WO2016056467A1 - アノダイズ処理用マスキングシート - Google Patents
アノダイズ処理用マスキングシート Download PDFInfo
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- WO2016056467A1 WO2016056467A1 PCT/JP2015/077992 JP2015077992W WO2016056467A1 WO 2016056467 A1 WO2016056467 A1 WO 2016056467A1 JP 2015077992 W JP2015077992 W JP 2015077992W WO 2016056467 A1 WO2016056467 A1 WO 2016056467A1
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- masking sheet
- sensitive adhesive
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- weight
- masking
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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
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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
- C09J107/00—Adhesives based on natural rubber
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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
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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
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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
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/383—Natural or synthetic rubber
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/022—Anodisation on selected surface areas
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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- 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
- C09J2203/31—Applications of adhesives in processes or use of adhesives in the form of films or foils as a masking tape for painting
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
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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
- C09J2407/00—Presence of natural rubber
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2425/00—Presence of styrenic polymer
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- C09J2453/00—Presence of block copolymer
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- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2481/00—Presence of sulfur containing polymers
- C09J2481/006—Presence of sulfur containing polymers in the substrate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2493/00—Presence of natural resin
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- C09J2495/00—Presence of bitume
Definitions
- the present invention relates to a masking sheet for anodizing treatment.
- This application claims priority based on Japanese Patent Application No. 2014-205587 filed on Oct. 6, 2014, the entire contents of which are incorporated herein by reference.
- the pressure-sensitive adhesive sheet used for masking during chemical treatment typically includes a film-like pressure-sensitive adhesive (pressure-sensitive adhesive layer) and a base material that supports the pressure-sensitive adhesive.
- Patent Document 1 describes an adhesive tape that includes a base material made of a metal foil and can be preferably used for masking applications.
- an adhesive sheet typically an aluminum foil or the like, which is based on a metal material
- Masking is performed using an adhesive sheet having a metal foil as a base material.
- the present invention has been made in view of such circumstances, and an object thereof is to provide a masking sheet for anodizing treatment that can satisfactorily prevent chemical solution from entering during anodizing treatment in a configuration using a non-metallic substrate. .
- the masking sheet for anodizing treatment contains the base material which has a 1st surface and a 2nd surface, and the adhesive layer arrange
- the base material is a non-metallic base material.
- the relationship between the elastic modulus Et ′ of the masking sheet and the thickness Hs of the substrate satisfies the following formula: 0.7 N / mm ⁇ E ′ ⁇ Hs 3 . According to the masking sheet satisfying such a relationship, it is possible to effectively prevent the chemical solution from entering during the anodizing process in the configuration using the non-metallic substrate.
- the masking sheet preferably has an elastic modulus Et ′ of 1.0 GPa or more. According to the masking sheet having such an elastic modulus Et ′, good chemical solution intrusion preventing property can be realized even if it is thinner.
- the masking sheet disclosed here preferably has a thickness of 0.30 mm or less.
- Such a masking sheet that is comparatively thin and excellent in chemical solution intrusion prevention during anodizing treatment can be preferably used, for example, in a mode that is used as a masking sheet for subsequent coating of articles to be treated after anodizing treatment. .
- the masking sheet disclosed herein preferably has a 90 degree peel strength with respect to duralumin A2024 of 1.0 to 25 N / 20 mm.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a tackifier.
- the pressure-sensitive adhesive contains a tackifier, the pressure-sensitive adhesive force (for example, 90 ° peel strength) to the object to be treated is improved, and the masking reliability tends to be improved.
- the content of the tackifier can be, for example, 10 to 85% by weight of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is a rubber-based pressure-sensitive adhesive.
- a masking sheet provided with a rubber-based adhesive layer is peeled off from the article to be treated after the anodizing treatment, an event in which the adhesive remains on the surface of the article to be treated tends not to occur. That is, it is preferable because it tends to be excellent in non-glue remaining property with respect to the article to be processed.
- the rubber-based pressure-sensitive adhesive As a preferable example of the rubber-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive in which 95% by weight or more of the rubber-based polymer contained in the pressure-sensitive adhesive is made of natural rubber can be given.
- the natural rubber for example, a natural rubber having a Mooney viscosity MS 1 + 4 (100 ° C.) of more than 70 can be preferably used.
- the rubber-based pressure-sensitive adhesive using natural rubber having a relatively high molecular weight as a base polymer tends to exhibit good chemical resistance.
- the rubber adhesive may contain about 20 to 40 parts by weight of a terpene resin with respect to 100 parts by weight of the rubber polymer.
- the pressure-sensitive adhesive layer having such a composition tends to exhibit good adhesion to the adherend.
- the pressure-sensitive adhesive layer of the masking sheet disclosed herein is a pressure-sensitive adhesive crosslinked by a reaction between a hydroxyl group-containing polymer and a hydroxyl group-reactive crosslinking agent (that is, a pressure-sensitive adhesive containing a crosslinked structure of a hydroxyl group-containing polymer and a hydroxyl group-reactive crosslinking agent). ).
- a masking sheet having such a pressure-sensitive adhesive layer is preferable because blocking between end faces of the pressure-sensitive adhesive layer tends to be suppressed.
- the shape accuracy of the outer edge portion of the adhesive layer in the one adhesive piece is It becomes hard to be damaged. This advantageously contributes to improving the stability (certainty) of the performance of preventing the chemical solution from entering from the outer edge of the adhesive piece in the anodizing process performed by attaching the one adhesive piece to the article to be processed. Can do.
- the masking sheet disclosed herein can be configured such that the chemical solution intrusion into the masking sheet is visible from the outer surface side of the masking sheet.
- the masking sheet configured as described above can easily grasp the state of chemical solution intrusion into the masking sheet without peeling off the masking sheet attached to the object to be processed. Therefore, for example, it can be preferably used in a mode in which it is subsequently used as a masking sheet for coating after anodizing treatment.
- FIG. 1 is a cross-sectional view schematically showing a configuration of a masking sheet according to an embodiment.
- FIG. 2 is a cross-sectional view schematically showing a configuration of a masking sheet according to another embodiment.
- the masking sheet disclosed here comprises a substrate having a first surface and a second surface, and an adhesive layer provided on the first surface side of the substrate.
- the base material is a non-metallic base material.
- FIG. 1 A typical configuration example of a masking sheet according to an embodiment is schematically shown in FIG.
- This masking sheet 10 includes a sheet-like substrate (for example, a resin sheet) 1 having a first surface 1A and a second surface 1B, and an adhesive layer 2 provided on the first surface 1A side.
- the masking sheet 10 is used by being attached to a non-processing target portion (masking target portion) of the processing target article. By performing the anodizing process in a state where the masking sheet 10 is attached to the non-processing target part, the non-processing target part is protected from the anodizing chemical.
- the masking sheet 10 before use typically has a surface (adhesive surface) 2 ⁇ / b> A of the adhesive layer 2 facing at least the adhesive layer 2. It can be in a form protected by a release liner 3 whose side to be used is a release surface.
- the second surface 1B of the substrate 1 (the surface opposite to the first surface 1A and also serves as the outer surface 10B of the masking sheet 10) is a release surface.
- the masking sheet 10 may be wound in a roll shape so that the pressure-sensitive adhesive layer 2 is in contact with the second surface 1B and the surface (adhesive surface) 2A is protected.
- the masking sheet in the technology disclosed herein is characterized by satisfying 0.7 N / mm ⁇ Et ′ ⁇ Hs 3 .
- the value of Et ′ ⁇ Hs 3 is proportional to the bending rigidity of the masking sheet.
- the present inventor has configured the masking sheet so that the bending rigidity of the masking sheet is larger than a certain level, specifically, Et ′ ⁇ Hs 3 is larger than 0.7 N / mm, and thereby anodizing treatment is performed. It was found that the chemical solution intrusion into the masking sheet was significantly suppressed.
- the masking sheet satisfying the above relational expression it is not necessary to elucidate the reason why the above-described effect can be obtained by the masking sheet satisfying the above relational expression.
- the following may be considered. That is, as one factor that the chemical solution intrusion during anodizing treatment proceeds by changing the metal substrate to a non-metal substrate, a non-metal substrate (typically compared to a masking sheet using a metal substrate) In the masking sheet using the insulator, it is considered that the distortion of the electric field due to the masking sheet being affixed during the anodizing process (when energized) increases.
- the generation of gas mainly gas generated by electrolysis, that is, electrolytic gas
- electrolytic gas mainly gas generated by electrolysis, that is, electrolytic gas
- the electrolytic gas generated near the outer edge of the masking sheet lowers the adhesion of the masking sheet by trying to push the masking sheet up from the surface of the article to be processed, and advances the infiltration of chemicals from the outer edge of the masking sheet. Can be a factor.
- the masking sheet can be resisted against the force that the electrolytic gas tries to push up the masking sheet (ie, press down the electrolytic gas) even during anodizing. It becomes easy to maintain the state of being in close contact with the surface of the article to be treated. This is considered to improve the chemical solution intrusion prevention property during anodizing treatment.
- Et ′ ⁇ Hs 3 of the masking sheet disclosed herein is typically greater than 0.8 N / mm, preferably greater than 1.0 N / mm, more preferably greater than 1.5 N / mm, and even more preferably 2. It can be greater than 0 N / mm (eg, greater than 2.2 N / mm).
- the upper limit of Et ′ ⁇ Hs 3 is not particularly limited.
- Et ′ ⁇ Hs 3 is usually about 10 ⁇ 10 3 N / mm or less. It is appropriate and is preferably about 1 ⁇ 10 3 N / mm or less (for example, about 0.5 ⁇ 10 3 N / mm or less).
- the elastic modulus Et 'of the masking sheet can be measured using a commercially available dynamic viscoelasticity measuring device. Specifically, a sample (masking sheet) to be measured is cut into a strip shape having a length of 30 mm and a width of 5 mm to produce a test piece. Using a dynamic viscoelasticity measuring apparatus (RSA-III, manufactured by TA Instruments Inc.), this test piece was measured in a tensile measurement mode with a distance between chucks of 23 mm, a heating rate of 10 ° C./min, and a frequency. The tensile storage elastic modulus in the temperature range of 0 ° C. to 100 ° C.
- the reason why the elastic modulus Et ′ of the masking sheet is obtained as the value of “per cross-sectional area of the substrate” is that the elastic modulus of the adhesive is usually small enough to be ignored compared to the elastic modulus of the substrate ( If the cross-sectional area of the adhesive layer is included in the cross-sectional area used to calculate the tensile storage elastic modulus (typically less than 1% of the elastic modulus of the base material), it is difficult to grasp the characteristics of the masking sheet that meets the purpose of this application. This is because.
- the elastic modulus of the pressure-sensitive adhesive is extremely small as compared with the elastic modulus of the base material, from the viewpoint of solving the problems of the present invention, the elastic modulus (that is, the basis) required by the above method using a masking sheet as a sample.
- the tensile storage elastic modulus Et ′ per cross-sectional area of the material and the elastic modulus Es ′ of the base material (this Es ′ is Et, except that the base material cut into a strip shape having a length of 30 mm and a width of 5 mm is used as a sample. Measured in the same way as').
- the value of the elastic modulus Es ′ of the substrate can be used as an alternative value of the elastic modulus Et ′ of the masking sheet or at least a practically sufficient approximate value.
- Et ′ and Es ′ in the present specification can be interchanged with each other unless otherwise specified.
- Et ′ ⁇ Hs 3 and Es ′ ⁇ Hs 3 can be read each other.
- the elastic modulus Et ′ of the masking sheet is not particularly limited as long as the above-described Et ′ ⁇ Hs 3 is obtained.
- Et ′ can be, for example, 0.3 GPa or more (typically 0.5 GPa or more).
- Et ′ is advantageously 1.0 GPa (that is, 1.0 ⁇ 10 3 N / mm 2 ) or more, 1.5 GPa or more is preferable, and 2.0 GPa or more is more preferable.
- the upper limit of Et ′ is not particularly limited.
- Et ′ can be adjusted by the structure of the base material, the material used, the combination thereof, and the like.
- the thickness Ht of the masking sheet is not particularly limited.
- the technique disclosed here can be implemented in an embodiment in which, for example, Ht is 7 mm or less (typically 5 mm or less, for example, 1 mm or less).
- Ht can be 0.50 mm or less, preferably 0.30 mm or less, more preferably 0.25 mm or less (for example 0.20 mm or less), and 0.15 mm or less (typically 0). More preferably less than .15 mm).
- the end face of the masking sheet is It becomes easy to reduce the quantity which a liquid thing accumulates.
- the lower limit of Ht is not particularly limited, but is usually 0.04 mm or more, preferably 0.06 mm or more.
- the masking sheet disclosed herein can be preferably implemented in an embodiment in which Ht is more than 0.08 mm (typically 0.09 mm or more, for example, 0.10 mm or more).
- the thickness Ht of the masking sheet refers to the thickness of the part that is attached to the adherend (the article to be processed).
- the thickness of the release liner 3 is not included.
- the non-metallic base material constituting the masking sheet means a base material whose main constituent material is a non-metallic material, and is typically approximately 50% by weight or more or approximately 50% by volume or more.
- a substrate that is a non-metallic material.
- non-metallic material refers to all materials other than metallic materials, and is a concept including organic materials and inorganic non-metallic materials.
- the non-metallic base material may be a single-layer base material composed of one layer, or may be a base material having a laminated structure of two or more layers in the entire region or a partial region.
- the non-metallic substrate may include a layer formed of any one selected from organic materials and inorganic non-metallic materials, and a layer formed of a blend or composite (composite material) of two or more materials.
- the non-metallic substrate includes a layer made of a metallic material, a layer made of a blend or a composite of an organic material or an inorganic non-metallic material and a metallic material, as long as the main constituent material is a non-metallic material. obtain.
- Non-limiting examples of organic materials include synthetic organic materials, natural organic materials, semi-synthetic organic materials, recycled organic materials and the like.
- the organic material can be used alone or as a blend of two or more, for example, in the form of a film, in the form of a matrix in which other materials are dispersed, in the form of impregnated in other materials, in the form of fibers, in the form of powder Etc. can be used.
- Non-limiting examples of inorganic non-metallic materials include various glasses and ceramics. In view of the flexibility of the masking sheet and the like, the inorganic nonmetallic material can be used as a blend or a composite with an organic material, typically in a fibrous or powdery form.
- a thin film of an inorganic nonmetallic material may be formed on the entire surface or partially on the surface of another layer, for example, by a technique such as vapor deposition.
- the metal material can be preferably used as a blend or composite with an organic material, typically in the form of a fiber or powder.
- a thin film of a metal material may be formed on the entire surface or partially on the surface of another layer, for example, by a technique such as vapor deposition or plating.
- the base material of the masking sheet disclosed here various film-like base materials can be preferably used.
- the “resin film” means a resin film having a non-porous structure and typically containing substantially no bubbles (voidless). Therefore, the said resin film is the concept distinguished from a foam film and a nonwoven fabric.
- the resin film may have a single-layer structure or a multilayer structure having two or more layers (for example, a three-layer structure).
- the resin material constituting the resin film examples include polyester resin, polyolefin resin, polyamide resin (PA), polyimide resin (PI), polyamideimide resin (PAI), polyether ether ketone resin (PEEK), and polyether sulfone.
- the resin film may be formed using a resin material containing one kind of such resin alone, or may be formed using a resin material in which two or more kinds are blended. Also good.
- the resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).
- polyester resins examples include polyester resins, PPS resins, and polyolefin resins.
- the polyester-based resin refers to a resin containing polyester in a proportion exceeding 50% by weight.
- the PPS resin refers to a resin containing PPS in a proportion exceeding 50% by weight
- the polyolefin-based resin refers to a resin containing polyolefin in a proportion exceeding 50% by weight.
- polyester resin typically, a polyester resin containing as a main component a polyester obtained by polycondensation of a dicarboxylic acid and a diol is used.
- dicarboxylic acid constituting the polyester examples include phthalic acid, isophthalic acid, terephthalic acid, 2-methyl terephthalic acid, 5-sulfoisophthalic acid, 4,4′-diphenyl dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid.
- Aromatic dicarboxylic acids are preferred because a substrate exhibiting a suitable elastic modulus Es ′ can be easily obtained in the technology disclosed herein.
- preferred dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
- 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more) of the dicarboxylic acid constituting the polyester is terephthalic acid, 2,6-naphthalenedicarboxylic acid, or a combination thereof.
- the dicarboxylic acid may be composed substantially of terephthalic acid, substantially 2,6-naphthalenedicarboxylic acid, or substantially only terephthalic acid and 2,6-naphthalenedicarboxylic acid.
- diol constituting the polyester examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,4-butanediol, Aliphatic diols such as 1,6-hexanediol, 1,8-octanediol, polyoxytetramethylene glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4 -Cycloaliphatic dimethylol and other alicyclic diols, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) s Aromatic diols such as phone; and the like.
- aliphatic diols are preferable from the viewpoint of transparency and the like, and ethylene glycol is particularly preferable from the viewpoint of the elastic modulus Es ′ of the substrate.
- 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 substantially composed only of ethylene glycol.
- polyester resin examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate.
- polyolefin resin one kind of polyolefin can be used alone, or two or more kinds of polyolefins can be used in combination.
- the polyolefin may be, for example, an ⁇ -olefin homopolymer, a copolymer of two or more ⁇ -olefins, a copolymer of one or two or more ⁇ -olefins with other vinyl monomers, and the like.
- Specific examples include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), and ethylene-propylene rubber (EPR), ethylene-propylene-butene copolymers, ethylene-butene copolymers, and ethylene-ethyl acrylate.
- a copolymer etc. are mentioned. Both low density (LD) polyolefins and high density (HD) polyolefins can be used.
- polyolefin resin films include unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and medium density polyethylene (MDPE).
- CPP unstretched polypropylene
- OPP biaxially stretched polypropylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- MDPE medium density polyethylene
- examples thereof include a film, a high density polyethylene (HDPE) film, a polyethylene (PE) film obtained by blending two or more kinds of polyethylene (PE), and a PP / PE blend film obtained by blending polypropylene (PP) and polyethylene (PE).
- the resin film that can be preferably used for the base material of the masking sheet disclosed herein include PET film, PEN film, PPS film, PEEK film, CPP film, and OPP film.
- Preferable examples from the viewpoint of obtaining Et ′ ⁇ Hs 3 suitable for thinner substrates include PET film, PEN film, PPS film and PEEK film.
- a PET film and a PPS film are particularly preferable from the viewpoint of availability of the base material, and the PET film is particularly preferable.
- a light stabilizer In the resin film, a light stabilizer, an antioxidant, an antistatic agent, a colorant (dye, pigment, etc.), a filler, a slip agent, an antiblocking agent and the like are known as long as the effect of the present invention is not significantly hindered. These additives can be blended as necessary.
- the compounding quantity of an additive is not specifically limited, According to the use etc. of a masking sheet, it can set suitably.
- the method for producing the resin film is not particularly limited.
- conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting, and calendar roll molding can be appropriately employed.
- the base material may be substantially composed of such a base film.
- the base material may include an auxiliary layer in addition to the base film.
- the auxiliary layer include a visibility adjusting layer (for example, a colored layer) and an antistatic layer provided on the first surface or the second surface of the base film.
- Such a surface treatment may be a treatment for improving the adhesion between the base material and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material.
- the composition of the primer is not particularly limited and can be appropriately selected from known ones.
- the thickness of the undercoat layer is not particularly limited, but is usually about 0.01 to 1 ⁇ m, preferably about 0.1 to 1 ⁇ m.
- the second surface of the base material may be subjected to conventionally known surface treatment such as peeling treatment or antistatic treatment as necessary.
- conventionally known surface treatment such as peeling treatment or antistatic treatment as necessary.
- the second surface of the substrate is subjected to treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, and alkali treatment. May be.
- the thickness Hs of the base material is not particularly limited as long as the above-described Et ′ ⁇ Hs 3 is obtained.
- the masking sheet disclosed here can be implemented, for example, in an embodiment in which Hs is 5 mm or less (typically 3 mm or less). From the viewpoint of handleability and workability of the masking sheet, Hs is usually 1 mm or less (for example, 0.50 mm or less). In a preferred embodiment, Hs can be 0.30 mm or less, preferably 0.20 mm or less, and more preferably 0.15 mm or less (for example, 0.12 mm or less). By using a substrate having a small Hs, it becomes easy to reduce the thickness Ht of the masking sheet.
- the lower limit of Hs is not particularly limited, but is usually 0.03 mm or more, preferably 0.05 mm or more (typically more than 0.05 mm). From the viewpoint of realizing higher Et ′ ⁇ Hs 3 in a substrate that is easily available or easily manufactured, Hs may be 0.07 mm or more, or 0.08 mm or more (for example, 0.10 mm or more). Good.
- the elastic modulus Es ′ of the base material is not particularly limited as long as the above-described Et ′ ⁇ Hs 3 can be realized in the masking sheet formed using the base material.
- Es ′ can be, for example, 0.3 GPa or more (typically 0.5 GPa or more). From the viewpoint that a masking sheet showing good chemical solution intrusion prevention property can be easily constructed even if a thinner base material is used, Es ′ is advantageously 1.0 GPa or more, preferably 1.5 GPa or more. 0.0 GPa or more is more preferable.
- the upper limit of Es ′ is not particularly limited.
- Es ′ can be adjusted by the structure of the base material, the material used, the combination thereof, and the like.
- the pressure-sensitive adhesive layer in the technology disclosed herein typically exhibits a soft solid (viscoelastic body) state in a temperature range near room temperature, and has a property of easily adhering to an adherend by pressure ( A layer composed of an adhesive).
- the adhesive here is generally complex elastic modulus E * (1 Hz) as defined in “C. A. Dahlquist,“ Adhesion: Fundamental and Practice ”, McLaren & Sons, (1966) P. 143”. ⁇ 10 ⁇ 7 > dyne / cm ⁇ 2 > material (typically a material having the above properties at 25 [deg.] C.).
- the pressure-sensitive adhesive layer in the technology disclosed herein includes a water-dispersed pressure-sensitive adhesive composition, a water-soluble pressure-sensitive adhesive composition, a solvent-type pressure-sensitive adhesive composition, a hot-melt pressure-sensitive adhesive composition, and an active energy ray-curable pressure-sensitive adhesive composition. It can be a pressure-sensitive adhesive layer formed from various forms of pressure-sensitive adhesive compositions. From the viewpoint of chemical solution penetration, a solvent-type pressure-sensitive adhesive composition can be preferably used.
- the composition of the pressure-sensitive adhesive is not particularly limited.
- the pressure-sensitive adhesive is a rubber polymer, acrylic polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, polyamide polymer, fluorine polymer or the like known in the field of pressure sensitive adhesives at room temperature.
- One or more of various polymers exhibiting elasticity may be included as a base polymer (a main component of the polymer component, that is, a component occupying more than 50% by weight).
- Examples of preferred adhesives from the viewpoint of resistance to chemicals and the like include rubber adhesives, acrylic adhesives, and silicone adhesives.
- the rubber-based pressure-sensitive adhesive refers to a pressure-sensitive adhesive in which the base polymer of the pressure-sensitive adhesive is one type or two or more types of rubber-based polymers.
- An acrylic polymer means a polymer containing monomer units derived from acrylic monomers in the polymer structure, and typically a polymer containing monomer units derived from acrylic monomers in a proportion exceeding 50% by weight.
- the acrylic monomer refers to a monomer having at least one (meth) acryloyl group in one molecule.
- the said (meth) acryloyl group is the meaning which points out an acryloyl group and a methacryloyl group comprehensively.
- a pressure-sensitive adhesive layer (rubber-based pressure-sensitive adhesive layer) mainly composed of a rubber-based pressure-sensitive adhesive can be preferably used.
- the rubber-based pressure-sensitive adhesive may contain one or more rubber-based polymers selected from natural rubber and synthetic rubber.
- the “main component” means a component contained in an amount exceeding 50% by weight unless otherwise specified.
- the natural rubber is not particularly limited, and for example, standard malaysian rubber (SMR), standard vietnamese rubber (SVR), ribbed smoked sheet (RSS), pale crepe and the like can be used.
- SMR standard malaysian rubber
- SVR standard vietnamese rubber
- RSS ribbed smoked sheet
- pale crepe and the like can be used.
- the Mooney viscosity of the natural rubber contained in the rubber adhesive is not particularly limited.
- the natural rubber has a Mooney viscosity (Mooney viscosity MS 1 + 4 (100 ° C.)) of about 10 or more (typically 30 or more, preferably 50 or more, more preferably 65) under the measurement condition of MS (1 + 4) 100 ° C. Or more).
- the Mooney viscosity MS 1 + 4 (100 ° C.) of the natural rubber is typically 150 or less, and usually 120 or less (for example, 100 or less).
- natural rubber having a Mooney viscosity MS 1 + 4 (100 ° C.) of about 10 to 100 eg, about 30 to 95
- natural rubber having a Mooney viscosity MS 1 + 4 (100 ° C.) of about 50 to 90 eg, about 65 to 85
- natural rubber having a Mooney viscosity MS 1 + 4 (100 ° C.) of more than 70 typically greater than 70 and 90 or less, for example, about 72 to 85
- the Mooney viscosity can be adjusted by a general method such as mastication.
- the natural rubber in a preferred embodiment, can be used in a form in which mastication is not performed or the degree of mastication is low.
- a rubber-based pressure-sensitive adhesive containing natural rubber tends to exhibit good chemical resistance since the natural rubber has a relatively high molecular weight (that is, a long molecular chain).
- the Mooney viscosity MS 1 + 4 (100 ° C.) is greater than 70 (typically greater than 70 and less than or equal to 100), more preferably greater than or equal to 75 (typically 75 to 100).
- 80 or more (typically 80 to 100, 85 or more, for example 85 to 120 or 85 to 100) natural rubber may be preferably used.
- Such natural rubber having a relatively high Mooney viscosity MS 1 + 4 (100 ° C.) is, for example, a non-crosslinked adhesive layer as described later, or a rubber-based adhesive having a composition in which the rubber-based polymer is substantially made of natural rubber. It can be particularly preferably employed in the agent layer (which can be a non-crosslinked type pressure-sensitive adhesive layer).
- the synthetic rubber examples include polyisoprene, polybutadiene, polyisobutylene, butyl rubber, styrene butadiene rubber (SBR), styrene block copolymer, and the like.
- Other examples of the synthetic rubber include ethylene propylene rubber, propylene butene rubber, and ethylene propylene butene rubber.
- Still another example of the synthetic rubber is a graft-modified natural rubber obtained by grafting other monomers to natural rubber.
- the other monomer may be one or more monomers that can be grafted to natural rubber, such as an acrylic monomer and styrene.
- the styrene block copolymer examples include a styrene isoprene block copolymer, a styrene butadiene block copolymer, and hydrogenated products thereof.
- the styrene isoprene block copolymer refers to a copolymer having at least one styrene block and isoprene block. The same applies to the styrene-butadiene copolymer.
- the styrene block refers to a segment containing styrene as a main monomer (meaning a copolymerization component exceeding 50% by weight; the same shall apply hereinafter).
- a segment consisting essentially of styrene is a typical example of a styrene block as used herein. The same applies to the isoprene block and butadiene block.
- the styrenic block copolymer has a styrene content of 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 12 to 35% by weight (eg 15 to 30% by weight). ) Can be used.
- the styrene content refers to the weight ratio of the styrene component to the total weight of the block copolymer, and can be measured by NMR (nuclear magnetic resonance spectroscopy).
- the styrenic block copolymer may be a polymer having a linear structure such as a diblock copolymer or a triblock copolymer as a main component, and a polymer having a radial structure as a main component. You may do.
- An example of a preferable rubber-based pressure-sensitive adhesive is a pressure-sensitive adhesive containing natural rubber and synthetic rubber as a rubber-based polymer.
- synthetic rubber used in combination with natural rubber for example, one or more of the various synthetic rubbers described above can be employed.
- a synthetic rubber having a composition in which a styrene component is copolymerized, such as a styrene block copolymer or SBR, can be preferably used.
- a combination of natural rubber and a styrene isoprene block copolymer is particularly preferred from the standpoint of non-glue residue.
- the styrene isoprene block copolymer one having a styrene content of 5 to 50% by weight, preferably 10 to 45% by weight, more preferably 12 to 35% by weight (for example, 15 to 30% by weight) may be used. it can. Further, a styrene isoprene block copolymer mainly composed of a polymer having a radial structure is preferable. As a commercial item of the styrene isoprene block copolymer which can be used preferably, a brand name "Quintac 3460C" (made by Nippon Zeon Co., Ltd.) is mentioned, for example.
- the content ratio is not particularly limited.
- the composition may include 10 to 110 parts by weight (preferably 15 to 80 parts by weight, more preferably 20 to 40 parts by weight) of synthetic rubber with respect to 100 parts by weight of natural rubber.
- the ratio of the total weight of natural rubber and synthetic rubber to the total weight of the pressure-sensitive adhesive layer is typically 30 to 90% by weight, preferably 40 to 80% by weight, more preferably It can be 40 to 70% by weight, for example 45 to 60% by weight.
- the ratio of the total weight of natural rubber and synthetic rubber to the total weight of the pressure-sensitive adhesive layer is 20 to 70% by weight (more preferably 20 to 60% by weight, for example 30 to 60% by weight). can do.
- the rubber-based polymer contained in the pressure-sensitive adhesive is substantially a natural rubber-based pressure-sensitive adhesive, that is, 95% by weight or more (typically 98% by weight or more). For example, 99% by weight or more).
- a pressure-sensitive adhesive in which the rubber-based polymer is substantially composed of synthetic rubber that is, 95% by weight or more (typically 98% by weight or more, for example, 99% by weight)
- the above is an adhesive made of synthetic rubber.
- the technique disclosed here can be preferably implemented in the form of a masking sheet having an adhesive layer made of a non-crosslinking type adhesive.
- the “pressure-sensitive adhesive layer composed of a non-crosslinking type pressure-sensitive adhesive” refers to an intentional treatment for forming a chemical bond between base polymers when the pressure-sensitive adhesive layer is formed (that is, a crosslinking treatment, for example, It refers to a pressure-sensitive adhesive layer in which a crosslinking agent is not blended). Since such a pressure-sensitive adhesive layer tends to be excellent in flexibility, it has good followability to unevenness that may exist on the surface of the adherend, and can exhibit good adhesion to the surface of the adherend.
- the surface may have unevenness of up to about 20 ⁇ m), or before or after application of the masking sheet
- a pressure-sensitive adhesive layer made of a non-crosslinking type pressure-sensitive adhesive.
- the technology disclosed herein includes, for example, a non-crosslinking type rubber-based pressure-sensitive adhesive layer, and the rubber-based polymer contained in the rubber-based pressure-sensitive adhesive layer is substantially made of natural rubber, and the Mooney viscosity MS of the natural rubber is 1 + 4 (100 ° C.) is greater than 70 (typically greater than 70 and less than or equal to 100), more preferably greater than or equal to 75 (typically 75 to 100), for example greater than or equal to 80 (typically 80 to 100; 85 or more, such as 85 to 120 or 85 to 100).
- the pressure-sensitive adhesive layer in the technique disclosed herein may contain a tackifier in addition to the base polymer.
- a tackifier By including a tackifier, the adhesive force to the adherend (the article to be treated) can be improved, and the masking performance or its reliability (stability) can be enhanced.
- the tackifier known rosin resins, petroleum resins, terpene resins, phenol resins and the like can be used.
- rosin resin examples include disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, rosin derivatives such as fumarated rosin, phenol-modified rosin, rosin ester, and the like.
- phenol-modified rosin examples include those obtained by adding a phenol to a natural rosin or rosin derivative, or a phenol-modified rosin obtained by reacting a resole-type phenol resin with a natural rosin or rosin derivative. It is done. Phenol-modified rosin can be used as a metal salt.
- the rosin ester examples include esterified products obtained by reacting the rosin resin with a polyhydric alcohol.
- rosin phenol resin may be an esterified product.
- terpene resins include terpene resins, terpene phenol resins, aromatic modified terpene resins, hydrogenated terpene resins, and the like.
- Examples of petroleum resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, aliphatic / aromatic copolymer (C5 / C9) petroleum resins, and hydrogenated products thereof.
- C5 / C9 petroleum resins aliphatic / aromatic copolymer
- hydrogenated products thereof for example, alicyclic petroleum resins obtained by hydrogenating aromatic petroleum resins, various modified products thereof (for example, maleic anhydride modified products) and the like.
- terpene resins include terpene resins and modified terpene resins.
- the terpene resin include polymers of terpenes (typically monoterpenes) such as ⁇ -pinene, ⁇ -pinene, d-limonene, l-limonene, and dipentene.
- the terpene resin may be a homopolymer of one terpene or a copolymer of two or more terpenes. Examples of one type of terpene homopolymer include ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer and the like.
- modified terpene resin examples include those obtained by modifying the terpene resin as described above (phenol modification, styrene modification, hydrogenation modification, hydrocarbon modification, etc.). Specific examples include terpene phenol resins, styrene-modified terpene resins, hydrogenated terpene resins, and the like.
- terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, and a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin) and a terpene homopolymer or copolymer. It is a concept including both a polymer (terpene resin, typically unmodified terpene resin) and a phenol-modified polymer (phenol-modified terpene resin).
- phenolic resins include condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin and formaldehyde.
- Other examples of phenolic resins include resole obtained by addition reaction of the above phenols with formaldehyde in the presence of an alkali catalyst, and novolak obtained by condensation reaction of the above phenols with formaldehyde in the presence of an acid catalyst. It is done.
- tackifier that can be preferably used, the trade name “Quinton D-200” (maleic anhydride-modified C5 / C9 petroleum resin, softening point of about 100 ° C., Nippon Zeon Co., Ltd.)
- Product name “Sumilite PR12603N” phenol-modified rosin, softening point about 130 ° C., manufactured by Sumitomo Bakelite Co., Ltd.
- trade name “YS Resin PX1150” terpene resin, softening point about 115 ° C., manufactured by Yasuhara Chemical Co., Ltd.
- the content of the tackifier is not particularly limited, and can be set so that appropriate adhesive performance is exhibited depending on the purpose and application.
- the content of the tackifier relative to 100 parts by weight of the base polymer can be, for example, 5 to 500 parts by weight.
- the content of the tackifier with respect to 100 parts by weight of the base polymer can be 20 to 350 parts by weight, preferably 50 to 300 parts by weight, and more preferably 65 to 250 parts by weight. preferable.
- the content of the tackifier with respect to 100 parts by weight of the base polymer can be, for example, 20 to 150 parts by weight, preferably 30 to 120 parts by weight, more preferably 40 to 100 parts by weight. is there.
- the content of the tackifier described above can be preferably applied to, for example, a rubber-based pressure-sensitive adhesive (typically, a pressure-sensitive adhesive containing a combination of natural rubber and synthetic rubber).
- the content of the tackifier with respect to 100 parts by weight of the base polymer can be, for example, 5 to 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 60 parts by weight. Parts by weight (for example, 20 to 40 parts by weight).
- the content of the tackifier described above can be preferably applied to, for example, a pressure-sensitive adhesive (preferably a non-crosslinked type pressure-sensitive adhesive) whose rubber-based polymer is substantially made of natural rubber.
- the masking sheet disclosed herein can be implemented in an embodiment in which the proportion of the tackifier in the pressure-sensitive adhesive layer is, for example, 10 to 85% by weight.
- the ratio of the tackifier in the pressure-sensitive adhesive layer is usually preferably 15% by weight or more, and more preferably 20% by weight or more.
- the proportion of the tackifier in the pressure-sensitive adhesive layer is usually suitably 75% by weight or less, and 70% by weight or less.
- the proportion of the tackifier in the pressure-sensitive adhesive layer may be 40% by weight or more, and may be 50% by weight or more (for example, 60% by weight or more).
- a ratio of tackifier can be preferably applied to, for example, a rubber-based pressure-sensitive adhesive (typically a pressure-sensitive adhesive containing a combination of natural rubber and synthetic rubber).
- the proportion of the tackifier in the pressure-sensitive adhesive layer can be 10 to 70% by weight, and more preferably 10 to 50% by weight (for example, 15 to 35% by weight).
- a ratio of the tackifier can be preferably applied to, for example, a pressure-sensitive adhesive (preferably a non-crosslinked type pressure-sensitive adhesive) in which the rubber polymer is substantially made of natural rubber.
- the tackifier those having a softening point (softening temperature) of about 60 ° C. or higher (preferably about 80 ° C. or higher, more preferably about 90 ° C. or higher) can be preferably used.
- a softening point equal to or higher than the lower limit value described above, a pressure-sensitive adhesive layer excellent in non-glue residue is easily formed.
- the upper limit of the softening point is not particularly limited, and can be, for example, about 200 ° C. or lower (typically 180 ° C. or lower).
- the softening point of the tackifier can be measured based on the softening point test method (ring and ball method) specified in JIS K2207.
- the tackifier may be preferably used in an aspect including a tackifier having a softening point of 120 ° C or higher. Only a tackifier having a softening point of 120 ° C or higher may be used, or a tackifier having a softening point of 120 ° C or higher and a tackifier having a softening point of less than 120 ° C may be used in combination. In the latter case, the proportion of the tackifier having a softening point of 120 ° C. or higher in the tackifier used is usually suitably 5% by weight or more, and 10% by weight or more (for example, 15% by weight or more). It is preferable to do. The upper limit of the proportion of the tackifier having a softening point of 120 ° C. or higher can be, for example, 95% by weight or less, and is usually 70% by weight or less (for example, less than 50% by weight).
- the tackifier may be preferably used in an aspect including a tackifier having a softening point of less than 120 ° C. Only a tackifier having a softening point of less than 120 ° C may be used, or a tackifier having a softening point of 120 ° C or higher and a tackifier having a softening point of less than 120 ° C may be used in combination. In the latter case, the proportion of the tackifier having a softening point of less than 120 ° C. in the tackifier used can be, for example, 30% by weight or more, and is usually suitably 50% by weight or more. It is preferable to set it as weight% or more.
- the proportion of the tackifier having a softening point of less than 120 ° C. may be 95% by weight or more, or 100% by weight.
- a terpene resin having a softening point lower than 120 ° C. typically 80 ° C. or higher and lower than 120 ° C.
- the tackifier can be used singly or in combination of two or more.
- a combination of a petroleum resin and a rosin resin can be preferably employed as the tackifier.
- the combination of petroleum resin and rosin resin can be preferably employ
- the relationship between the amounts used is not particularly limited.
- the amount of the petroleum resin used relative to 1 part by weight of the rosin resin can be, for example, 0.1 to 20 parts by weight, usually 0.7 to 15 parts by weight. 0 to 10 parts by weight (typically more than 1.0 part by weight and 10 parts by weight or less) is preferable.
- a more preferable result can be realized by setting the amount of the petroleum resin used to 1 to 8 parts by weight of the rosin resin to 1.5 to 8 parts by weight.
- the amount of the rosin resin used relative to 100 parts by weight of the petroleum resin can be, for example, 10 to 200 parts by weight, usually 20 to 120 parts by weight. 30 to 80 parts by weight is preferable.
- the above-described relationship between the amount of the petroleum resin and rosin resin used can be preferably applied to, for example, a rubber-based adhesive (typically, an adhesive including a combination of natural rubber and synthetic rubber).
- a terpene-based resin can be preferably employed as a tackifier.
- a pressure-sensitive adhesive preferably a non-crosslinked type pressure-sensitive adhesive
- the rubber-based polymer is substantially made of natural rubber.
- the technology disclosed herein is that more than 50% by weight (more preferably 70% by weight or more, typically 85% by weight or more, for example 95% by weight or more) of the tackifier is a terpene resin (typically terpene). Resin) can be preferably implemented.
- the natural rubber may have, for example, a Mooney viscosity MS 1 + 4 (100 ° C.) of 80 or more (typically 80 to 100).
- the pressure-sensitive adhesive layer in the technology disclosed herein can be formed from a pressure-sensitive adhesive composition containing a crosslinking agent.
- a crosslinking agent tends to improve the non-glue residue of the masking sheet.
- crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyl etherified melamine crosslinking agents, metal chelate crosslinking agents, and the like. Any known or commonly used crosslinking agent in the field of pressure-sensitive adhesives can be used.
- a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
- the amount of the crosslinking agent used can be, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the base polymer, and usually 1 to 8 parts by weight is appropriate. is there. Alternatively, substantially no cross-linking agent may be used.
- an isocyanate-based crosslinking agent can be mentioned.
- the isocyanate-based crosslinking agent is typically an isocyanate having two or more isocyanate groups in one molecule.
- the isocyanate may be either an aromatic isocyanate or an aliphatic isocyanate.
- the isocyanate is preferably an aromatic isocyanate.
- a commercial item of an aromatic isocyanate type crosslinking agent a brand name "Coronate L" (made by Nippon Polyurethane Co., Ltd.) is mentioned, for example.
- An isocyanate type crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
- the isocyanate is preferably a polyisocyanate having 3 or more isocyanate groups in one molecule, more preferably selected from the group consisting of aromatic polyisocyanates and aliphatic polyisocyanates. At least one.
- the polyisocyanate include polyhydric alcohol adducts of aromatic diisocyanates and polyhydric alcohol adducts of aliphatic diisocyanates.
- a compound containing an isocyanate group at the terminal obtained by reacting a polyhydric alcohol with an excess amount of the diisocyanate can be preferably used as the polyisocyanate.
- aromatic diisocyanate examples include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like.
- tolylene diisocyanate is exemplified as a preferable example from the viewpoint of reactivity and the like.
- Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, isophorone diisocyanate, Examples thereof include cyclohexyl diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Of these, 1,6-hexamethylene diisocyanate is a preferred example from the viewpoint of reactivity and the like.
- polyhydric alcohol examples include aliphatic polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Of these, trimethylolpropane is preferable.
- the pressure-sensitive adhesive layer in the technology disclosed herein can be formed from a pressure-sensitive adhesive composition containing a hydroxyl group-containing polymer.
- the hydroxyl group-containing polymer is preferably used in combination with a hydroxyl group reactive crosslinking agent.
- the separation property of the pressure-sensitive adhesive means that when two pressure-sensitive adhesive layers that are adhered (self-adhering) to each other by being separated are separated from each other, stringing of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer (adhesion) The phenomenon that the agent is locally stretched into a filament or thin film) is prevented or suppressed, or the adhesive is broken and separated early in the stringing (that is, before the adhesive layer is greatly deformed). .
- the separation property of the pressure-sensitive adhesive is sometimes referred to as “glue breakage”.
- the combined use of a hydroxyl group-containing polymer and a hydroxyl group reactive crosslinking agent is particularly significant in a masking sheet that can be used in a half-cut form as described later, for example.
- rubber-based pressure-sensitive adhesives tend to be easily blocked (strongly self-adhesive), and therefore a masking sheet having a rubber-based pressure-sensitive adhesive layer should be used in combination with a hydroxyl group-containing polymer and a hydroxyl group reactive crosslinking agent. Is particularly significant.
- hydroxyl group-reactive crosslinking agent a compound having a functional group that reacts with a hydroxyl group (for example, an isocyanate group, an epoxy group, a melamine group, an aldehyde group, etc.) (preferably two functional groups that react with a hydroxyl group in one molecule).
- a compound having the above can be used.
- the hydroxyl group-containing polymer a polymer having an average of 1 or more (typically 1.5 or more) hydroxyl groups per molecule can be preferably used.
- the number average molecular weight (Mn) of the hydroxyl group-containing polymer is not particularly limited and can be, for example, about 500 to 500,000. From the viewpoint of compatibility with other components and reactivity, the Mn of the hydroxyl group-containing polymer is usually about 500 to 50,000, preferably about 500 to 20,000, preferably about 500 to 10,000 (for example, about 500 to 5,000). ) Is more preferable. Mn can be measured according to ASTM D2503.
- Non-limiting examples of the hydroxyl group-containing polymer include polyethylene polyols such as polyethylene glycol, polypropylene polyols such as polypropylene glycol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol and the like.
- Preferable examples from the viewpoint of compatibility with the base polymer include hydrogenated polyisoprene polyol, polyisoprene polyol, polybutadiene polyol, and hydrogenated polybutadiene polyol.
- the hydroxyl value [mgKOH / g] of the hydroxyl group-containing polymer is preferably 5 or more (typically 10 or more, for example, 20 or more) from the viewpoint of reactivity. Moreover, it is preferable that the hydroxyl value [mgKOH / g] of a hydroxyl-containing polymer is 95 or less (typically 80 or less) from a viewpoint of the adhesive force of an adhesive layer. In a preferred embodiment, a hydroxyl group-containing polymer having a hydroxyl value [mgKOH / g] in the range of 20 to 80 can be used. The hydroxyl value can be measured according to JIS K1557: 1970.
- hydroxyl group-containing polymer examples include, for example, Poly bd R-45HT (liquid polybutadiene having a hydroxyl group at the terminal, Mn 2800, hydroxyl value 46.6 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Poly ip (liquid polybutadiene having a hydroxyl group at the terminal) Isoprene, Mn 2500, hydroxyl value 46.6 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd., Epol (liquid hydrogenated polyisoprene having a hydroxyl group at the terminal, Mn 2500, hydroxyl value 50.5 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), GI- 1000 (liquid polybutadiene having a hydroxyl group, Mn 1500, hydroxyl value 60 to 75 mg KOH / g, manufactured by Nippon Sod
- the content of the hydroxyl group-containing polymer with respect to 100 parts by weight of the base polymer is not particularly limited. Usually, the content of the hydroxyl group-containing polymer with respect to 100 parts by weight of the base polymer is suitably about 1 to 20 parts by weight, and about 2 to 15 parts by weight (for example, about 2.5 to 10 parts by weight). It is preferable.
- the content of the hydroxyl group-containing polymer is such that the A value in the following formula (1) is preferably 1 to 12000, more preferably 10 to 5000, still more preferably 25 to 2500 (typically 50 to 1000, For example, it can be set to be 75 to 500).
- A (Hydroxyl value of hydroxyl group-containing polymer [mgKOH / g]) ⁇ (Number of parts by weight of hydroxyl group-containing polymer with respect to 100 parts by weight of base polymer) (1)
- the increase in the A value tends to improve the adhesiveness of the pressure-sensitive adhesive layer.
- a value is not too large, there exists a tendency for adhesiveness (for example, 90 degree
- the content of the hydroxyl group-containing polymer is such that the B value in the following formula (2) is preferably 0.1 to 20, more preferably 0.2 to 10, still more preferably 0.3 to 5, For example, it can be set to be 0.4-3.
- B (Hydroxyl value of hydroxyl group-containing polymer [mgKOH / g] ⁇ Hydroxyl group-containing polymer weight [g]) / Weight of adhesive layer [g] (2)
- the relationship between the hydroxyl group-containing polymer content and the hydroxyl group-reactive crosslinking agent content is not particularly limited.
- the amount of the hydroxyl group-containing polymer used relative to 1 part by weight of the hydroxyl group reactive crosslinking agent can be, for example, 0.1 to 20 parts by weight, and is usually 0.5 to 15 from the viewpoint of effectively exhibiting the advantages of crosslinking.
- the amount is suitably 1 part by weight, preferably 1 to 10 parts by weight or less, more preferably more than 1 part by weight and 5 parts by weight or less (eg 1.2 to 3 parts by weight).
- the pressure-sensitive adhesive composition may contain one or more urethanization catalysts.
- a hydroxyl group-containing polymer for example, an isocyanate-based crosslinking agent
- a urethanization catalyst for example, an isocyanate-based crosslinking agent
- the urethanization catalyst include tin compounds such as dibutyltin dilaurate and dioctyltin dilaurate, metal carboxylates such as zinc, cobalt, copper, and bismuth, and 1,4-diazabicyclo [2.2.2] octane.
- Examples include amine compounds, chelate compounds of metals such as iron, titanium, and zirconium. Further, organic acid bismuth salts (alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, and bismuth resin acid resin mainly composed of two or more of them) And bismuth salts of aromatic organic acids such as benzoic acid, cinnamic acid and p-oxycinnamic acid.
- organic acid bismuth salts alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid, podocarpic acid, and bismuth resin acid resin mainly composed of two or more of them
- bismuth salts of aromatic organic acids such as benzoic acid, cinnamic acid and p-oxycinnamic acid.
- iron chelate compounds dibutyltin dilaurate, dioctyltin dilaurate, and bismuth resinate are preferable in terms of compatibility with the pressure-sensitive adhesive and urethanization reaction, and iron chelate compounds in terms of reactivity. More preferred.
- the content of the urethanization catalyst is not particularly limited. For example, 0.001 to 2.0 parts by weight (preferably 0.005 to 1.5 parts by weight, more preferably 0.008 to 1.5 parts by weight with respect to 100 parts by weight of the base polymer). 1.0 part by weight).
- the pressure-sensitive adhesive layer in the technology disclosed herein is a leveling agent, a crosslinking aid, a plasticizer, a softening agent, a colorant (dye, pigment, etc.), and a filler as long as the effects of the present invention are not significantly hindered.
- a known additive that can be used for the pressure-sensitive adhesive such as an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant, or a light stabilizer, may be included as necessary.
- an anti-aging agent for example, a phenol-based anti-aging agent can be preferably used.
- the blending amount of the antioxidant is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the base polymer.
- trade name “NOCRACK NS-6” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
- the masking sheet disclosed here can be formed by a conventionally known method.
- a method (direct method) of forming the pressure-sensitive adhesive layer by directly applying (typically applying) the pressure-sensitive adhesive composition to the substrate as described above and drying it can be employed.
- a method for forming a pressure-sensitive adhesive layer on the surface by applying a pressure-sensitive adhesive composition to a surface having a peelable property (peeling surface) and drying it, and transferring the pressure-sensitive adhesive layer to a substrate (transfer method) May be adopted. These methods may be combined.
- peelable property peelable property
- transfer method May be adopted.
- the pressure-sensitive adhesive composition can be performed using a conventionally known coater such as a gravure roll coater, a die coater, or a bar coater. From the viewpoint of promoting the crosslinking reaction and improving productivity, the pressure-sensitive adhesive composition is preferably dried under heating.
- the drying temperature can be, for example, about 40 to 150 ° C., and is usually preferably about 60 to 130 ° C.
- the thickness of an adhesive layer is not specifically limited, It can adjust suitably according to the objective.
- the thickness of the pressure-sensitive adhesive layer can be, for example, about 1 ⁇ m to 100 ⁇ m. From the viewpoint of adhesion to the adherend surface, the preferred thickness is 5 ⁇ m or more, more preferably 10 ⁇ m or more. For applications that are applied to the shot peening surface, the thickness of the pressure-sensitive adhesive layer is preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more.
- the thickness of the pressure-sensitive adhesive layer is preferably 80 ⁇ m or less, more preferably 60 ⁇ m or less, and even more preferably. Is 50 ⁇ m or less. In one preferred example of the masking sheet disclosed herein, the thickness of the pressure-sensitive adhesive layer can be 20 to 40 ⁇ m.
- the release liner is not particularly limited.
- a release liner having a release treatment layer on the surface of a liner substrate such as a resin film or paper (may be a paper laminated with a resin such as polyethylene), or a fluorine-based release liner.
- a release liner made of a low adhesive material such as a polymer (polytetrafluoroethylene, etc.) or a polyolefin resin (polyethylene, polypropylene, etc.) can be used.
- the release treatment layer may be formed, for example, by surface-treating the liner base material with a release agent such as silicone-based, long-chain alkyl-based, olefin-based, fluorine-based, or molybdenum sulfide.
- a release agent such as silicone-based, long-chain alkyl-based, olefin-based, fluorine-based, or molybdenum sulfide.
- a release treatment layer formed using a silicone-based release agent can be preferably employed.
- a release treatment layer formed using a non-silicone release agent can be employed.
- the non-silicone release agent include a long-chain alkyl release agent, an olefin release agent, and a fluorine release agent.
- preferable non-silicone release agents include long-chain alkyl release agents and olefin release agents. Of these, long-chain alkyl release agents are preferred.
- the release agent used for forming the release treatment layer on the second surface of the substrate the same one can be preferably used.
- the mode of anodizing treatment performed using the masking sheet disclosed herein is not particularly limited, and general chromic acid anodizing treatment, phosphoric acid anodizing treatment, boric acid anodizing treatment, sulfuric acid anodizing treatment, sulfuric acid-boric acid anodizing treatment Etc.
- the material and shape of the article to be anodized (article to be processed) are not particularly limited.
- the article to be treated is typically a light metal member.
- the “light metal member” refers to a metal member having a surface composed of a simple light metal such as aluminum, magnesium, titanium, or an alloy (light alloy) containing the light metal as a main component.
- the “aluminum member” means a metal member having a surface made of aluminum or an aluminum alloy (an alloy containing aluminum as a main component).
- the aluminum alloy include 2000 series alloy, 3000 series alloy, 4000 series alloy, 5000 series alloy, 6000 series alloy and 7000 series alloy.
- a preferable application object of the masking sheet disclosed herein includes an aluminum member having a surface made of aluminum (typically 1000 series aluminum) or 2000 series alloy (for example, duralumin A2024, duralumin A2017, etc.).
- articles to be anodized include metal members used as exterior parts for transport equipment and other structural members.
- transportation equipment include automobiles (including passenger cars, trucks, buses, auto three-wheelers, tractors, snow vehicles, bulldozers, amphibious vehicles, etc.), railway vehicles (trains such as Shinkansen, diesel cars, linear motors). Cars, cable cars, monorails, trolley buses, etc.), aircraft (including airplanes, helicopters, air cushion boats, etc.), ships (including large ships, small ships, water scooters, etc.), etc.
- One preferred example is an aluminum member (typically a duralumin member) for an aircraft exterior panel.
- the surface of the metal member subjected to anodizing treatment may be subjected to shot peening treatment in advance. Further, the metal member may be milled for the purpose of thickness adjustment or the like. Or you may perform processing, such as usual washing
- an etching process may be provided between the shot peening process and the chemical process (anodizing process).
- the masking sheet for the etching process may be used as the masking sheet for the anodizing process after the etching process. Alternatively, the masking sheet for the etching process may be peeled off after the etching process and a new masking sheet for the anodizing process may be attached. Good.
- the masking sheet disclosed herein is preferably used as a masking sheet that is used by being attached to a non-treatment target portion of the metal member, for example, when anodizing the metal member. Can be done.
- it is suitable as a masking sheet for anodizing treatment of light metal members.
- the masking sheet disclosed herein can be preferably applied to an article (typically a metal member, particularly a light metal member such as aluminum or aluminum alloy) that is further processed (subsequent processing) after anodizing.
- the subsequent process may be an undercoat layer (primer layer) forming process, a coating process, or the like performed on the article after the anodizing process.
- the subsequent process may be a process of sealing the anodic oxide film formed by the anodizing process.
- the subsequent process may be a chemical process (for example, a process for applying a liquid such as a water-based or solvent-based primer or a water-based or solvent-based paint), or a process other than the chemical process (such as a powder coating process). Dry treatment).
- the masking sheet disclosed herein has a 90-degree peel strength (vs. duralumin 90-degree peel strength) measured with a flat plate made of duralumin A2024 as an adherend, for example, about 0.5 N / It can implement in the aspect which is 20 mm or more.
- the 90 ° peel strength against duralumin is usually advantageously 1.0 N / 20 mm or more, 1.5 N / 20 mm or more (for example, 2.0 N / 20 mm or more). ) Is preferable.
- the 90 ° peel strength against duralumin is preferably 3.0 N / 20 mm or more, for example, 4.5 N / 20 mm or more.
- the upper limit of the 90 ° peel strength against duralumin is not particularly limited, but is usually 25 N / 20 mm or less, and 20 N / 20 mm or less (typically 15 N / 20 mm or less) from the viewpoint of peeling workability and non-glue residue. For example, 10 N / 20 mm or less).
- the 90 ° peel strength against duralumin is 300 mm / 90 in the 90 ° direction from the surface of the duralumin plate 30 minutes after the masking sheet is attached to the duralumin plate (duralumin A2024 flat plate) at a measurement temperature of 23 ° C. It can be measured by peeling at a pulling rate of minutes.
- the 90-degree peel strength against duralumin can be adjusted by, for example, the composition of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet, the thickness of the pressure-sensitive adhesive layer, and the like.
- the masking sheet disclosed herein has good non-glue residue on the article to be treated (adhered body).
- the masking sheet disclosed herein has good non-glue residue on the article to be treated (adhered body).
- the masking sheet disclosed herein has good non-glue residue on the article to be treated (adhered body).
- the 90-degree peel strength measurement for duralumin it is preferable that no adhesive residue is left on the duralumin plate as the adherend.
- the masking sheet disclosed herein preferably has a chemical solution penetration distance (to a duralumin flat plate) of 5 mm or less in the chemical solution penetration prevention evaluation described in the examples described later. More preferably, it is more preferably 1 mm or less.
- the masking sheet excellent in chemical solution intrusion prevention property can be preferably used in such a manner that after the anodizing treatment, the subsequent treatment step is performed in a state where the masking sheet is subsequently attached to the adherend.
- the masking sheet disclosed herein can also be used for masking a portion not to be painted (a portion not to be treated) in a painting step performed after the anodizing treatment step.
- the coating step may be a step of performing a coating process on the processing target article to which the masking sheet that has been pasted on the processing target article at the time of anodizing treatment is continuously (continuously) pasted.
- paint refers to a concept including a so-called undercoat (sometimes referred to as a primer), intermediate coat, finish paint (sometimes called a top coat), and the like.
- the form of the paint used in the coating process is not particularly limited, and may be a form of water-based paint, solvent-based paint, powder paint, or the like.
- the end face of the adhesive layer depends on the composition of the solvent that forms the paint and the composition of the adhesive layer. It is possible that the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may dissolve into the paint accumulated in the layer. Thereafter, when the coating material accumulated on the other surface of the pressure-sensitive adhesive layer is dried, the pressure-sensitive adhesive dissolved from the pressure-sensitive adhesive layer typically forms a thin film spreading outward from the masking sheet. This thin film tends to remain (glue residue) on the article to be processed when the masking sheet is peeled off.
- the thickness Ht of the masking sheet used continuously from the anodizing process to the coating process is preferably 0.30 mm or less, more preferably 0.25 mm or less (for example 0.20 mm or less), and 0.15 mm or less (typical More specifically, it is more preferably less than 0.15 mm.
- the masking sheet before being attached to the object to be processed can be grasped as a masking pressure-sensitive adhesive product for masking the non-processing object part of the object to be processed.
- a masking pressure-sensitive adhesive product for masking the non-processing object part of the object to be processed.
- Such an adhesive product can be configured as a masking sheet with a release liner including, for example, any masking sheet disclosed herein and a release liner that protects the adhesive surface of the masking sheet.
- a masking sheet 10 constituting a masking sheet with a release liner (pressure-sensitive adhesive product) 100 is adjacent on a continuous (one-line) release liner 3.
- the pressure-sensitive adhesive product 100 has a masking sheet 10 held on the release liner 3 from the second surface 1 ⁇ / b> B side of the substrate 1 to the pressure-sensitive adhesive layer side surface 3 ⁇ / b> A.
- the cutting mode in which the masking sheet is divided and the release liner is not divided in this way, and the cutting state formed by such a cutting mode may be referred to as “half cut”.
- the adhesive product 100 in a half-cut form typically separates the first adhesive piece 10a from the second adhesive piece 10b and the release liner 3 while leaving the second adhesive piece 10b on the release liner 3, and the separation.
- the first pressure-sensitive adhesive piece 10a thus used is used in a mode of being affixed to the masking target portion of the processing target article. In this way, by handling the first adhesive piece 10a before application as the half-cut adhesive product 100, the same handling can be performed regardless of the size and the outer shape of the first adhesive piece 10a. This is particularly significant when the first adhesive piece 10a has a relatively complicated shape or when the size of the first adhesive piece 10a is relatively small. Moreover, since at least a part of the release liner 3 protrudes from the first adhesive piece 10a, it is advantageous in terms of operability (pickup property) when the first adhesive piece 10a is peeled off from the release liner 3.
- the adjacent first pressure-sensitive adhesive piece 10a and the second pressure-sensitive adhesive piece 10b are cut (half-cut) after a lapse of time, for example, as shown in FIG.
- the pressure-sensitive adhesive layers 2a and 2b tend to come into contact with each other at the opposing cut end faces.
- the elapsed time after half-cutting, the storage conditions of the pressure-sensitive adhesive product, blocking occurs on the opposing end surfaces of the pressure-sensitive adhesive layers 2a and 2b, and the second pressure-sensitive adhesive piece 10b to the first pressure-sensitive adhesive piece 10a. In some cases, stringing or the like may occur.
- the end face of the pressure-sensitive adhesive layer 2a can be irreversibly deformed.
- the deformed portion can be a starting point for entering the chemical solution. Therefore, in the masking pressure-sensitive adhesive product in a half-cut form, the blocking of the pressure-sensitive adhesive on the cut end surface is suppressed, or the separation of the pressure-sensitive adhesive is improved, thereby preventing or suppressing the occurrence of the stringing or the like. Thus, the masking performance or its reliability (stability) can be further improved.
- a technique of crosslinking the pressure-sensitive adhesive by a reaction between a hydroxyl group-containing polymer and a hydroxyl group reactive crosslinking agent can be preferably employed as one technique for preventing or suppressing the occurrence of the above stringing or the like. That is, it is effective to use a pressure-sensitive adhesive containing a crosslinked structure of a hydroxyl group-containing polymer and a hydroxyl group reactive crosslinking agent.
- the pressure-sensitive adhesive having such a crosslinked structure can be grasped as a pressure-sensitive adhesive containing a urethane bond, for example, when an isocyanate-based crosslinking agent is employed as the hydroxyl group-reactive crosslinking agent.
- crosslinked by reaction with a hydroxyl-containing polymer and a hydroxyl-reactive crosslinking agent the separability of the adhesive at the time of isolate
- a pressure-sensitive adhesive product comprising a pressure-sensitive adhesive layer composed of a rubber adhesive having a strong self-adhesive property in a half-cut form, it is crosslinked by a reaction between a hydroxyl group-containing polymer and a hydroxyl group reactive crosslinking agent. It is effective to provide a rubber pressure-sensitive adhesive layer.
- the matter disclosed by this specification includes a base material having a first surface and a second surface, and a pressure-sensitive adhesive layer disposed on the first surface side of the base material, and the pressure-sensitive adhesive layer
- a pressure-sensitive adhesive sheet for a masking sheet in which the pressure-sensitive adhesive that constitutes is constituted by a pressure-sensitive adhesive crosslinked by the reaction of a hydroxyl group-containing polymer and a hydroxyl group-reactive crosslinking agent, is included.
- the pressure-sensitive adhesive sheet having such a configuration is suitable for use in a mode in which the occurrence of the above stringing or the like is prevented or suppressed (that is, separability is good), and is attached to the adherend after being half-cut. .
- the release liner constituting the adhesive product in a half-cut form is not particularly limited, and for example, the various release liners described above can be appropriately selected and used.
- a release liner having a release treatment layer on the surface of a liner substrate made of paper (typically, a paper on which polyethylene resin is laminated on one or both sides) or a release treatment layer on the surface of a resin film is provided.
- a release liner can be preferably employed.
- a release liner having a release treatment layer on the laminate surface of a liner substrate (polyethylene laminated paper) having a structure in which polyethylene resin is laminated on paper can be mentioned.
- the release treatment layer is not particularly limited, and for example, a layer formed using a silicone release agent can be preferably used.
- a release treatment layer formed using a non-silicone release agent such as a long-chain alkyl release agent or an olefin release agent is also preferable. Thereby, it is suppressed that peeling becomes light too much, and the operativity in the case of half cut operation and the separation operation of the half-cut adhesive piece can be improved.
- the masking sheet disclosed herein can be configured so that the chemical solution intrusion into the masking sheet is visible from the outer surface side of the masking sheet.
- the outer surface of the masking sheet refers to the surface opposite to the adhesive surface.
- the second surface of the substrate also serves as the outer surface of the masking sheet.
- the entry of the chemical into the masking sheet means that the masking sheet attached to the adherend is viewed from the outer surface side and is located on the inner side (center side) of the outer peripheral line of the masking sheet.
- the chemical solution enters the inner side (adhesive surface side) of the outer surface. Therefore, in this specification, the chemical solution intrusion into the masking sheet means that the chemical solution enters from the interface between the adhesive surface of the masking sheet and the surface of the adherend and the masking sheet sticking range (masking region), and the masking sheet.
- “visually visible” that the chemical solution has entered the masking sheet means that the chemical solution can be detected by human vision.
- the invasion of the chemical liquid into the masking sheet is visually recognized by identifying the difference in appearance between the area where the chemical liquid has entered and the area where the chemical liquid has not entered, by human vision.
- the difference in the appearance may be various changes that occur as the chemical solution enters and can be recognized through vision. For example, one or more changes among color change (color change), light transmittance change, uniformity change (for example, appearance irregularities and spots), refractive index change, fluorescence intensity change, etc. possible.
- the color change may be one or more of chromaticity, saturation, and lightness.
- the masking sheet disclosed herein may be capable of visually detecting the intrusion of the chemical into the masking sheet while being attached to the adherend (that is, without peeling from the adherend). It is preferable that the said masking sheet is comprised so that a chemical
- instruments such as a magnifying glass and a remote observation scope are used for the purpose of facilitating and improving the judgment of whether the level of chemical penetration is below the standard level or reducing the burden on the operator. It is not hindered to use.
- the masking sheet only has to be able to visually recognize the invasion of the chemical solution as a whole when viewed from the outer surface side.
- the outer surface of the masking sheet is divided into a plurality of virtual areas, it is only necessary that at least a part of the area can visually recognize the chemical intrusion, and all of the individual areas can visually recognize the chemical intrusion alone. That is not required. Of course, all the regions may be able to visually recognize the chemical solution intrusion alone.
- the masking sheet disclosed herein is typically configured so that at least a part of the masking sheet as viewed from the outside shows light transmittance.
- the visibility (visibility) of entering the chemical solution tends to be increased.
- the degree of light transmittance of the masking sheet can be evaluated by, for example, a haze value.
- the “haze value” refers to the ratio of diffusely transmitted light to total transmitted light when the measurement object is irradiated with visible light. Also called cloudy price.
- the haze value can be expressed by the following formula.
- Th is the haze value (%)
- Td is the scattered light transmittance
- Tt is the total light transmittance.
- Th (%) Td / Tt ⁇ 100
- the haze value can be adjusted by selecting the composition, thickness, surface state and the like of the base material and the pressure-sensitive adhesive layer constituting the masking sheet. The haze value can be measured according to the method described in Examples described later.
- mode has an area
- the masking sheet preferably has a haze value of 70% or less, more preferably 50% or less, and even more preferably 35% or less.
- the lower limit of the haze value is not particularly limited, and may be, for example, 5% or more (typically 10% or more).
- it is preferable that at least the haze value of the high visibility region is in the above range. Both the haze value of the high visibility region and the haze value of the low visibility region may be in the above range.
- the color of the masking sheet is not particularly limited, and may be colored or colorless.
- colored means to include black and metal colors.
- Colorless means white.
- a colorless masking sheet is preferable.
- the masking sheet is preferably configured so that the masking sheet itself has appropriate visibility.
- the visibility of the masking sheet increases, the position and shape of the masking sheet tend to be easily grasped visually. This is advantageous in visually detecting defects such as misalignment of the masking sheet, generation of wrinkles, peeling, and forgetting to attach the masking sheet.
- the masking sheet disclosed here has a relatively high area (high visibility area) and a relatively low area (low visibility area) as viewed from the outer surface side of the masking sheet. Can be configured to. According to such a configuration, the visibility of the masking sheet can be increased due to the presence of the low visibility region. Therefore, according to the masking sheet having the above-described configuration, the visibility of the chemical solution intrusion and the visibility of the masking sheet can be suitably achieved.
- the high visibility region and the low visibility region can be configured such that the visibility of the chemical solution intrusion changes discontinuously between these regions. Or you may comprise so that the visibility of chemical
- the shape and arrangement of the high visibility region and the low visibility region are not particularly limited.
- the high visibility region and the low visibility region can be arranged so as to be mixed when viewed from the outer surface of the masking sheet.
- the high visibility region and the low visibility region are mixed (distributed) almost uniformly over the entire masking sheet.
- the low-visibility areas are arranged almost uniformly in the high-visibility areas, for example, in a linear shape (stripe shape, wave shape, etc.) or a dotted shape (circular shape, polygonal shape, irregular shape, etc.). be able to.
- the masking sheet configured as described above is easy to use because it can exhibit the same performance even if it is cut into an arbitrary shape.
- the low visibility region may be a region having a relatively high haze value compared to the high visibility region.
- the haze value of the low visibility region is not particularly limited as long as it is higher than the haze value of the high visibility region.
- the haze value of the low visibility region may be, for example, 95% or more, or substantially 100%.
- the difference in haze value between the high visibility region and the low visibility region can be typically 15% or more, for example, 30% or more. From the viewpoint of better exhibiting the effect of providing the high visibility region and the low visibility region, the difference in haze value is preferably 50% or more, and more preferably 70% or more.
- a masking sheet having a high visibility region and a low visibility region can be obtained, for example, by using a base material on which a visibility adjusting layer corresponding to the shape and arrangement of the low visibility region is formed.
- the visibility adjusting layer can be, for example, a colored layer formed by printing an ink containing an appropriate colorant (pigment, dye) on a substrate.
- the visibility adjusting layer may be a metal vapor deposition layer formed by vapor-depositing a metal on a base material. From the viewpoint of avoiding the visibility adjusting layer from being affected by the chemical solution, it is advantageous to form the visibility adjusting layer on the first surface of the substrate.
- a method of roughening a partial region of the first surface or the second surface of the substrate to reduce the light transmittance of the region can be exemplified.
- the roughening can be performed by appropriately employing a chemical method such as chemical treatment or a physical method such as formation of scratches.
- the masking sheet disclosed herein can be configured such that the color of the chemical solution intrusion portion changes due to the chemical solution intrusion.
- the chemical solution intrusion can be easily visually recognized by detecting the discoloration of the masking sheet.
- the location where the color change occurs is not particularly limited as long as the color change is visible from the outer surface side of the masking sheet.
- it may be a color change of the base material, a color change of the pressure-sensitive adhesive layer, or a color change of the base material and the pressure-sensitive adhesive layer.
- the masking sheet can contain a component that promotes discoloration. By this, the visibility of chemical solution intrusion can be enhanced.
- an indicator that develops or changes color under acidic conditions can be included in the adhesive layer.
- the said indicator may be mix
- a mode in which the masking sheet is disposed only on the outer peripheral portion, a mode in which the masking sheet is disposed at a position corresponding to the mark, or the like can be employed.
- the thickness of the base material in the masking sheet having visibility can be, for example, 0.50 mm or less, preferably 0.30 mm or less, more preferably 0.20 mm or less, and still more preferably. Is 0.15 mm or less (for example, 0.12 mm or less).
- the thickness of the substrate may be 0.10 mm or less, and may be 0.09 mm or less.
- the masking sheet for anodizing treatment disclosed herein can be suitably used for uses other than anodizing treatment (typically, masking uses during chemical treatment). Accordingly, the matters disclosed by this specification include, for example, the following.
- a masking sheet for chemical treatment A substrate having a first surface and a second surface; Including a pressure-sensitive adhesive layer disposed on the first surface side of the base material, The substrate is a non-metallic substrate;
- the relationship between the elastic modulus Et ′ of the masking sheet and the thickness Hs of the substrate is expressed by the following formula: 0.7 N / mm ⁇ Et ′ ⁇ Hs 3 (typically 0.8 N / mm ⁇ Et ′ ⁇ Hs 3 , Preferably 1.0 N / mm ⁇ Et ′ ⁇ Hs 3 );
- the masking sheet according to (1), wherein the elastic modulus Et ′ of the masking sheet is 1.0 GPa or more (typically 1.5 GPa to 20 GPa, preferably 2.0 GPa to 10 GPa).
- a masking sheet for chemical treatment A substrate having a first surface and a second surface; Including a pressure-sensitive adhesive layer disposed on the first surface side of the base material,
- the substrate is a non-metallic substrate;
- the relationship between the elastic modulus Es ′ of the substrate and the thickness Hs of the substrate is represented by the following formula: 0.7 N / mm ⁇ Es ′ ⁇ Hs 3 (typically 0.8 N / mm ⁇ Es ′ ⁇ Hs 3 , Preferably 1.0 N / mm ⁇ Es ′ ⁇ Hs 3 );
- the masking sheet according to (3), wherein the elastic modulus Es ′ of the substrate is 1.0 GPa or more (typically 1.5 GPa to 20 GPa, preferably 2.0 GPa to 10 GPa).
- a thickness of the masking sheet is 1 mm or less (preferably 0.50 mm or less, more preferably 0.30 mm or less, further preferably 0.15 mm or less, typically 0.05 mm or more)
- the substrate is a polyester resin film (for example, PET film or PEN film) having a thickness of 0.06 mm or more (typically 0.06 to 0.50 mm).
- the 90-degree peel strength against duralumin A2024 is 1.0 to 25 N / 20 mm (eg, 3.0 to 25 N / 20 mm, preferably 5 to 20 N / 20 mm).
- the masking sheet described in 1. (10)
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a tackifier, and the content of the tackifier is 10 to 85% by weight of the pressure-sensitive adhesive layer, and any of the above (1) to (9) Masking sheet according to crab.
- the masking sheet according to (11), wherein 95% by weight or more of the rubber-based polymer contained in the rubber-based pressure-sensitive adhesive is natural rubber.
- the rubber-based pressure-sensitive adhesive contains 20 to 40 parts by weight of a terpene-based resin (typically a terpene resin) with respect to 100 parts by weight of the rubber-based polymer contained in the pressure-sensitive adhesive.
- the masking sheet as described.
- the pressure-sensitive adhesive layer comprises a non-crosslinking type pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive crosslinked by a reaction between a hydroxyl group-containing polymer (preferably a hydroxyl group-containing polymer having Mn of 5000 or less) and a hydroxyl group-reactive crosslinking agent.
- a hydroxyl group-containing polymer preferably a hydroxyl group-containing polymer having Mn of 5000 or less
- a hydroxyl group-reactive crosslinking agent preferably a hydroxyl group-containing polymer having Mn of 5000 or less
- Adhesive composition A 100 parts of natural rubber (MS (1 + 4) natural rubber having Mooney viscosity of 75 at 100 ° C.), styrene isoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3460C”, radial structure, styrene content 25%) 30 parts, 80 parts maleic anhydride-modified C5 / C9 petroleum resin (trade name “Quinton D-200” manufactured by Nippon Zeon Co., Ltd.), 40 parts phenol-modified rosin (trade name “Sumilite PR12603N” manufactured by Sumitomo Bakelite Co., Ltd.) Dissolve 1 part of a phenolic anti-aging agent (trade name “NOCRACK NS-6”, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) in toluene, and use aromatic isocyanate as a cross-link
- Adhesive composition B 100 parts of natural rubber (MS (1 + 4) natural rubber having Mooney viscosity of 75 at 100 ° C.), styrene isoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., trade name “Quintac 3460C”, radial structure, styrene content 25%) 30 parts, 200 parts of maleic anhydride-modified C5 / C9 petroleum resin (trade name “Quinton D-200” manufactured by Nippon Zeon Co., Ltd.), 40 parts of phenol-modified rosin (trade name “Sumilite PR12603N” manufactured by Sumitomo Bakelite Co., Ltd.) Hydroxyl group-containing polymer (trade name “Epol” manufactured by Idemitsu Kosan Co., Ltd .; 4.5 parts of liquid hydrogenated polyisoprene having a hydroxyl group at its terminal, number average molecular weight 2500, hydroxyl value 50.5 mg K
- Adhesive composition C 100 parts of natural rubber, 30 parts of terpene resin (manufactured by Yasuhara Chemical Co., Ltd., trade name “YS Resin PX1150”) and 3 parts of phenolic anti-aging agent (trade name “Noklak NS-6”, produced by Ouchi Shinsei Chemical Co., Ltd.) are toluene To prepare an adhesive composition C.
- a pale crepe having a Mooney viscosity MS 1 + 4 (100 ° C.) of 90 or more (thick pale crepe No. 1X) was used without further mastication.
- Example 1 The pressure-sensitive adhesive composition A was applied to one side of a release liner obtained by treating a high-quality paper laminated with polyethylene resin on both sides with a silicone-based release agent, and dried at 100 ° C. for 3 minutes in a hot air circulation oven. A pressure-sensitive adhesive layer having a thickness of 30 ⁇ m was formed.
- a masking sheet according to Example 1 was obtained by bonding a first surface of a 125 ⁇ m-thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) as a substrate to the pressure-sensitive adhesive layer on the release liner. The release liner was left on the pressure-sensitive adhesive layer as it was and used to protect the pressure-sensitive adhesive surface of the masking sheet.
- Examples 2 to 4 As in Example 1, except that PET films having thicknesses of 100 ⁇ m (Example 2), 75 ⁇ m (Example 3) and 50 ⁇ m (Example 4) were used as the base materials (both manufactured by Toray Industries, Inc., trade name “Lumirror”). Masking sheets according to Examples 2 to 4 were obtained.
- Example 5 Masking sheets according to Examples 5 and 6 were obtained in the same manner as in Example 1 except that 75 ⁇ m (Example 5) and 50 ⁇ m (Example 6) PEN films (both manufactured by Teijin Limited) were used as substrates. .
- Example 7 A masking sheet according to Examples 7 and 8 was obtained in the same manner as in Example 1 except that a PPS film having a thickness of 75 ⁇ m (Example 7) and a thickness of 100 ⁇ m (Example 8) was used as the substrate. It was.
- Example 9 A masking sheet according to Example 9 was obtained in the same manner as in Example 1 except that a CPP film (manufactured by Toray Industries, Inc.) having a thickness of 100 ⁇ m was used as the substrate.
- a CPP film manufactured by Toray Industries, Inc.
- Example 10 A masking sheet according to Example 10 was obtained in the same manner as in Example 2 except that the adhesive composition B was used in place of the adhesive composition A.
- Example 11 A masking sheet according to Example 11 was obtained in the same manner as in Example 2 except that the adhesive composition C was used in place of the adhesive composition A.
- Vs duralumin plate The masking sheet according to each example was punched into a circle having a diameter of 25 mm together with the release liner protecting the adhesive surface. In a standard environment of 23 ° C. and 65% RH, the release liner was removed from the punched masking sheet (test piece), and the pressure-sensitive adhesive surface thus exposed was pressed against the adherend by reciprocating a 2 kg roller once. . As the adherend, a duralumin plate (flat plate made of duralumin A2024) having been previously degreased and having a length of 200 mm, a width of 100 mm, and a thickness of 1 mm was used.
- the sample with the test piece attached in this manner was allowed to stand for 30 minutes in the above standard environment, and then immersed in a chromic acid anodizing solution and subjected to anodizing treatment for 35 minutes under the conditions of a liquid temperature of 40 ° C. and a voltage of 20V. .
- a chromic acid anodizing solution for 35 minutes under the conditions of a liquid temperature of 40 ° C. and a voltage of 20V.
- N 5
- the chemical solution penetration distance from the outer edge of the test piece was measured in the radial direction, and the longest penetration distance in each sample was defined as the chemical solution penetration distance for the sample.
- the average value of the chemical solution penetration distance which concerns on five samples was computed.
- Vs. milling duralumin plate instead of the duralumin flat plate, a duralumin plate (milled plate) whose surface was milled was used as the adherend. About the other point, it carried out similarly to the above, the masking sheet concerning each example was affixed on the to-be-adhered body, the anodizing process was performed, and the chemical solution penetration distance was measured.
- the infiltration range of the chemical solution was clearly visible from the outer surface side of the masking sheet.
- the masking sheets of Examples 1 to 6 were treated with the chemical solution under the same conditions as the anodizing treatment except that the duralumin flat plate was used as the adherend and no current was applied. No intrusion was observed.
- the samples after the anodizing treatment according to each example were gently washed with water and allowed to dry naturally at room temperature. Thereafter, for two of the five samples, the tester manually pulled the test piece from the duralumin plate. This peeling was performed at a tensile speed of about 0.3 m / min in the direction of 90 degrees from the surface of the duralumin plate. The surface of the duralumin plate after the test piece was peeled was visually observed to check for the presence of adhesive residue. As a result, no adhesive residue was observed in any of Examples 1 to 11.
- the remaining three of the five samples were spray-coated with a solvent-based paint “Epora # 3000S” (manufactured by Nippon Special Paint Co., Ltd.) over the entire surface of the duralumin plate where the test piece was attached.
- the amount of the paint sprayed was such that the thickness of the coating film formed after drying was about 10 ⁇ m.
- the sprayed paint was dried at about 100 ° C. After the paint was sufficiently dried and cured, the tester manually pulled the specimen from the duralumin plate. This peeling was performed at a tensile speed of about 0.3 m / min in the direction of 90 degrees from the surface of the duralumin plate. When the surface of the duralumin plate after the test piece was peeled was visually observed, no adhesive residue was observed in any case.
- the 90 ° peel strength (vs. duralumin 90 ° peel strength) was measured by the method described above using a flat plate made of duralumin A2024 as an adherend, and found to be 6.5 N / 20 mm.
- the masking sheets of Examples 1 to 9 and Example 11 were similarly measured for 90 ° peel strength against duralumin, and both were 1.0 N / 20 mm or more (more specifically, 3.0 N / 20 mm or more and 25 N / 20 mm or less). It was confirmed that there was. In any of the masking sheets of Examples 1 to 11, no adhesive residue on the duralumin plate was observed.
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Abstract
Description
本出願は、2014年10月6日に出願された日本国特許出願2014-205587に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
なお、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明することがあり、重複する説明は省略または簡略化することがある。
一実施形態に係るマスキングシートの典型的な構成例を図1に模式的に示す。このマスキングシート10は、第一面1Aおよび第二面1Bを有するシート状の基材(例えば樹脂シート)1と、その第一面1A側に設けられた粘着剤層2とを備える。マスキングシート10は、処理対象物品の非処理対象部分(マスキング対象部分)に貼り付けて使用される。非処理対象部分にマスキングシート10が貼り付けられた状態でアノダイズ処理を行うことにより、該非処理対象部分がアノダイズ薬液から保護される。
ここに開示される技術において、マスキングシートを構成する非金属基材とは、主構成材料が非金属材料である基材を意味し、典型的には概ね50重量%以上または概ね50体積%以上が非金属材料である基材をいう。ここで非金属材料とは、金属材料以外の材料全般を指し、有機材料および無機非金属材料を包含する概念である。上記非金属基材は、1層により構成された単層構造の基材であってもよく、全領域または一部の領域において2層以上の積層構造を有する基材であってもよい。このような積層構造を構成する各層は、互いに組成または構成の異なる層であってもよく、組成および構成が同一の層であってもよい。上記非金属基材は、有機材料および無機非金属材料から選択されるいずれかにより形成された層や、2種以上の材料のブレンド物または複合物(複合材料)により形成された層を含み得る。また、上記非金属基材は、主構成材料が非金属材料である限りにおいて、金属材料からなる層や、有機材料または無機非金属材料と金属材料とのブレンド物や複合物からなる層を含み得る。
ここに開示される技術における粘着剤層は、典型的には、室温付近の温度域において柔らかい固体(粘弾性体)の状態を呈し、圧力により簡単に被着体に接着する性質を有する材料(粘着剤)から構成された層をいう。ここでいう粘着剤は、「C. A. Dahlquist, “Adhesion : Fundamental and Practice”, McLaren & Sons, (1966) P. 143」に定義されているとおり、一般的に、複素引張弾性率E*(1Hz)<107dyne/cm2を満たす性質を有する材料(典型的には、25℃において上記性質を有する材料)である。
上記スチレン系ブロック共重合体は、ジブロック共重合体やトリブロック共重合体等の直鎖構造のポリマーを主成分とするものであってもよく、放射状(radial)構造のポリマーを主成分とするものであってもよい。
特に限定するものではないが、天然ゴムと合成ゴムとの合計重量が粘着剤層全体の重量に占める割合は、典型的には30~90重量%、好ましくは40~80重量%、より好ましくは40~70重量%、例えば45~60重量%とすることができる。また、好ましい一態様において、天然ゴムと合成ゴムとの合計重量が粘着剤層全体の重量に占める割合を20~70重量%(より好ましくは20~60重量%、例えば30~60重量%)とすることができる。
テルペン系樹脂の例としては、テルペン樹脂、テルペンフェノール樹脂、芳香族変性テルペン樹脂、水素化テルペン樹脂等が挙げられる。
テルペン樹脂の例としては、α-ピネン、β-ピネン、d-リモネン、l-リモネン、ジペンテン等のテルペン類(典型的にはモノテルペン類)の重合体が含まれる。上記テルペン樹脂は、1種のテルペン類の単独重合体であってもよく、2種以上のテルペン類の共重合体であってもよい。1種のテルペン類の単独重合体としては、α-ピネン重合体、β-ピネン重合体、ジペンテン重合体等が挙げられる。
変性テルペン樹脂の例としては、上述のようなテルペン樹脂を変性(フェノール変性、スチレン変性、水素添加変性、炭化水素変性等)したものが挙げられる。具体的には、テルペンフェノール樹脂、スチレン変性テルペン樹脂、水素添加テルペン樹脂等が例示される。ここで「テルペンフェノール樹脂」とは、テルペン残基およびフェノール残基を含むポリマーを指し、テルペンとフェノール化合物との共重合体(テルペン-フェノール共重合体樹脂)と、テルペンの単独重合体または共重合体(テルペン樹脂、典型的には未変性テルペン樹脂)をフェノール変性したもの(フェノール変性テルペン樹脂)との双方を包含する概念である。
好ましい一態様において、ベースポリマー100重量部に対する粘着付与剤の含有量を20~350重量部とすることができ、50~300重量部とすることが好ましく、65~250重量部とすることがさらに好ましい。好ましい他の一態様において、ベースポリマー100重量部に対する粘着付与剤の含有量は、例えば20~150重量部とすることができ、好ましくは30~120重量部、さらに好ましくは40~100重量部である。上述した粘着付与剤の含有量は、例えば、ゴム系粘着剤(典型的には、天然ゴムと合成ゴムとを組み合わせて含む粘着剤)に好ましく適用され得る。
また、好ましいさらに他の一態様において、ベースポリマー100重量部に対する粘着付与剤の含有量は、例えば5~100重量部とすることができ、好ましくは10~80重量部、より好ましくは15~60重量部(例えば20~40重量部)である。上述した粘着付与剤の含有量は、例えば、ゴム系ポリマーが実質的に天然ゴムからなる粘着剤(好ましくは非架橋タイプの粘着剤)に好ましく適用され得る。
好ましい一態様において、粘着剤層に占める粘着付与剤の割合は、40重量%以上としてもよく、さらに50重量%以上(例えば60重量%以上)としてもよい。かかる粘着付与剤の割合は、例えば、ゴム系粘着剤(典型的には、天然ゴムと合成ゴムとを組み合わせて含む粘着剤)に好ましく適用され得る。
好ましい他の一態様において、粘着剤層に占める粘着付与剤の割合は、10~70重量%とすることができ、10~50重量%(例えば15~35重量%)とすることがより好ましい。かかる粘着付与剤の割合は、例えば、ゴム系ポリマーが実質的に天然ゴムからなる粘着剤(好ましくは非架橋タイプの粘着剤)に好ましく適用され得る。
A=(水酸基含有ポリマーの水酸基価[mgKOH/g])×(ベースポリマー100重量部に対する水酸基含有ポリマーの重量部数) ・・・(1)
A値の増大により、粘着剤層の糊切れ性が向上する傾向にある。また、A値が大きすぎないことにより、粘着性(例えば、対ジュラルミン90度剥離強度)が向上する傾向にある。
B=(水酸基含有ポリマーの水酸基価[mgKOH/g]×水酸基含有ポリマーの重量[g])/粘着剤層の重量[g] ・・・(2)
B値の増大により、粘着剤層の糊切れ性が向上する傾向にある。また、B値が大きすぎないことにより、粘着性が向上する傾向にある。
ここに開示されるマスキングシートは、従来公知の方法によって形成することができる。例えば、上述のような基材に粘着剤組成物を直接付与(典型的には塗布)して乾燥させることにより粘着剤層を形成する方法(直接法)を採用することができる。また、剥離性を有する表面(剥離面)に粘着剤組成物を付与して乾燥させることにより該表面上に粘着剤層を形成し、その粘着剤層を基材に転写する方法(転写法)を採用してもよい。これらの方法を組み合わせてもよい。上記剥離面としては、剥離ライナーの表面や、剥離処理された基材背面等を利用し得る。
また、粘着剤層の端面からの薬液の浸み込み(粘着剤の膨潤による薬液浸入)を抑制する観点から、粘着剤層の厚さは、好ましくは80μm以下、より好ましくは60μm以下、さらに好ましくは50μm以下である。ここに開示されるマスキングシートの一好適例において、粘着剤層の厚さを20~40μmとすることができる。
他の一態様において、非シリコーン系の剥離剤を用いて形成された剥離処理層を採用することができる。非シリコーン系剥離剤の具体例には、長鎖アルキル系剥離剤、オレフィン系剥離剤およびフッ素系剥離剤が含まれる。好ましい非シリコーン系剥離剤として、長鎖アルキル系剥離剤およびオレフィン系剥離剤が例示される。なかでも長鎖アルキル系剥離剤が好ましい。
基材の第二面に剥離処理層を形成するために用いられる剥離剤としても、同様のものを好ましく採用し得る。
対ジュラルミン90度剥離強度は、例えば、粘着シートを構成する粘着剤層の組成や該粘着剤層の厚さ等により調節することができる。
処理対象物品に貼り付けられる前のマスキングシートは、該処理対象物品の非処理対象部分をマスクするためのマスキング用粘着製品として把握され得る。このような粘着製品は、例えば、ここに開示されるいずれかのマスキングシートと、該マスキングシートの粘着面を保護する剥離ライナーと、を含む剥離ライナー付きマスキングシートとして構成され得る。上記粘着製品の好ましい一形態として、例えば図3に示すように、剥離ライナー付きマスキングシート(粘着製品)100を構成するマスキングシート10が、連続する(ひとつながりの)剥離ライナー3上において、隣接する第1粘着片10aと第2粘着片10bとに分割されている形態が挙げられる。例えば図3に示す例では、円形の第1粘着片10aの外周と、この第1粘着片10aを囲む第2粘着片10bの内周とが隣接している。このような粘着製品100は、例えば図4に示すように、剥離ライナー3上に保持されたマスキングシート10を、基材1の第二面1B側から、剥離ライナー3の粘着剤層側表面3Aに至りかつ剥離ライナー3の背面(粘着剤層側表面とは反対の表面)3Bに到達しない深さ(すなわち、剥離ライナー3を少なくとも完全には分割しない深さ)で切断することにより得ることができる。以下、このようにマスキングシートを分割しかつ剥離ライナーを分割しない切断態様や、このような切断態様により形成された切断状態を、「ハーフカット」ということがある。
ここに開示されるマスキングシートは、好ましい一態様において、該マスキングシートへの薬液浸入を、該マスキングシートの外面側から視認可能に構成することができる。ここで、マスキングシートの外面とは、粘着面とは反対側の表面を指す。通常は、基材の第二面が該マスキングシートの外面を兼ねる。
Th(%)=Td/Tt×100
ヘイズ値は、マスキングシートを構成する基材や粘着剤層の組成、厚さ、表面状態等の選択により調節することができる。ヘイズ値の測定は、後述する実施例に記載の方法に従って行うことができる。
後述するように高視認性領域と低視認性領域とを有するマスキングシートでは、少なくとも高視認性領域のヘイズ値が上記範囲にあることが好ましい。高視認性領域のヘイズ値および低視認性領域のヘイズ値がいずれも上記範囲にあってもよい。
ここに開示されるマスキングシートは、該マスキングシートの外面側からみて、薬液浸入の視認性が相対的に高い領域(高視認性領域)と相対的に低い領域(低視認性領域)とが存在するように構成することができる。このような構成によると、低視認性領域が存在することにより、マスキングシートの可視性を高めることができる。したがって、上記構成のマスキングシートによると、薬液浸入の視認性と、マスキングシートの可視性とを好適に両立させることができる。
第一面および第二面を有する基材と、
上記基材の上記第一面側に配置された粘着剤層とを含み、
上記基材は非金属基材であり、
上記マスキングシートの弾性率Et’と上記基材の厚さHsとの関係が次式:0.7N/mm<Et’×Hs3(典型的には0.8N/mm<Et’×Hs3、好ましくは1.0N/mm<Et’×Hs3);を満たす、薬液処理用マスキングシート。
(2) 上記マスキングシートの弾性率Et’が1.0GPa以上(典型的には1.5GPa~20GPa、好ましくは2.0GPa~10GPa)である、上記(1)に記載のマスキングシート。
(3) 薬液処理用のマスキングシートであって、
第一面および第二面を有する基材と、
上記基材の上記第一面側に配置された粘着剤層とを含み、
上記基材は非金属基材であり、
上記基材の弾性率Es’と上記基材の厚さHsとの関係が次式:0.7N/mm<Es’×Hs3(典型的には0.8N/mm<Es’×Hs3、好ましくは1.0N/mm<Es’×Hs3);を満たす、薬液処理用マスキングシート。
(4) 上記基材の弾性率Es’が1.0GPa以上(典型的には1.5GPa~20GPa、好ましくは2.0GPa~10GPa)である、上記(3)に記載のマスキングシート。
(5) 上記マスキングシートの厚さが1mm以下(好ましくは0.50mm以下、より好ましくは0.30mm以下、さらに好ましくは0.15mm以下、典型的には0.05mm以上)である、上記(1)~(4)のいずれかに記載のマスキングシート。
(6) 上記基材が単層の樹脂フィルムである、上記(1)~(5)のいずれかに記載のマスキングシート。
(7) 上記基材が厚さ0.06mm以上(典型的には0.06~0.50mm)のポリエステル系樹脂フィルム(例えば、PETフィルムまたはPENフィルム)である、上記(1)~(6)のいずれかに記載のマスキングシート。
(8) 上記基材が厚さ0.06mm以上(典型的には0.06~0.50mm)のPPS樹脂フィルムである、上記(1)~(7)のいずれかに記載のマスキングシート。
(9) ジュラルミンA2024に対する90度剥離強度が1.0~25N/20mm(例えば3.0~25N/20mm、好ましくは5~20N/20mm)である、上記(1)~(8)のいずれかに記載のマスキングシート。
(10) 上記粘着剤層を構成する粘着剤は粘着付与剤を含み、上記粘着付与剤の含有量は上記粘着剤層の10~85重量%である、上記(1)~(9)のいずれかに記載のマスキングシート。
(11) 上記粘着剤層を構成する粘着剤はゴム系粘着剤である、上記(1)~(10)のいずれかに記載のマスキングシート。
(12) 上記粘着剤層を構成する粘着剤は、天然ゴムおよび合成ゴムを含む、上記(1)~(11)のいずれかに記載のマスキングシート。
(13)上記粘着剤層を構成する粘着剤は、粘着付与剤として石油系樹脂とロジン系樹脂とを含む、上記(1)~(12)のいずれかに記載のマスキングシート。
(14) 上記ゴム系粘着剤に含まれるゴム系ポリマーの95重量%以上が天然ゴムである、上記(11)に記載のマスキングシート。
(15) 前記ゴム系粘着剤は、該粘着剤に含まれるゴム系ポリマー100重量部に対して20~40重量部のテルペン系樹脂(典型的にはテルペン樹脂)を含む、上記(14)に記載のマスキングシート。
(16) 上記天然ゴムのムーニー粘度MS1+4(100℃)が80以上である、上記(14)または(15)のいずれかに記載のマスキングシート。
(17) 上記粘着剤層は非架橋タイプの粘着剤からなる、上記(1)~(16)のいずれかに記載のマスキングシート。
(18) 上記粘着剤層は、水酸基含有ポリマー(好ましくは、Mnが5000以下の水酸基含有ポリマー)と水酸基反応性架橋剤との反応により架橋した粘着剤により構成されている、上記(1)~(16)のいずれかに記載のマスキングシート。
(19) 上記マスキングシートへの薬液浸入を該マスキングシートの外面側から視認可能に構成されている、上記(1)~(18)のいずれかに記載のマスキングシート。
(20) 金属部材のアノダイズ処理に用いられる、上記(1)~(19)のいずれかに記載のマスキングシート。
(粘着剤組成物A)
天然ゴム(MS(1+4)100℃におけるムーニー粘度が75の天然ゴム)100部、スチレンイソプレンブロック共重合体(日本ゼオン社製、商品名「クインタック3460C」、放射状構造、スチレン含有量25%)30部、無水マレイン酸変性C5/C9系石油樹脂(日本ゼオン社製、商品名「クイントンD-200」)80部、フェノール変性ロジン(住友ベークライト社製、商品名「スミライトPR12603N」)40部およびフェノール系老化防止剤(大内新興化学工業社製、商品名「ノクラックNS-6」)1部をトルエンに溶解し、架橋剤として芳香族イソシアネート(日本ポリウレタン社製、商品名「コロネー卜L」;トリレンジイソシアネートのトリメチロールプロパン付加物)3部を加えて、粘着剤組成物Aを調製した。
天然ゴム(MS(1+4)100℃におけるムーニー粘度が75の天然ゴム)100部、スチレンイソプレンブロック共重合体(日本ゼオン社製、商品名「クインタック3460C」、放射状構造、スチレン含有量25%)30部、無水マレイン酸変性C5/C9系石油樹脂(日本ゼオン社製、商品名「クイントンD-200」)200部、フェノール変性ロジン(住友ベークライト社製、商品名「スミライトPR12603N」)40部、水酸基含有ポリマー(出光興産社製の商品名「エポール」;末端に水酸基を有する液状の水添ポリイソプレン、数平均分子量2500、水酸基価50.5mgKOH/g)4.5部およびフェノール系老化防止剤(大内新興化学工業社製、商品名「ノクラックNS-6」)1部をトルエンに溶解し、架橋剤として芳香族イソシアネート(日本ポリウレタン社製、商品名「コロネー卜L」;トリレンジイソシアネートのトリメチロールプロパン付加物)3部を加えて、粘着剤組成物Bを調製した。
天然ゴム100部、テルペン樹脂(ヤスハラケミカル社製、商品名「YSレジンPX1150」)30部およびフェノール系老化防止剤(大内新興化学工業社製、商品名「ノクラックNS-6」)3部をトルエンに溶解して、粘着剤組成物Cを調製した。上記天然ゴムとしては、ムーニー粘度MS1+4(100℃)90以上のペールクレープ(厚手ペールクレープ1X号)を、それ以上の素練りを行うことなく使用した。
(例1)
両面にポリエチレン樹脂がラミネートされた上質紙をシリコーン系剥離剤で処理してなる剥離ライナーの片面に粘着剤組成物Aを塗布し、熱風循環式オーブンにて100℃で3分間乾燥させて、厚さ30μmの粘着剤層を形成した。基材としての厚さ125μmのPETフィルム(東レ社製、商品名「ルミラー」)の第一面を上記剥離ライナー上の粘着剤層に貼り合わせて、例1に係るマスキングシートを得た。上記剥離ライナーはそのまま粘着剤層上に残し、マスキングシートの粘着面の保護に使用した。
基材として厚さ100μm(例2)、75μm(例3)および50μm(例4)のPETフィルム(いずれも東レ社製、商品名「ルミラー」)をそれぞれ使用した他は例1と同様にして、例2~4に係るマスキングシートを得た。
基材として厚さ75μm(例5)および50μm(例6)のPENフィルム(いずれも帝人社製)をそれぞれ使用した他は例1と同様にして、例5,6に係るマスキングシートを得た。
基材として厚さ75μm(例7)および厚さ100μm(例8)のPPSフィルム(いずれも東レ社製)を使用した他は例1と同様にして、例7,8に係るマスキングシートを得た。
基材として厚さ100μmのCPPフィルム(東レ社製)を使用した他は例1と同様にして、例9に係るマスキングシートを得た。
粘着剤組成物Aに代えて粘着剤組成物Bを使用した他は例2と同様にして、例10に係るマスキングシートを得た。
粘着剤組成物Aに代えて粘着剤組成物Cを使用した他は例2と同様にして、例11に係るマスキングシートを得た。
(対ジュラルミン平板)
各例に係るマスキングシートを、粘着面を保護する剥離ライナーごと、直径25mmの円形に打ち抜いた。23℃、65%RHの標準環境下において、打ち抜かれたマスキングシート(試験片)から剥離ライナーを除去し、これにより露出した粘着面を被着体に、2kgのローラーを1往復させて圧着した。被着体としては、あらかじめ脱脂した縦200mm、横100mm、厚さ1mmのジュラルミン板(ジュラルミンA2024からなる平板)を使用した。このようにして試験片を貼り付けたサンプルを上記標準環境下に30分放置した後、クロム酸アノダイズ液に浸漬し、液温40℃、電圧20Vの条件で、35分間のアノダイズ処理を行った。各例に係るマスキングシートにつき、それぞれ5つのサンプルを作製して上記アノダイズ処理を行った(すなわちN=5)。
アノダイズ処理後のサンプルにマスキングシート(試験片)が貼り付けられた状態のまま、薬液の浸入状況をマスキングシートの背面側から目視で確認した。薬液の浸入が認められた場合には、試験片の外縁からの薬液浸入距離を径方向に測定し、各サンプルにおける最も長い浸入距離を当該サンプルについての薬液浸入距離とした。各例に係るマスキングシートについて、5つのサンプルに係る薬液浸入距離の平均値を算出した。
上記ジュラルミン平板に代えて、表面がフライス加工されたジュラルミン板(フライス加工板)を被着体に使用した。その他の点については上記と同様にして、各例に係るマスキングシートを被着体に貼り付けてアノダイズ処理を行い、薬液浸入距離を測定した。
1A 第一面
1B 第二面
2 粘着剤層
2a 第1粘着片の粘着剤層
2b 第2粘着片の粘着剤層
2A 表面(粘着面)
3 剥離ライナー
3A 表面
3B 背面
10 マスキングシート
10a 第1粘着片
10b 第2粘着片
10B 外面
100 剥離ライナー付き粘着シート(粘着製品)
Claims (10)
- アノダイズ処理用のマスキングシートであって、
第一面および第二面を有する基材と、
前記基材の前記第一面側に配置された粘着剤層とを含み、
前記基材は非金属基材であり、
前記マスキングシートの弾性率Et’と前記基材の厚さHsとの関係が次式:0.7N/mm<Et’×Hs3;を満たす、アノダイズ処理用マスキングシート。 - 前記マスキングシートの弾性率Et’が1.0GPa以上である、請求項1に記載のマスキングシート。
- 前記マスキングシートの厚さが0.30mm以下である、請求項1または2に記載のマスキングシート。
- ジュラルミンA2024に対する90度剥離強度が1.0~25N/20mmである、請求項1から3のいずれか一項に記載のマスキングシート。
- 前記粘着剤層を構成する粘着剤は粘着付与剤を含み、前記粘着付与剤の含有量は前記粘着剤層の10~85重量%である、請求項1から4のいずれか一項に記載のマスキングシート。
- 前記粘着剤層を構成する粘着剤はゴム系粘着剤である、請求項1から5のいずれか一項に記載のマスキングシート。
- 前記ゴム系粘着剤に含まれるゴム系ポリマーの95重量%以上が天然ゴムである、請求項6に記載のマスキングシート。
- 前記ゴム系粘着剤は、該粘着剤に含まれるゴム系ポリマー100重量部に対して20~40重量部のテルペン系樹脂を含む、請求項6または7に記載のマスキングシート。
- 前記粘着剤層は、水酸基含有ポリマーと水酸基反応性架橋剤との反応により架橋した粘着剤により構成されている、請求項1から8のいずれか一項に記載のマスキングシート。
- 前記マスキングシートへの薬液浸入を該マスキングシートの外面側から視認可能に構成されている、請求項1から9のいずれか一項に記載のマスキングシート。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017179069A (ja) * | 2016-03-29 | 2017-10-05 | 日東電工株式会社 | マスキングシート |
JP2017214060A (ja) * | 2016-05-31 | 2017-12-07 | 株式会社クラレ | インナーライナー、空気入りタイヤ、及びそれらの製造方法 |
JP7072735B1 (ja) * | 2021-03-31 | 2022-05-20 | 株式会社寺岡製作所 | 粘着組成物及び粘着テープ |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3562902A2 (en) * | 2016-12-30 | 2019-11-06 | 3M Innovative Properties Company | Tapes and methods of use for masking aluminum surfaces in chromic acid anodization |
EP3792324A4 (en) * | 2018-05-10 | 2022-01-26 | Nitto Shinko Corporation | HOT MELT ADHESIVE FILM |
CN110556331B (zh) * | 2019-09-19 | 2023-03-14 | 苏州芯慧联半导体科技有限公司 | 一种复合材料及使用该材料的静电卡盘的制造方法 |
CN113512361B (zh) * | 2021-02-22 | 2022-10-04 | 烟台大学 | 一种高粘接强度虫胶及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60238497A (ja) * | 1984-05-09 | 1985-11-27 | Nitto Electric Ind Co Ltd | 部分メツキなどの部分処理方法 |
JPH0234680A (ja) * | 1988-07-25 | 1990-02-05 | Hitachi Chem Co Ltd | マスキングテープ用粘着剤 |
JPH09134991A (ja) * | 1995-11-07 | 1997-05-20 | Soken Chem & Eng Co Ltd | リードフレームメッキマスキング用粘着テープ |
WO2006057149A1 (ja) * | 2004-11-24 | 2006-06-01 | Kuraray Co., Ltd. | 水溶性フィルムロール及び水溶性フィルムの繰り出し方法 |
JP2007231340A (ja) * | 2006-02-28 | 2007-09-13 | Fujifilm Corp | ナノ構造体の製造方法 |
JP2010018831A (ja) * | 2008-07-09 | 2010-01-28 | Ibiden Co Ltd | 受熱部材、及び、排気管放熱システム |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0241163Y2 (ja) * | 1984-11-12 | 1990-11-01 | ||
US5516581A (en) * | 1990-12-20 | 1996-05-14 | Minnesota Mining And Manufacturing Company | Removable adhesive tape |
JP3738038B2 (ja) * | 1993-08-11 | 2006-01-25 | ニチバン株式会社 | 粘着剤組成物及びマスキングテープ |
JP3622931B2 (ja) * | 1996-04-04 | 2005-02-23 | ソニーケミカル株式会社 | 塗装マスキングテープ用基材及び塗装マスキングテープ |
US5941890A (en) * | 1998-06-26 | 1999-08-24 | Ethicon Endo-Surgery, Inc. | Implantable surgical marker |
SG82087A1 (en) * | 1999-09-10 | 2001-07-24 | Sumitomo Chemical Co | Pressure sensitive adhesive |
JP2003119441A (ja) * | 2001-10-10 | 2003-04-23 | Sekisui Chem Co Ltd | メッキ用マスキングテープ |
US20060134407A1 (en) * | 2003-01-31 | 2006-06-22 | Takashi Yoshitomi | Adhesive sheet and layered product |
JP4051438B2 (ja) * | 2003-02-21 | 2008-02-27 | Dowaメタルテック株式会社 | 金属セラミック複合部材に対するメッキ方法、パターン製造成方法、および湿式処理装置、並びにパワーモジュール用金属セラミックス複合部材 |
WO2009133175A1 (de) * | 2008-04-30 | 2009-11-05 | Tesa Se | Klebeband |
JP2010042328A (ja) * | 2008-08-08 | 2010-02-25 | Eagle Ind Co Ltd | 表面処理用治具 |
JP2010126698A (ja) * | 2008-11-28 | 2010-06-10 | Furukawa Electric Co Ltd:The | マスキング用剥離性粘着テープ |
JP5116706B2 (ja) * | 2009-02-20 | 2013-01-09 | 日東電工株式会社 | 表面保護シート |
DE102009027283A1 (de) * | 2009-04-03 | 2010-10-07 | Tesa Se | Klebefolie zum Verschließen von Gefäßen und Kanälen, Herstellung und Verwendung dieser |
JP2011148943A (ja) * | 2010-01-25 | 2011-08-04 | Nitto Denko Corp | 保護シートおよびその利用 |
US8530021B2 (en) * | 2011-03-08 | 2013-09-10 | 3M Innovative Properties Company | Microstructured tape |
JP6009812B2 (ja) * | 2011-06-17 | 2016-10-19 | 日東電工株式会社 | 粘着フィルム |
FI20115683A0 (fi) * | 2011-06-30 | 2011-06-30 | Beneq Oy | Pinnankäsittelylaite |
JP5955579B2 (ja) * | 2011-07-21 | 2016-07-20 | 日東電工株式会社 | ガラスエッチング用保護シート |
CA2849931C (en) * | 2011-10-31 | 2019-03-12 | Intertape Polymer Corp. | Pressure-chromic tape and methods of making same |
JP2013253317A (ja) * | 2012-05-08 | 2013-12-19 | Fujifilm Corp | 半導体装置用基板、半導体装置、調光型照明装置、自己発光表示装置、太陽電池および反射型液晶表示装置 |
WO2014097903A1 (ja) * | 2012-12-21 | 2014-06-26 | 日東電工株式会社 | 粘着テープ |
JP6046500B2 (ja) * | 2013-01-17 | 2016-12-14 | 日東電工株式会社 | 薬液処理用保護シート |
-
2015
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60238497A (ja) * | 1984-05-09 | 1985-11-27 | Nitto Electric Ind Co Ltd | 部分メツキなどの部分処理方法 |
JPH0234680A (ja) * | 1988-07-25 | 1990-02-05 | Hitachi Chem Co Ltd | マスキングテープ用粘着剤 |
JPH09134991A (ja) * | 1995-11-07 | 1997-05-20 | Soken Chem & Eng Co Ltd | リードフレームメッキマスキング用粘着テープ |
WO2006057149A1 (ja) * | 2004-11-24 | 2006-06-01 | Kuraray Co., Ltd. | 水溶性フィルムロール及び水溶性フィルムの繰り出し方法 |
JP2007231340A (ja) * | 2006-02-28 | 2007-09-13 | Fujifilm Corp | ナノ構造体の製造方法 |
JP2010018831A (ja) * | 2008-07-09 | 2010-01-28 | Ibiden Co Ltd | 受熱部材、及び、排気管放熱システム |
Non-Patent Citations (1)
Title |
---|
See also references of EP3205751A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017179069A (ja) * | 2016-03-29 | 2017-10-05 | 日東電工株式会社 | マスキングシート |
JP2017214060A (ja) * | 2016-05-31 | 2017-12-07 | 株式会社クラレ | インナーライナー、空気入りタイヤ、及びそれらの製造方法 |
JP7072735B1 (ja) * | 2021-03-31 | 2022-05-20 | 株式会社寺岡製作所 | 粘着組成物及び粘着テープ |
WO2022208814A1 (ja) * | 2021-03-31 | 2022-10-06 | 株式会社寺岡製作所 | 粘着組成物及び粘着テープ |
TWI814280B (zh) * | 2021-03-31 | 2023-09-01 | 日商寺岡製作所股份有限公司 | 黏著組成物及黏貼帶 |
Also Published As
Publication number | Publication date |
---|---|
EP3205751A4 (en) | 2018-05-23 |
JPWO2016056468A1 (ja) | 2017-07-27 |
JPWO2016056470A1 (ja) | 2017-08-31 |
TWI690581B (zh) | 2020-04-11 |
JP6588454B2 (ja) | 2019-10-09 |
US20170292042A1 (en) | 2017-10-12 |
JPWO2016056467A1 (ja) | 2017-07-27 |
JPWO2016056469A1 (ja) | 2017-08-17 |
US20170306185A1 (en) | 2017-10-26 |
TW201621086A (zh) | 2016-06-16 |
EP3205751A1 (en) | 2017-08-16 |
WO2016056468A1 (ja) | 2016-04-14 |
TW201621094A (zh) | 2016-06-16 |
TW201619322A (zh) | 2016-06-01 |
EP3205697A4 (en) | 2018-05-09 |
JP6474422B2 (ja) | 2019-02-27 |
WO2016056469A1 (ja) | 2016-04-14 |
TW201623507A (zh) | 2016-07-01 |
WO2016056470A1 (ja) | 2016-04-14 |
EP3205697A1 (en) | 2017-08-16 |
JP6633534B2 (ja) | 2020-01-22 |
TWI687554B (zh) | 2020-03-11 |
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