前記基材層および前記剥離ライナー基材層を備えており、
前記粘着剤層、前記基材層および前記剥離ライナー基材層は、それぞれ同じか異なる濃度比で放射性炭素14を含む樹脂を含有する、請求項5に記載の方法。 - 前記粘着シートは、前記基材層および/または前記剥離ライナー基材層として、ポリエステル樹脂フィルム層を備えており、
前記ポリエステル樹脂フィルム層は、所定の濃度比で放射性炭素14を含む構成要素である、請求項5または6に記載の方法。 - 前記粘着シートは両面接着性の粘着シートであり、電子機器を構成する部品の固定部材である、請求項5~7のいずれか一項に記載の方法。
- 請求項1~8のいずれか一項に記載の方法に用いられる粘着シートであって、
(A)基材層の少なくとも一方の面に粘着剤層が配置された粘着シート;
(B)基材層の少なくとも一方の面に粘着剤層が配置された粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;および
(C)粘着剤層からなる粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;
のいずれかの構成を有しており、
前記基材層、前記粘着剤層、および、前記剥離ライナー基材層の少なくとも1つが、所定の濃度比で放射性炭素14を含む樹脂を含有する、粘着シート。 - (A)基材層の少なくとも一方の面に粘着剤層が配置された粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;および
(B)粘着剤層からなる粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;
のいずれかの構成を有しており、
前記基材層、前記粘着剤層、および、前記剥離ライナー基材層のいずれも、放射性炭素14を含む樹脂を含有する、粘着シート。 - (A)基材層の少なくとも一方の面に粘着剤層が配置された粘着シート;
(B)基材層の少なくとも一方の面に粘着剤層が配置された粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;および
(C)粘着剤層からなる粘着シートと、さらに該粘着剤層の粘着面を保護する剥離ライナーとを備える剥離ライナー付き粘着シート;
のいずれかの構成を有する粘着シートであって、
前記基材層および/または前記剥離ライナー基材層として、ポリエステル樹脂フィルム層を備えており、
前記ポリエステル樹脂フィルムのバイオマス炭素比は5%以上である、粘着シート。
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2019
- 2019-02-22 CN CN201980092689.6A patent/CN113490846A/zh active Pending
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JPWO2020170448A1 (ja) | 2021-12-16 |
CN113490846A (zh) | 2021-10-08 |
JP7288498B2 (ja) | 2023-06-07 |
KR102671286B1 (ko) | 2024-06-03 |
KR20210127992A (ko) | 2021-10-25 |
US20220146454A1 (en) | 2022-05-12 |
EP3929577A4 (en) | 2022-10-05 |
EP3929577A1 (en) | 2021-12-29 |
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