WO2013073142A1 - Pressure-sensitive adhesive film or sheet, surface protecting film or sheet, and method for using pressure-sensitive adhesive film or sheet to protect surface of article - Google Patents
Pressure-sensitive adhesive film or sheet, surface protecting film or sheet, and method for using pressure-sensitive adhesive film or sheet to protect surface of article Download PDFInfo
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- WO2013073142A1 WO2013073142A1 PCT/JP2012/007185 JP2012007185W WO2013073142A1 WO 2013073142 A1 WO2013073142 A1 WO 2013073142A1 JP 2012007185 W JP2012007185 W JP 2012007185W WO 2013073142 A1 WO2013073142 A1 WO 2013073142A1
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
-
- 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
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- 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
- 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
-
- 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
- C09J2431/00—Presence of polyvinyl acetate
Definitions
- the present invention relates to a pressure-sensitive adhesive film or sheet, a surface protective film or sheet, and a method of using the pressure-sensitive adhesive film or sheet to protect the surface of an article.
- An adhesive film or sheet has been used as a surface protective film for protecting the surface of a product from dust adhesion, dirt, scratches, and the like. In recent years, it is also used as a surface protective film for precision electronic components.
- the adhesive film or sheet is required to have a moderately strong adhesive force between the adhesive layer and the adherend.
- This moderate strength is the strength that does not spontaneously peel off or fall off due to light vibration or impact, and can be peeled smoothly without leaving an adhesive layer on the adherend surface. Say strength.
- An adhesive film or sheet satisfying such required characteristics includes a film or sheet made of an ethylene-vinyl acetate copolymer.
- Patent Document 1 Japanese Patent Laid-Open No. 6-145616
- an adhesive layer is formed on 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 7% by weight and a melt flow rate of 2 to 20 g / 10 min.
- a surface protective film characterized by comprising 0.5 to 2 parts by weight of a tackifier is described. This surface protective film exhibits moderate initial adhesive strength, and even when subjected to heat treatment, particularly UV irradiation, the adhesive strength is not significantly increased, and there is no contamination to the object to be protected. Has been.
- Patent Document 2 Japanese Patent Laid-Open No. 2008-255233 discloses a polypropylene resin base layer (A) and an adhesive layer (B) comprising an ethylene / vinyl acetate copolymer having a vinyl acetate unit content of 7.5 to 50% by weight.
- An adhesive film or sheet consisting of This pressure-sensitive adhesive film or sheet has a high interlayer adhesion strength between the base material layer and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer has an appropriate pressure-sensitive adhesive force with respect to the surface of the article to be adhered, and the base material layer has a softening temperature, heat Excellent thermal properties such as deformation temperature, mechanical properties such as tensile strength, impact resistance, and stiffness, optical properties such as haze, gloss, and light transmittance. In addition, there is almost no generation of fish eyes, smooth surface and appearance. It is said to be very good.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2010-171419 describes (A) an ethylene / vinyl acetate copolymer resin and (B) a C9 aromatic hydrocarbon resin having high compatibility with (A).
- This solar cell encapsulant sheet is said to be excellent in workability when performing processing such as melting and processing, and further excellent in light resistance and heat resistance while having high transparency and high stability.
- Patent Document 1 Japanese Patent Application Laid-Open No. 6-1456166
- Japanese Patent Application Laid-Open No. 6-145616 Japanese Patent Application Laid-Open No. 6-145616
- Japanese Patent Application Laid-Open No. 6-145616 Japanese Patent Application Laid-Open No. 6-145616
- the adhesive layer tends to remain on the adherend surface when the adhesive film is peeled off. That is, the contamination resistance with respect to a to-be-adhered body will fall.
- tackifiers are relatively expensive and there is a concern about supply concerns accompanying an increase in global demand, there has also been a demand to reduce the amount of tackifier used.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-255233
- Patent Document 2 Japanese Patent Application Laid-Open No. 2008-255233
- the present invention has been made in view of the problems as described above.
- the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is pressure-bonded to an adherend under room temperature conditions without positively heating, it has a desired pressure-sensitive adhesive force. It is to provide a pressure-sensitive adhesive film or sheet in which the amount of the agent used is reduced.
- a pressure-sensitive adhesive film or sheet comprising an adhesive layer containing a tackifier having a hydrogenation rate in the range of 50% or more and less than 90%.
- a surface protective film or sheet comprising the pressure-sensitive adhesive film or sheet is provided.
- an ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less and a tackifier having a hydrogenation rate of 50% or more and less than 90%. Even if the addition amount of the pressure-sensitive adhesive resin is small, a pressure-sensitive adhesive film or sheet having a desired adhesive strength can be obtained.
- a method of using the pressure-sensitive adhesive film or sheet to protect the surface of an article is provided.
- the pressure-sensitive adhesive film or sheet according to the present embodiment includes an ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less and a tackifier having a hydrogenation rate of 50% or more and less than 90%.
- An adhesive layer containing an agent is provided.
- the adhesive force between the adhesive layer and the adherend in the present invention is not to adhere and adhere the adhesive layer to the adherend under heating conditions equal to or higher than the melting point of the adhesive such as a hot melt adhesive, It represents the delamination strength when the pressure-sensitive adhesive layer is bonded to the adherend in a temperature atmosphere below the melting point.
- the ethylene / vinyl acetate copolymer (EVA) which is an essential component of the present invention is a copolymer of ethylene and vinyl acetate.
- the ethylene / vinyl acetate copolymer of the present invention has a vinyl acetate component unit content of 7.5% to 20% by mass, preferably 8% to 15% by mass, and particularly preferably 9%. It is 12% by mass or more.
- a pressure-sensitive adhesive film or sheet having an appropriate initial adhesive force can be obtained.
- the vinyl acetate content is not less than the above lower limit value, a pressure-sensitive adhesive film or sheet having even better initial adhesive strength can be obtained.
- the vinyl acetate content is not more than the above upper limit, a pressure-sensitive adhesive film or sheet in which the progress of the adhesive force over time is suppressed can be obtained. That is, the contamination resistance to the adherend is further improved.
- the ethylene / vinyl acetate copolymer of this embodiment is not particularly limited, but preferably has a melt flow rate (MFR) at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 1 g / 10 min or more and 50 g. / 10 minutes or less, particularly preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less.
- MFR melt flow rate
- the ethylene / vinyl acetate copolymer of this embodiment is not particularly limited, but preferably has a melt flow rate (MFR) at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 1 g / 10 min or more and 50 g. / 10 minutes or less, particularly preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less.
- Tackifier The tackifier which is an essential component of the present invention is blended in order to improve the adhesive strength of the adhesive layer.
- tackifiers include hydrogenated petroleum resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic-aromatic copolymer hydrocarbon resins, and alicyclic hydrocarbon resins. ; Hydrogenated product of terpene resin such as pinene resin, coumarone indene resin, terpene phenol resin; Hydrogenated product of polymerized rosin resin; Hydrogenated product of (alkyl) phenolic resin; Hydrogenation of xylene resin A hydrogenated product of a styrenic resin.
- hydrogenated petroleum resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic-aromatic copolymer hydrocarbon resins, and alicyclic hydrocarbon resins.
- Hydrogenated product of terpene resin such as pinene resin, coumarone indene resin, terpene phenol resin
- Hydrogenated product of polymerized rosin resin Hydrogenated product of (alkyl)
- hydrogenated products of petroleum resins are preferable, and hydrogenated products of alicyclic hydrocarbon resins (also referred to as alicyclic saturated hydrocarbon resins) are particularly preferable.
- These tackifiers may contain an olefin resin.
- hydrogenated products of petroleum resins include hydrogenated products of resins mainly composed of C 8 to C 10 vinyl aromatic hydrocarbons such as vinyltoluene, indene and ⁇ -methylstyrene.
- hydrogenated terpene resins include hydrogenated products such as ⁇ -pinene polymers, ⁇ -pinene polymers, dipentene polymers, and terpene / phenol copolymers.
- Examples of the hydrogenated polymerized rosin resin include hydrogenated rosin, hydrogenated rosin glycerin ester or polymer thereof, and hydrogenated rosin pentaerythritol ester or polymer thereof.
- Examples of the hydrogenated product of the styrene resin include hydrogenated products such as a homopolymer of a styrene monomer, a styrene / olefin copolymer, and a vinyltoluene / ⁇ -methylstyrene copolymer.
- the tackifier of the present invention has a hydrogenation rate in the range of 50% to less than 90%, preferably in the range of 55% to 80%, particularly preferably in the range of 60% to 70%. It is. When the hydrogenation rate is within the above range, a pressure-sensitive adhesive film or sheet having a desired adhesive force can be obtained in a smaller amount, and the amount of tackifier used can be reduced.
- the tackifier is not particularly limited, but the softening temperature measured according to JIS K2207-1996 ring and ball method is preferably 80 ° C. or higher, more preferably 85 ° C. or higher. When the softening temperature is equal to or higher than the above lower limit, the initial pressure-sensitive adhesive strength of the resulting pressure-sensitive adhesive film or sheet is further excellent, and the handling property is also excellent.
- the tackifier is not particularly limited, but the softening temperature measured in accordance with the JIS K2207-1996 ring and ball method is preferably 150 ° C. or lower, more preferably 140 ° C. or lower. When the softening temperature is not more than the above upper limit, it is possible to further suppress the pressure-sensitive adhesive film or sheet from being obtained.
- the content of the tackifier in the present embodiment is not particularly limited, but preferably 0.1 mass when the total amount of the ethylene / vinyl acetate copolymer and the tackifier is 100 parts by mass. Part or more, more preferably 0.3 part by weight or more, and particularly preferably 0.5 part by weight or more. When the content of the tackifier is equal to or higher than the lower limit, a pressure-sensitive adhesive film or sheet having further excellent initial adhesive strength can be obtained.
- the tackifier content is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.2 parts by mass or less, and particularly preferably 1. 5 parts by mass or less. When the content of the tackifier is not more than the above upper limit, a pressure-sensitive pressure-sensitive adhesive film or sheet having an even better balance between the suppression of the progress of the adhesive force over time and the stain resistance to the adherend is obtained. Can do.
- the adhesive layer in the present embodiment contains additives usually used in the polymer field such as an antioxidant, an ultraviolet absorber, a light stabilizer, and an antiblocking agent to the extent that the properties of the adhesive layer are not impaired. Furthermore, you may mix
- the pressure-sensitive adhesive film or sheet in this embodiment can be obtained, for example, by molding a resin composition containing the ethylene / vinyl acetate copolymer and the tackifier into a single layer film or sheet.
- the obtained single layer film or sheet corresponds to the adhesive layer of the present embodiment.
- It can also be obtained by forming an adhesive layer on at least one surface of the substrate using the resin composition. Usually, a method of forming an adhesive layer on at least one surface of the substrate using the latter resin composition is used.
- the substrate to be used is not particularly limited, but one or more thermoplastic resins such as polyester, polyamide, and polyolefin are used. Examples include various stretched or unstretched thermoplastic resin films or sheets used.
- the polyolefin polypropylene, block type or random type propylene polymer having an ethylene component as a copolymer component; ethylene polymer such as low density polyethylene, high density polyethylene, linear low density or ultra low density polyethylene, etc. Ethylene-propylene copolymer and the like.
- the substrate paper; metal foil; non-woven fabric, etc. are also used.
- a substrate containing polyolefin such as polyethylene and polypropylene is particularly preferable.
- the base material containing polyolefin is used, the interlayer adhesiveness of an adhesion layer and a base material is favorable, and the film or sheet excellent in transparency is obtained.
- thermoplastic resin film for the purpose of preventing deterioration, for example, an antioxidant; an ultraviolet absorber; a light stabilizer such as a hindered amine light stabilizer; an antistatic agent; carbon black, calcium oxide
- blend additives such as fillers, such as magnesium oxide, a silica, a zinc oxide, and a titanium oxide, and a pigment, in the thermoplastic resin used as a base material as needed.
- the thickness of the substrate is not particularly limited, but is usually 1 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 200 ⁇ m or less.
- the resin composition used for forming the pressure-sensitive adhesive layer of the present embodiment includes, for example, the ethylene / vinyl acetate copolymer, the tackifier, and, if necessary, other additives simultaneously or sequentially. Obtained by dry blending or melt blending. Various mixers such as a Henschel mixer and a tumbler mixer can be used for the dry blending. In the case of melt blending, a kneading apparatus such as a single or twin screw extruder, a Banbury mixer, a roll or a kneader can be used. For example, melt kneading is performed at a temperature of about 140 ° C to 230 ° C.
- Method for forming adhesive layer on substrate The method for forming an adhesive layer made of the resin composition of the present embodiment on a substrate is, for example, a solution coating method in which a solution of a resin composition or a hot melt is applied to the substrate; After the coating, the formed adhesive layer is transferred and transferred; the resin composition is extruded and coated on the substrate; and the substrate and the resin composition are combined in two or more layers.
- Extrusion molding method; Extrusion laminating resin composition on substrate; Extrusion laminating adhesive layer and resin composition in two layers; Adhesive layer and supporting substrate forming material such as film or laminate layer Can be carried out in accordance with a known method such as thermal lamination.
- a method in which a resin composition is co-extruded in a multilayer of two layers or three or more layers by an inflation method or a T-die method together with a base material made of a thermoplastic resin is preferable.
- the thickness of the pressure-sensitive adhesive layer formed on the substrate is appropriately determined according to the pressure-sensitive adhesive force and the like, but is generally 1 ⁇ m or more and 250 ⁇ m or less, more preferably 5 ⁇ m or more and 100 ⁇ m or less. In the case of a single layer film or sheet having no substrate, it is preferably 5 ⁇ m or more and 300 ⁇ m or less, more preferably 10 ⁇ m or more and 200 ⁇ m or less.
- the pressure-sensitive adhesive film or sheet in the present embodiment is attached only by pressure without positively heating so that the adhesive layer faces the surface of a hard (rigid) adherend. When not needed, it is easily peeled off by hand, leaving no contaminants on the surface of the adherend.
- the adherend include product surface protection such as a synthetic resin plate, a decorative plate, a metal plate, and a coated steel plate. Further, for window glass surface protection, surface protection at the time of carving and painting of automobiles, and soldering of printed circuit boards.
- liquid crystal panel plates which are constituent members of liquid crystal display devices, plasma display devices, organic thin film EL devices, etc .; reflectors, retardation plates, prism sheets, light guide plates, polarizing plates, plasma display panel plates, organic phosphor thin films And precision electronic components such as transparent electrodes, flexible printed circuit boards, and rigid printed circuit boards.
- the pressure-sensitive adhesive film or sheet in this embodiment is particularly suitably used as a film or sheet for protecting these surfaces.
- a method of using the pressure-sensitive adhesive film or sheet as described above for protecting the surface of an article can be provided.
- the article to be surface protected include the adherend described above.
- Tackifier 2 Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-100, softening temperature 100 ° C, hydrogenation rate 60% to 70%)
- Tackifier 3 Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-115, softening temperature 115 ° C., hydrogenation rate 60% to 70%)
- Tackifier 4 Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-135, softening temperature 135 ° C., hydrogenation rate 60% to 70%)
- Tackifier 5 Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon P-
Abstract
This pressure-sensitive adhesive film or sheet is provided with an adhesive layer containing: an ethylene-vinyl acetate copolymer having 7.5-20 mass% inclusive of contained vinyl acetate; and a tackifier having a hydrogenation rate of at least 50% and less than 90%.
Description
本発明は、感圧型粘着フィルムまたはシート、表面保護フィルムまたはシート、および感圧型粘着フィルムまたはシートを物品の表面を保護するために使用する方法に関する。
The present invention relates to a pressure-sensitive adhesive film or sheet, a surface protective film or sheet, and a method of using the pressure-sensitive adhesive film or sheet to protect the surface of an article.
粘着フィルムまたはシートは、製品の表面を塵の付着、汚れ、傷などから保護するための表面保護フィルムとして用いられてきた。
近年、精密電子部品の表面保護フィルムとしても用いられている。 An adhesive film or sheet has been used as a surface protective film for protecting the surface of a product from dust adhesion, dirt, scratches, and the like.
In recent years, it is also used as a surface protective film for precision electronic components.
近年、精密電子部品の表面保護フィルムとしても用いられている。 An adhesive film or sheet has been used as a surface protective film for protecting the surface of a product from dust adhesion, dirt, scratches, and the like.
In recent years, it is also used as a surface protective film for precision electronic components.
粘着フィルムまたはシートには、粘着層と被着体との粘着力は適度に強いことが求められる。この適度な強さとは、自然に自己剥離したり軽い振動や衝撃で脱落したりすることが無い強さであり、かつ、剥離するときには被着体表面に粘着層を残すことなくスムーズに剥離できる強さをいう。
The adhesive film or sheet is required to have a moderately strong adhesive force between the adhesive layer and the adherend. This moderate strength is the strength that does not spontaneously peel off or fall off due to light vibration or impact, and can be peeled smoothly without leaving an adhesive layer on the adherend surface. Say strength.
このような要求特性を満たす粘着フィルムまたはシートには、エチレン－酢酸ビニル共重合体からなるフィルムまたはシートがある。
An adhesive film or sheet satisfying such required characteristics includes a film or sheet made of an ethylene-vinyl acetate copolymer.
特許文献１（特開平６－１４５６１６号）には、粘着層が、酢酸ビニル含有量３～７重量％およびメルトフローレート２～２０ｇ／１０分を有するエチレン－酢酸ビニル共重合体１００重量部に対して粘着付与剤を０．５～２重量部含ませたものからなることを特徴とする表面保護フィルムが記載されている。この表面保護フィルムは、適度の初期粘着力が発揮され、加熱処理、特にＵＶ照射が施されたとしても、粘着力が著しく上昇することがなく、また、被保護物への汚染性もないとされている。
In Patent Document 1 (Japanese Patent Laid-Open No. 6-145616), an adhesive layer is formed on 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 7% by weight and a melt flow rate of 2 to 20 g / 10 min. On the other hand, a surface protective film characterized by comprising 0.5 to 2 parts by weight of a tackifier is described. This surface protective film exhibits moderate initial adhesive strength, and even when subjected to heat treatment, particularly UV irradiation, the adhesive strength is not significantly increased, and there is no contamination to the object to be protected. Has been.
特許文献２（特開２００８－２５５２３３号）には、ポリプロピレン樹脂基材層（Ａ）と酢酸ビニル単位含量が７．５～５０重量％のエチレン・酢酸ビニル共重合体からなる粘着層（Ｂ）とからなる粘着フィルムまたはシートが記載されている。
この粘着フィルムまたはシートは、基材層と粘着層との層間接着強度が高く、粘着層は被粘着対象物品面に対し適度な粘着力を有し、かつ、その基材層は軟化温度、熱変形温度などの熱的特性、引張強度、耐衝撃性、スティフネスなどの機械特性、ヘイズ、グロス、光透過度などの光学特性に優れ、加えてフィッシュアイの発生がほとんど無く、表面平滑で外観も極めて良好であるとされている。 Patent Document 2 (Japanese Patent Laid-Open No. 2008-255233) discloses a polypropylene resin base layer (A) and an adhesive layer (B) comprising an ethylene / vinyl acetate copolymer having a vinyl acetate unit content of 7.5 to 50% by weight. An adhesive film or sheet consisting of
This pressure-sensitive adhesive film or sheet has a high interlayer adhesion strength between the base material layer and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer has an appropriate pressure-sensitive adhesive force with respect to the surface of the article to be adhered, and the base material layer has a softening temperature, heat Excellent thermal properties such as deformation temperature, mechanical properties such as tensile strength, impact resistance, and stiffness, optical properties such as haze, gloss, and light transmittance. In addition, there is almost no generation of fish eyes, smooth surface and appearance. It is said to be very good.
この粘着フィルムまたはシートは、基材層と粘着層との層間接着強度が高く、粘着層は被粘着対象物品面に対し適度な粘着力を有し、かつ、その基材層は軟化温度、熱変形温度などの熱的特性、引張強度、耐衝撃性、スティフネスなどの機械特性、ヘイズ、グロス、光透過度などの光学特性に優れ、加えてフィッシュアイの発生がほとんど無く、表面平滑で外観も極めて良好であるとされている。 Patent Document 2 (Japanese Patent Laid-Open No. 2008-255233) discloses a polypropylene resin base layer (A) and an adhesive layer (B) comprising an ethylene / vinyl acetate copolymer having a vinyl acetate unit content of 7.5 to 50% by weight. An adhesive film or sheet consisting of
This pressure-sensitive adhesive film or sheet has a high interlayer adhesion strength between the base material layer and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer has an appropriate pressure-sensitive adhesive force with respect to the surface of the article to be adhered, and the base material layer has a softening temperature, heat Excellent thermal properties such as deformation temperature, mechanical properties such as tensile strength, impact resistance, and stiffness, optical properties such as haze, gloss, and light transmittance. In addition, there is almost no generation of fish eyes, smooth surface and appearance. It is said to be very good.
一方、特許文献３（特開２０１０－１７１４１９号）には、（Ａ）エチレン・酢酸ビニル共重合体樹脂、及び、（Ａ）との相溶性が高い（Ｂ）Ｃ９系芳香族炭化水素樹脂の水素化物を含み、上記（Ｂ）Ｃ９系芳香族炭化水素樹脂の水素化物の水素化率が４０％以上である太陽電池用封止材シートが記載されている。
この太陽電池用封止材シートは、溶融・加工等の処理を行う際の加工性に優れ、さらに高い透明性を有しつつ耐光性および耐熱性に優れ、安定性が高いとされている。 On the other hand, Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-171419) describes (A) an ethylene / vinyl acetate copolymer resin and (B) a C9 aromatic hydrocarbon resin having high compatibility with (A). A solar cell encapsulant sheet containing a hydride and having a hydrogenation rate of the hydride of the above (B) C9-based aromatic hydrocarbon resin is 40% or more is described.
This solar cell encapsulant sheet is said to be excellent in workability when performing processing such as melting and processing, and further excellent in light resistance and heat resistance while having high transparency and high stability.
この太陽電池用封止材シートは、溶融・加工等の処理を行う際の加工性に優れ、さらに高い透明性を有しつつ耐光性および耐熱性に優れ、安定性が高いとされている。 On the other hand, Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-171419) describes (A) an ethylene / vinyl acetate copolymer resin and (B) a C9 aromatic hydrocarbon resin having high compatibility with (A). A solar cell encapsulant sheet containing a hydride and having a hydrogenation rate of the hydride of the above (B) C9-based aromatic hydrocarbon resin is 40% or more is described.
This solar cell encapsulant sheet is said to be excellent in workability when performing processing such as melting and processing, and further excellent in light resistance and heat resistance while having high transparency and high stability.
特許文献１（特開平６－１４５６１６号公報）に記載の酢酸ビニル含有量３～７重量％のエチレン－酢酸ビニル共重合体からなるフィルムは、被着体に対して粘着力が十分ではなかった。そのため、所望の粘着力を得るために、粘着付与剤を多く含有させる必要があった。
しかしながら、粘着付与剤を粘着層に多く含有させると、粘着フィルムを剥離するときに被着体表面に粘着層が残りやすくなってしまった。つまり被着体に対する耐汚染性が低下してしまう。
また、粘着付与剤は比較的高価であり、さらに世界的な需要増加に伴う供給不安の懸念もあるため、粘着付与剤の使用量を減らしたいという要望もあった。 The film made of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 7% by weight described in Patent Document 1 (Japanese Patent Application Laid-Open No. 6-145616) does not have sufficient adhesion to the adherend. . Therefore, in order to obtain a desired adhesive strength, it is necessary to contain a large amount of tackifier.
However, when a large amount of tackifier is contained in the adhesive layer, the adhesive layer tends to remain on the adherend surface when the adhesive film is peeled off. That is, the contamination resistance with respect to a to-be-adhered body will fall.
In addition, since tackifiers are relatively expensive and there is a concern about supply concerns accompanying an increase in global demand, there has also been a demand to reduce the amount of tackifier used.
しかしながら、粘着付与剤を粘着層に多く含有させると、粘着フィルムを剥離するときに被着体表面に粘着層が残りやすくなってしまった。つまり被着体に対する耐汚染性が低下してしまう。
また、粘着付与剤は比較的高価であり、さらに世界的な需要増加に伴う供給不安の懸念もあるため、粘着付与剤の使用量を減らしたいという要望もあった。 The film made of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 7% by weight described in Patent Document 1 (Japanese Patent Application Laid-Open No. 6-145616) does not have sufficient adhesion to the adherend. . Therefore, in order to obtain a desired adhesive strength, it is necessary to contain a large amount of tackifier.
However, when a large amount of tackifier is contained in the adhesive layer, the adhesive layer tends to remain on the adherend surface when the adhesive film is peeled off. That is, the contamination resistance with respect to a to-be-adhered body will fall.
In addition, since tackifiers are relatively expensive and there is a concern about supply concerns accompanying an increase in global demand, there has also been a demand to reduce the amount of tackifier used.
また、特許文献２（特開２００８－２５５２３３号公報）に記載の酢酸ビニル単位含量が７．５～５０重量％のエチレン－酢酸ビニル共重合体も、被着体に対して粘着力が十分ではなかった。また、粘着力が初期粘着力よりも経時的に強くなっていくという経時的昂進の傾向が強かった。
In addition, an ethylene-vinyl acetate copolymer having a vinyl acetate unit content of 7.5 to 50% by weight described in Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-255233) also has insufficient adhesion to the adherend. There wasn't. In addition, the tendency to progress over time was strong, with the adhesive strength becoming stronger with time than the initial adhesive strength.
本発明は上述のような課題に鑑みてなされたものであり、粘着層を積極的に加熱することなく室温条件下で被着体に圧着した場合、所望の粘着力を有しながら、粘着付与剤の使用量が低減された感圧型粘着フィルムまたはシートを提供することである。
The present invention has been made in view of the problems as described above. When the pressure-sensitive adhesive layer is pressure-bonded to an adherend under room temperature conditions without positively heating, it has a desired pressure-sensitive adhesive force. It is to provide a pressure-sensitive adhesive film or sheet in which the amount of the agent used is reduced.
本発明によれば、
酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、
水素化率が５０％以上９０％未満の範囲内にある粘着付与剤と
を含む粘着層を備える、感圧型粘着フィルムまたはシートが提供される。 According to the present invention,
An ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5 to 20% by mass;
There is provided a pressure-sensitive adhesive film or sheet comprising an adhesive layer containing a tackifier having a hydrogenation rate in the range of 50% or more and less than 90%.
酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、
水素化率が５０％以上９０％未満の範囲内にある粘着付与剤と
を含む粘着層を備える、感圧型粘着フィルムまたはシートが提供される。 According to the present invention,
An ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5 to 20% by mass;
There is provided a pressure-sensitive adhesive film or sheet comprising an adhesive layer containing a tackifier having a hydrogenation rate in the range of 50% or more and less than 90%.
さらに本発明によれば、
上記感圧型粘着フィルムまたはシートを含む、表面保護フィルムまたはシートが提供される。 Furthermore, according to the present invention,
A surface protective film or sheet comprising the pressure-sensitive adhesive film or sheet is provided.
上記感圧型粘着フィルムまたはシートを含む、表面保護フィルムまたはシートが提供される。 Furthermore, according to the present invention,
A surface protective film or sheet comprising the pressure-sensitive adhesive film or sheet is provided.
この発明によれば、酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、水素化率が５０％以上９０％未満の粘着付与剤とを含むことにより、粘着剤付与樹脂の添加量が少なくても、所望の粘着力を有する感圧型粘着フィルムまたはシートを得ることができる。
According to this invention, by containing an ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less, and a tackifier having a hydrogenation rate of 50% or more and less than 90%. Even if the addition amount of the pressure-sensitive adhesive resin is small, a pressure-sensitive adhesive film or sheet having a desired adhesive strength can be obtained.
さらに、本発明によれば、
上記感圧型粘着フィルムまたはシートを、物品の表面を保護するために使用する方法が提供される。 Furthermore, according to the present invention,
A method of using the pressure-sensitive adhesive film or sheet to protect the surface of an article is provided.
上記感圧型粘着フィルムまたはシートを、物品の表面を保護するために使用する方法が提供される。 Furthermore, according to the present invention,
A method of using the pressure-sensitive adhesive film or sheet to protect the surface of an article is provided.
本発明によれば、所望の粘着力を有しながら、粘着付与剤の使用量が低減された感圧型粘着フィルムまたはシートを提供することができる。
According to the present invention, it is possible to provide a pressure-sensitive adhesive film or sheet in which the amount of tackifier used is reduced while having a desired adhesive strength.
上述した目的、およびその他の目的、特徴および利点は、以下に述べる好適な実施の形態によってさらに明らかになる。
The above-described object and other objects, features, and advantages will be further clarified by the preferred embodiments described below.
以下に、本発明における実施の形態について説明する。
本実施形態における感圧型粘着フィルムまたはシートは、酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、水素化率が５０％以上９０％未満の粘着付与剤とを含む粘着層を備えている。
なお、本発明における粘着層と被着体との粘着力は、ホットメルト接着剤のような接着剤の融点以上の加熱条件下で被着体に粘着層を圧着して接着するものではなく、融点未満の温度雰囲気下で被着体に粘着層を圧着して接着したときの層間剥離強度のことを表す。 Embodiments according to the present invention will be described below.
The pressure-sensitive adhesive film or sheet according to the present embodiment includes an ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less and a tackifier having a hydrogenation rate of 50% or more and less than 90%. An adhesive layer containing an agent is provided.
In addition, the adhesive force between the adhesive layer and the adherend in the present invention is not to adhere and adhere the adhesive layer to the adherend under heating conditions equal to or higher than the melting point of the adhesive such as a hot melt adhesive, It represents the delamination strength when the pressure-sensitive adhesive layer is bonded to the adherend in a temperature atmosphere below the melting point.
本実施形態における感圧型粘着フィルムまたはシートは、酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、水素化率が５０％以上９０％未満の粘着付与剤とを含む粘着層を備えている。
なお、本発明における粘着層と被着体との粘着力は、ホットメルト接着剤のような接着剤の融点以上の加熱条件下で被着体に粘着層を圧着して接着するものではなく、融点未満の温度雰囲気下で被着体に粘着層を圧着して接着したときの層間剥離強度のことを表す。 Embodiments according to the present invention will be described below.
The pressure-sensitive adhesive film or sheet according to the present embodiment includes an ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less and a tackifier having a hydrogenation rate of 50% or more and less than 90%. An adhesive layer containing an agent is provided.
In addition, the adhesive force between the adhesive layer and the adherend in the present invention is not to adhere and adhere the adhesive layer to the adherend under heating conditions equal to or higher than the melting point of the adhesive such as a hot melt adhesive, It represents the delamination strength when the pressure-sensitive adhesive layer is bonded to the adherend in a temperature atmosphere below the melting point.
（粘着層）
はじめに、本実施形態における感圧型粘着フィルムまたはシートを構成する粘着層の各成分について説明する。 (Adhesive layer)
First, each component of the pressure-sensitive adhesive layer constituting the pressure-sensitive pressure-sensitive adhesive film or sheet in this embodiment will be described.
はじめに、本実施形態における感圧型粘着フィルムまたはシートを構成する粘着層の各成分について説明する。 (Adhesive layer)
First, each component of the pressure-sensitive adhesive layer constituting the pressure-sensitive pressure-sensitive adhesive film or sheet in this embodiment will be described.
「エチレン・酢酸ビニル共重合体」
本発明の必須成分であるエチレン・酢酸ビニル共重合体（ＥＶＡ）は、エチレンと酢酸ビニルとの共重合体である。
本発明のエチレン・酢酸ビニル共重合体は、酢酸ビニル成分の単位含有量が７．５質量％以上２０質量％以下であり、好ましくは８質量％以上１５質量％以下であり、とくに好ましくは９質量％以上１２質量％以下である。酢酸ビニル含有量が上記範囲内であると、適度な初期粘着力を有する感圧型粘着フィルムまたはシートが得られる。
酢酸ビニル含有量が上記下限値以上であると、初期粘着力がより一層優れる感圧型粘着フィルムまたはシートが得られる。一方、酢酸ビニル含有量が上記上限値以下であると、粘着力の経時的昂進が抑制された感圧型粘着フィルムまたはシートが得られる。つまり被着体に対する耐汚染性がより一層優れる。 "Ethylene / vinyl acetate copolymer"
The ethylene / vinyl acetate copolymer (EVA) which is an essential component of the present invention is a copolymer of ethylene and vinyl acetate.
The ethylene / vinyl acetate copolymer of the present invention has a vinyl acetate component unit content of 7.5% to 20% by mass, preferably 8% to 15% by mass, and particularly preferably 9%. It is 12% by mass or more. When the vinyl acetate content is within the above range, a pressure-sensitive adhesive film or sheet having an appropriate initial adhesive force can be obtained.
When the vinyl acetate content is not less than the above lower limit value, a pressure-sensitive adhesive film or sheet having even better initial adhesive strength can be obtained. On the other hand, when the vinyl acetate content is not more than the above upper limit, a pressure-sensitive adhesive film or sheet in which the progress of the adhesive force over time is suppressed can be obtained. That is, the contamination resistance to the adherend is further improved.
本発明の必須成分であるエチレン・酢酸ビニル共重合体（ＥＶＡ）は、エチレンと酢酸ビニルとの共重合体である。
本発明のエチレン・酢酸ビニル共重合体は、酢酸ビニル成分の単位含有量が７．５質量％以上２０質量％以下であり、好ましくは８質量％以上１５質量％以下であり、とくに好ましくは９質量％以上１２質量％以下である。酢酸ビニル含有量が上記範囲内であると、適度な初期粘着力を有する感圧型粘着フィルムまたはシートが得られる。
酢酸ビニル含有量が上記下限値以上であると、初期粘着力がより一層優れる感圧型粘着フィルムまたはシートが得られる。一方、酢酸ビニル含有量が上記上限値以下であると、粘着力の経時的昂進が抑制された感圧型粘着フィルムまたはシートが得られる。つまり被着体に対する耐汚染性がより一層優れる。 "Ethylene / vinyl acetate copolymer"
The ethylene / vinyl acetate copolymer (EVA) which is an essential component of the present invention is a copolymer of ethylene and vinyl acetate.
The ethylene / vinyl acetate copolymer of the present invention has a vinyl acetate component unit content of 7.5% to 20% by mass, preferably 8% to 15% by mass, and particularly preferably 9%. It is 12% by mass or more. When the vinyl acetate content is within the above range, a pressure-sensitive adhesive film or sheet having an appropriate initial adhesive force can be obtained.
When the vinyl acetate content is not less than the above lower limit value, a pressure-sensitive adhesive film or sheet having even better initial adhesive strength can be obtained. On the other hand, when the vinyl acetate content is not more than the above upper limit, a pressure-sensitive adhesive film or sheet in which the progress of the adhesive force over time is suppressed can be obtained. That is, the contamination resistance to the adherend is further improved.
また、本実施形態のエチレン・酢酸ビニル共重合体は、とくに限定はされないが、１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ７２１０－１９９９に準拠）が好ましくは１ｇ／１０分以上５０ｇ／１０分以下であり、とくに好ましくは２ｇ／１０分以上３０ｇ/１０分以下である。
ＭＦＲが上記下限値以上であると、フィルムの平滑性および初期粘着力がより一層優れる。一方、ＭＦＲが上記上限値以下であると、低分子成分が少なくなるため、フィルムのブロッキング性や保護基材への耐汚染性がより一層優れる。 The ethylene / vinyl acetate copolymer of this embodiment is not particularly limited, but preferably has a melt flow rate (MFR) at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 1 g / 10 min or more and 50 g. / 10 minutes or less, particularly preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less.
When the MFR is not less than the above lower limit, the smoothness and initial adhesive strength of the film are further improved. On the other hand, when the MFR is less than or equal to the above upper limit value, low molecular components are reduced, and thus the blocking property of the film and the stain resistance to the protective substrate are further improved.
ＭＦＲが上記下限値以上であると、フィルムの平滑性および初期粘着力がより一層優れる。一方、ＭＦＲが上記上限値以下であると、低分子成分が少なくなるため、フィルムのブロッキング性や保護基材への耐汚染性がより一層優れる。 The ethylene / vinyl acetate copolymer of this embodiment is not particularly limited, but preferably has a melt flow rate (MFR) at 190 ° C. under a load of 2160 g (according to JIS K7210-1999) of 1 g / 10 min or more and 50 g. / 10 minutes or less, particularly preferably 2 g / 10 minutes or more and 30 g / 10 minutes or less.
When the MFR is not less than the above lower limit, the smoothness and initial adhesive strength of the film are further improved. On the other hand, when the MFR is less than or equal to the above upper limit value, low molecular components are reduced, and thus the blocking property of the film and the stain resistance to the protective substrate are further improved.
「粘着付与剤」
本発明の必須成分である粘着付与剤は、粘着層の粘着力を向上させるために配合する。 "Tackifier"
The tackifier which is an essential component of the present invention is blended in order to improve the adhesive strength of the adhesive layer.
本発明の必須成分である粘着付与剤は、粘着層の粘着力を向上させるために配合する。 "Tackifier"
The tackifier which is an essential component of the present invention is blended in order to improve the adhesive strength of the adhesive layer.
粘着付与剤としては、例えば、脂肪族系炭化水素樹脂、芳香族系炭化水素樹脂、脂肪族－芳香族共重合体系炭化水素樹脂、脂環族系炭化水素樹脂などの石油系樹脂の水素添加物；ピネン樹脂、クマロンインデン系樹脂、テルペンフェノール系樹脂などのテルペン系樹脂の水素添加物；重合ロジン系樹脂の水素添加物；（アルキル）フェノール系樹脂の水素添加物；キシレン系樹脂の水素添加物；スチレン系樹脂の水素添加物などが挙げられる。これらの中でも、石油系樹脂の水素添加物が好ましく、脂環族系炭化水素樹脂の水素添加物（脂環族飽和炭化水素樹脂とも呼ぶ。）がとくに好ましい。
これらの粘着付与剤には、オレフィン樹脂が含まれていてもよい。
石油系樹脂の水素添加物としては、ビニルトルエン、インデン、α－メチルスチレンなどのＣ8～Ｃ10のビニル芳香族炭化水素を主成分とする樹脂の水素添加物などが挙げられる。
テルペン系樹脂の水素添加物としては、例えば、α－ピネン重合体、β－ピネン重合体、ジペンテン重合体、テルペン・フェノール共重合体などの水素添加物が挙げられる。
重合ロジン系樹脂の水素添加物としては、例えば、水素化ロジン、水素化ロジンのグリセリンエステルまたはその重合体、および水素化ロジンのペンタエリスリットエステルまたはその重合体などが挙げられる。
スチレン系樹脂の水素添加物としては、例えば、スチレン系モノマーの単独重合体、スチレン・オレフィン共重合体、ビニルトルエン・α－メチルスチレン共重合体などの水素添加物が挙げられる。 Examples of tackifiers include hydrogenated petroleum resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic-aromatic copolymer hydrocarbon resins, and alicyclic hydrocarbon resins. ; Hydrogenated product of terpene resin such as pinene resin, coumarone indene resin, terpene phenol resin; Hydrogenated product of polymerized rosin resin; Hydrogenated product of (alkyl) phenolic resin; Hydrogenation of xylene resin A hydrogenated product of a styrenic resin. Among these, hydrogenated products of petroleum resins are preferable, and hydrogenated products of alicyclic hydrocarbon resins (also referred to as alicyclic saturated hydrocarbon resins) are particularly preferable.
These tackifiers may contain an olefin resin.
Examples of hydrogenated products of petroleum resins include hydrogenated products of resins mainly composed of C 8 to C 10 vinyl aromatic hydrocarbons such as vinyltoluene, indene and α-methylstyrene.
Examples of hydrogenated terpene resins include hydrogenated products such as α-pinene polymers, β-pinene polymers, dipentene polymers, and terpene / phenol copolymers.
Examples of the hydrogenated polymerized rosin resin include hydrogenated rosin, hydrogenated rosin glycerin ester or polymer thereof, and hydrogenated rosin pentaerythritol ester or polymer thereof.
Examples of the hydrogenated product of the styrene resin include hydrogenated products such as a homopolymer of a styrene monomer, a styrene / olefin copolymer, and a vinyltoluene / α-methylstyrene copolymer.
これらの粘着付与剤には、オレフィン樹脂が含まれていてもよい。
石油系樹脂の水素添加物としては、ビニルトルエン、インデン、α－メチルスチレンなどのＣ8～Ｃ10のビニル芳香族炭化水素を主成分とする樹脂の水素添加物などが挙げられる。
テルペン系樹脂の水素添加物としては、例えば、α－ピネン重合体、β－ピネン重合体、ジペンテン重合体、テルペン・フェノール共重合体などの水素添加物が挙げられる。
重合ロジン系樹脂の水素添加物としては、例えば、水素化ロジン、水素化ロジンのグリセリンエステルまたはその重合体、および水素化ロジンのペンタエリスリットエステルまたはその重合体などが挙げられる。
スチレン系樹脂の水素添加物としては、例えば、スチレン系モノマーの単独重合体、スチレン・オレフィン共重合体、ビニルトルエン・α－メチルスチレン共重合体などの水素添加物が挙げられる。 Examples of tackifiers include hydrogenated petroleum resins such as aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic-aromatic copolymer hydrocarbon resins, and alicyclic hydrocarbon resins. ; Hydrogenated product of terpene resin such as pinene resin, coumarone indene resin, terpene phenol resin; Hydrogenated product of polymerized rosin resin; Hydrogenated product of (alkyl) phenolic resin; Hydrogenation of xylene resin A hydrogenated product of a styrenic resin. Among these, hydrogenated products of petroleum resins are preferable, and hydrogenated products of alicyclic hydrocarbon resins (also referred to as alicyclic saturated hydrocarbon resins) are particularly preferable.
These tackifiers may contain an olefin resin.
Examples of hydrogenated products of petroleum resins include hydrogenated products of resins mainly composed of C 8 to C 10 vinyl aromatic hydrocarbons such as vinyltoluene, indene and α-methylstyrene.
Examples of hydrogenated terpene resins include hydrogenated products such as α-pinene polymers, β-pinene polymers, dipentene polymers, and terpene / phenol copolymers.
Examples of the hydrogenated polymerized rosin resin include hydrogenated rosin, hydrogenated rosin glycerin ester or polymer thereof, and hydrogenated rosin pentaerythritol ester or polymer thereof.
Examples of the hydrogenated product of the styrene resin include hydrogenated products such as a homopolymer of a styrene monomer, a styrene / olefin copolymer, and a vinyltoluene / α-methylstyrene copolymer.
本発明の粘着付与剤は、水素化率が５０％以上９０％未満の範囲内であり、好ましくは５５％以上８０％以下の範囲内であり、とくに好ましくは６０％以上７０％以下の範囲内である。
水素化率が上記範囲内にあると、より少量で所望の粘着力を有する感圧型粘着フィルムまたはシートが得られるため、粘着付与剤の使用量を低減できる。 The tackifier of the present invention has a hydrogenation rate in the range of 50% to less than 90%, preferably in the range of 55% to 80%, particularly preferably in the range of 60% to 70%. It is.
When the hydrogenation rate is within the above range, a pressure-sensitive adhesive film or sheet having a desired adhesive force can be obtained in a smaller amount, and the amount of tackifier used can be reduced.
水素化率が上記範囲内にあると、より少量で所望の粘着力を有する感圧型粘着フィルムまたはシートが得られるため、粘着付与剤の使用量を低減できる。 The tackifier of the present invention has a hydrogenation rate in the range of 50% to less than 90%, preferably in the range of 55% to 80%, particularly preferably in the range of 60% to 70%. It is.
When the hydrogenation rate is within the above range, a pressure-sensitive adhesive film or sheet having a desired adhesive force can be obtained in a smaller amount, and the amount of tackifier used can be reduced.
なお、上記水素化率は、上記特許文献３（特開２０１０－１７１４１９号公報）に記載のＮＭＲ測定法により測定できる。具体的には、粘着付与剤の１Ｈ－ＮＭＲの７ｐｐｍ付近に現れる芳香環のＨ－スペクトル面積から以下の（１）式に基づいて計算する。
水素化率＝｛１－（粘着付与剤の水素添加物のスペクトル面積／未水素化粘着付与剤のスペクトル面積）｝×１００（％）・・・（１） The hydrogenation rate can be measured by the NMR measurement method described in Patent Document 3 (Japanese Patent Laid-Open No. 2010-171419). Specifically, it is calculated based on the following formula (1) from the H-spectral area of the aromatic ring appearing in the vicinity of 7 ppm of 1H-NMR of the tackifier.
Hydrogenation rate = {1− (spectral area of hydrogenated tackifier / spectral area of unhydrogenated tackifier)} × 100 (%) (1)
水素化率＝｛１－（粘着付与剤の水素添加物のスペクトル面積／未水素化粘着付与剤のスペクトル面積）｝×１００（％）・・・（１） The hydrogenation rate can be measured by the NMR measurement method described in Patent Document 3 (Japanese Patent Laid-Open No. 2010-171419). Specifically, it is calculated based on the following formula (1) from the H-spectral area of the aromatic ring appearing in the vicinity of 7 ppm of 1H-NMR of the tackifier.
Hydrogenation rate = {1− (spectral area of hydrogenated tackifier / spectral area of unhydrogenated tackifier)} × 100 (%) (1)
粘着付与剤は、とくに限定はされないが、ＪＩＳ Ｋ２２０７－１９９６環球法に準拠して測定した軟化温度が、好ましくは８０℃以上、より好ましくは８５℃以上である。軟化温度が上記下限値以上であると、得られる感圧型粘着フィルムまたはシートの初期粘着力がより一層優れ、かつハンドリング性にも優れる。
また、粘着付与剤は、とくに限定はされないが、ＪＩＳ Ｋ２２０７－１９９６環球法に準拠して測定した軟化温度が、好ましくは１５０℃以下であり、より好ましくは１４０℃以下である。軟化温度が上記上限値以下であると、得られる感圧型粘着フィルムまたはシートの粘着昂進をより一層抑制することができる。 The tackifier is not particularly limited, but the softening temperature measured according to JIS K2207-1996 ring and ball method is preferably 80 ° C. or higher, more preferably 85 ° C. or higher. When the softening temperature is equal to or higher than the above lower limit, the initial pressure-sensitive adhesive strength of the resulting pressure-sensitive adhesive film or sheet is further excellent, and the handling property is also excellent.
The tackifier is not particularly limited, but the softening temperature measured in accordance with the JIS K2207-1996 ring and ball method is preferably 150 ° C. or lower, more preferably 140 ° C. or lower. When the softening temperature is not more than the above upper limit, it is possible to further suppress the pressure-sensitive adhesive film or sheet from being obtained.
また、粘着付与剤は、とくに限定はされないが、ＪＩＳ Ｋ２２０７－１９９６環球法に準拠して測定した軟化温度が、好ましくは１５０℃以下であり、より好ましくは１４０℃以下である。軟化温度が上記上限値以下であると、得られる感圧型粘着フィルムまたはシートの粘着昂進をより一層抑制することができる。 The tackifier is not particularly limited, but the softening temperature measured according to JIS K2207-1996 ring and ball method is preferably 80 ° C. or higher, more preferably 85 ° C. or higher. When the softening temperature is equal to or higher than the above lower limit, the initial pressure-sensitive adhesive strength of the resulting pressure-sensitive adhesive film or sheet is further excellent, and the handling property is also excellent.
The tackifier is not particularly limited, but the softening temperature measured in accordance with the JIS K2207-1996 ring and ball method is preferably 150 ° C. or lower, more preferably 140 ° C. or lower. When the softening temperature is not more than the above upper limit, it is possible to further suppress the pressure-sensitive adhesive film or sheet from being obtained.
本実施形態における粘着付与剤の含有量は、とくに限定はされないが、上記エチレン・酢酸ビニル共重合体と、上記粘着付与剤との合計量を１００質量部としたとき、好ましくは０．１質量部以上であり、より好ましくは０．３質量部以上であり、とくに好ましくは０．５質量部以上である。粘着付与剤の含有量が上記下限値以上であると、初期粘着力がより一層優れた感圧型粘着フィルムまたはシートを得ることができる。
また、上記粘着付与剤の含有量は好ましくは５．０質量部以下であり、より好ましくは３．０質量部以下であり、更に好ましくは２．２質量部以下であり、とくに好ましくは１．５質量部以下である。粘着付与剤の含有量が上記上限値以下であると、粘着力の経時的昂進の抑制と、被着体への耐汚染性とのバランスがより一層優れた感圧型粘着フィルムまたはシートを得ることができる。 The content of the tackifier in the present embodiment is not particularly limited, but preferably 0.1 mass when the total amount of the ethylene / vinyl acetate copolymer and the tackifier is 100 parts by mass. Part or more, more preferably 0.3 part by weight or more, and particularly preferably 0.5 part by weight or more. When the content of the tackifier is equal to or higher than the lower limit, a pressure-sensitive adhesive film or sheet having further excellent initial adhesive strength can be obtained.
The tackifier content is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.2 parts by mass or less, and particularly preferably 1. 5 parts by mass or less. When the content of the tackifier is not more than the above upper limit, a pressure-sensitive pressure-sensitive adhesive film or sheet having an even better balance between the suppression of the progress of the adhesive force over time and the stain resistance to the adherend is obtained. Can do.
また、上記粘着付与剤の含有量は好ましくは５．０質量部以下であり、より好ましくは３．０質量部以下であり、更に好ましくは２．２質量部以下であり、とくに好ましくは１．５質量部以下である。粘着付与剤の含有量が上記上限値以下であると、粘着力の経時的昂進の抑制と、被着体への耐汚染性とのバランスがより一層優れた感圧型粘着フィルムまたはシートを得ることができる。 The content of the tackifier in the present embodiment is not particularly limited, but preferably 0.1 mass when the total amount of the ethylene / vinyl acetate copolymer and the tackifier is 100 parts by mass. Part or more, more preferably 0.3 part by weight or more, and particularly preferably 0.5 part by weight or more. When the content of the tackifier is equal to or higher than the lower limit, a pressure-sensitive adhesive film or sheet having further excellent initial adhesive strength can be obtained.
The tackifier content is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.2 parts by mass or less, and particularly preferably 1. 5 parts by mass or less. When the content of the tackifier is not more than the above upper limit, a pressure-sensitive pressure-sensitive adhesive film or sheet having an even better balance between the suppression of the progress of the adhesive force over time and the stain resistance to the adherend is obtained. Can do.
「他の添加剤」
また、本実施形態における粘着層には、粘着層の特性を損なわない程度に、酸化防止剤、紫外線吸収剤、光安定剤、およびアンチブロッキング剤などの高分子分野で通常使用される添加剤をさらに配合してもよい。 "Other additives"
In addition, the adhesive layer in the present embodiment contains additives usually used in the polymer field such as an antioxidant, an ultraviolet absorber, a light stabilizer, and an antiblocking agent to the extent that the properties of the adhesive layer are not impaired. Furthermore, you may mix | blend.
また、本実施形態における粘着層には、粘着層の特性を損なわない程度に、酸化防止剤、紫外線吸収剤、光安定剤、およびアンチブロッキング剤などの高分子分野で通常使用される添加剤をさらに配合してもよい。 "Other additives"
In addition, the adhesive layer in the present embodiment contains additives usually used in the polymer field such as an antioxidant, an ultraviolet absorber, a light stabilizer, and an antiblocking agent to the extent that the properties of the adhesive layer are not impaired. Furthermore, you may mix | blend.
（感圧型粘着フィルムまたはシートの製造方法）
本実施形態における感圧型粘着フィルムまたはシートは、例えば上記エチレン・酢酸ビニル共重合体と、上記粘着付与剤とを含む樹脂組成物を単層フィルムまたはシート状に成形することによって得られる。この場合は、得られた単層フィルムまたはシートが本実施形態の粘着層に相当する。また、上記樹脂組成物を用いて基材の少なくとも一方の面に粘着層を形成させることによっても得ることができる。
通常は、後者の上記樹脂組成物を用いて基材の少なくとも一方の面に粘着層を形成させる方法が用いられる。 (Method for producing pressure-sensitive adhesive film or sheet)
The pressure-sensitive adhesive film or sheet in this embodiment can be obtained, for example, by molding a resin composition containing the ethylene / vinyl acetate copolymer and the tackifier into a single layer film or sheet. In this case, the obtained single layer film or sheet corresponds to the adhesive layer of the present embodiment. It can also be obtained by forming an adhesive layer on at least one surface of the substrate using the resin composition.
Usually, a method of forming an adhesive layer on at least one surface of the substrate using the latter resin composition is used.
本実施形態における感圧型粘着フィルムまたはシートは、例えば上記エチレン・酢酸ビニル共重合体と、上記粘着付与剤とを含む樹脂組成物を単層フィルムまたはシート状に成形することによって得られる。この場合は、得られた単層フィルムまたはシートが本実施形態の粘着層に相当する。また、上記樹脂組成物を用いて基材の少なくとも一方の面に粘着層を形成させることによっても得ることができる。
通常は、後者の上記樹脂組成物を用いて基材の少なくとも一方の面に粘着層を形成させる方法が用いられる。 (Method for producing pressure-sensitive adhesive film or sheet)
The pressure-sensitive adhesive film or sheet in this embodiment can be obtained, for example, by molding a resin composition containing the ethylene / vinyl acetate copolymer and the tackifier into a single layer film or sheet. In this case, the obtained single layer film or sheet corresponds to the adhesive layer of the present embodiment. It can also be obtained by forming an adhesive layer on at least one surface of the substrate using the resin composition.
Usually, a method of forming an adhesive layer on at least one surface of the substrate using the latter resin composition is used.
「基材」
上記樹脂組成物からなる粘着層を基材の少なくとも一方の面に形成させる場合、使用する基材としては、とくに限定されないが、ポリエステル、ポリアミド、ポリオレフィンなどの熱可塑性樹脂を１種または２種以上用いてなる、延伸または未延伸の各種熱可塑性樹脂フィルムまたはシートが挙げられる。
ここで、ポリオレフィンとしては、ポリプロピレン、エチレン成分を共重合成分とするブロック系やランダム系のプロピレン系ポリマー；低密度ポリエチレン、高密度ポリエチレン、線状低密度や超低密度のポリエチレンなどのエチレン系ポリマー；エチレン－プロピレン共重合体などが挙げられる。
また、基材としては、紙；金属箔；不織布なども用いられる。
本実施形態においてはこれらの中でポリエチレン、ポリプロピレンなどのポリオレフィンを含む基材がとくに好ましい。
ポリオレフィンを含む基材を用いた場合、粘着層と基材との層間接着性が良好であり、また、透明性に優れたフィルムまたはシートが得られる。 "Base material"
When the adhesive layer made of the resin composition is formed on at least one surface of the substrate, the substrate to be used is not particularly limited, but one or more thermoplastic resins such as polyester, polyamide, and polyolefin are used. Examples include various stretched or unstretched thermoplastic resin films or sheets used.
Here, as the polyolefin, polypropylene, block type or random type propylene polymer having an ethylene component as a copolymer component; ethylene polymer such as low density polyethylene, high density polyethylene, linear low density or ultra low density polyethylene, etc. Ethylene-propylene copolymer and the like.
Further, as the substrate, paper; metal foil; non-woven fabric, etc. are also used.
In the present embodiment, among them, a substrate containing polyolefin such as polyethylene and polypropylene is particularly preferable.
When the base material containing polyolefin is used, the interlayer adhesiveness of an adhesion layer and a base material is favorable, and the film or sheet excellent in transparency is obtained.
上記樹脂組成物からなる粘着層を基材の少なくとも一方の面に形成させる場合、使用する基材としては、とくに限定されないが、ポリエステル、ポリアミド、ポリオレフィンなどの熱可塑性樹脂を１種または２種以上用いてなる、延伸または未延伸の各種熱可塑性樹脂フィルムまたはシートが挙げられる。
ここで、ポリオレフィンとしては、ポリプロピレン、エチレン成分を共重合成分とするブロック系やランダム系のプロピレン系ポリマー；低密度ポリエチレン、高密度ポリエチレン、線状低密度や超低密度のポリエチレンなどのエチレン系ポリマー；エチレン－プロピレン共重合体などが挙げられる。
また、基材としては、紙；金属箔；不織布なども用いられる。
本実施形態においてはこれらの中でポリエチレン、ポリプロピレンなどのポリオレフィンを含む基材がとくに好ましい。
ポリオレフィンを含む基材を用いた場合、粘着層と基材との層間接着性が良好であり、また、透明性に優れたフィルムまたはシートが得られる。 "Base material"
When the adhesive layer made of the resin composition is formed on at least one surface of the substrate, the substrate to be used is not particularly limited, but one or more thermoplastic resins such as polyester, polyamide, and polyolefin are used. Examples include various stretched or unstretched thermoplastic resin films or sheets used.
Here, as the polyolefin, polypropylene, block type or random type propylene polymer having an ethylene component as a copolymer component; ethylene polymer such as low density polyethylene, high density polyethylene, linear low density or ultra low density polyethylene, etc. Ethylene-propylene copolymer and the like.
Further, as the substrate, paper; metal foil; non-woven fabric, etc. are also used.
In the present embodiment, among them, a substrate containing polyolefin such as polyethylene and polypropylene is particularly preferable.
When the base material containing polyolefin is used, the interlayer adhesiveness of an adhesion layer and a base material is favorable, and the film or sheet excellent in transparency is obtained.
基材に熱可塑性樹脂フィルムを使用する場合には劣化防止などを目的に、例えば、酸化防止剤；紫外線吸収剤；ヒンダードアミン光安定剤などの光安定剤；帯電防止剤；カーボンブラック、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタンなどの充填剤や顔料などの添加剤を必要に応じて基材となる熱可塑性樹脂中にさらに配合してもよい。
In the case of using a thermoplastic resin film as a base material, for the purpose of preventing deterioration, for example, an antioxidant; an ultraviolet absorber; a light stabilizer such as a hindered amine light stabilizer; an antistatic agent; carbon black, calcium oxide, You may further mix | blend additives, such as fillers, such as magnesium oxide, a silica, a zinc oxide, and a titanium oxide, and a pigment, in the thermoplastic resin used as a base material as needed.
基材の厚さは、とくに限定されないが、通常は１μｍ以上５００μｍ以下であり、好ましくは１０μｍ以上２００μｍ以下である。
The thickness of the substrate is not particularly limited, but is usually 1 μm or more and 500 μm or less, preferably 10 μm or more and 200 μm or less.
「樹脂組成物の調製方法」
本実施形態の粘着層の形成に用いる上記樹脂組成物は、例えば、上記エチレン・酢酸ビニル共重合体と、上記粘着付与剤と、必要に応じて他の添加剤と、を同時または逐次的にドライブレンドまたはメルトブレンドすることにより得られる。
ドライブレンドには、ヘンシェルミキサー、タンブラーミキサーなどの各種ミキサーを用いることができる。
また、メルトブレンドする場合は、１軸または２軸押出機、バンバリーミキサー、ロール、ニーダーなどの混練装置を用いることができ、例えば、１４０℃以上２３０℃以下程度の温度で溶融混練する。 "Method for preparing resin composition"
The resin composition used for forming the pressure-sensitive adhesive layer of the present embodiment includes, for example, the ethylene / vinyl acetate copolymer, the tackifier, and, if necessary, other additives simultaneously or sequentially. Obtained by dry blending or melt blending.
Various mixers such as a Henschel mixer and a tumbler mixer can be used for the dry blending.
In the case of melt blending, a kneading apparatus such as a single or twin screw extruder, a Banbury mixer, a roll or a kneader can be used. For example, melt kneading is performed at a temperature of about 140 ° C to 230 ° C.
本実施形態の粘着層の形成に用いる上記樹脂組成物は、例えば、上記エチレン・酢酸ビニル共重合体と、上記粘着付与剤と、必要に応じて他の添加剤と、を同時または逐次的にドライブレンドまたはメルトブレンドすることにより得られる。
ドライブレンドには、ヘンシェルミキサー、タンブラーミキサーなどの各種ミキサーを用いることができる。
また、メルトブレンドする場合は、１軸または２軸押出機、バンバリーミキサー、ロール、ニーダーなどの混練装置を用いることができ、例えば、１４０℃以上２３０℃以下程度の温度で溶融混練する。 "Method for preparing resin composition"
The resin composition used for forming the pressure-sensitive adhesive layer of the present embodiment includes, for example, the ethylene / vinyl acetate copolymer, the tackifier, and, if necessary, other additives simultaneously or sequentially. Obtained by dry blending or melt blending.
Various mixers such as a Henschel mixer and a tumbler mixer can be used for the dry blending.
In the case of melt blending, a kneading apparatus such as a single or twin screw extruder, a Banbury mixer, a roll or a kneader can be used. For example, melt kneading is performed at a temperature of about 140 ° C to 230 ° C.
「粘着層の基材への形成方法」
本実施形態の樹脂組成物からなる粘着層を基材へ形成させる方法は、例えば、樹脂組成物の溶液もしくは熱溶融液を基材に塗布する溶液コート法；溶液コート法に準じセパレータ基材上に塗布後、形成した粘着層を移着転写する方法；樹脂組成物を基材上に押出し形成塗布するホットメルトコーティング法；基材と樹脂組成物を二層または三層以上の多層にて共押出し成形する方法；基材上に樹脂組成物を単層で押出ラミネートする方法；接着層と樹脂組成物を二層で押出ラミネートする方法；粘着層とフィルムやラミネート層などの支持基材形成材とをサーマルラミネートする方法；などの公知の方法に準じておこなうことができる。 "Method for forming adhesive layer on substrate"
The method for forming an adhesive layer made of the resin composition of the present embodiment on a substrate is, for example, a solution coating method in which a solution of a resin composition or a hot melt is applied to the substrate; After the coating, the formed adhesive layer is transferred and transferred; the resin composition is extruded and coated on the substrate; and the substrate and the resin composition are combined in two or more layers. Extrusion molding method; Extrusion laminating resin composition on substrate; Extrusion laminating adhesive layer and resin composition in two layers; Adhesive layer and supporting substrate forming material such as film or laminate layer Can be carried out in accordance with a known method such as thermal lamination.
本実施形態の樹脂組成物からなる粘着層を基材へ形成させる方法は、例えば、樹脂組成物の溶液もしくは熱溶融液を基材に塗布する溶液コート法；溶液コート法に準じセパレータ基材上に塗布後、形成した粘着層を移着転写する方法；樹脂組成物を基材上に押出し形成塗布するホットメルトコーティング法；基材と樹脂組成物を二層または三層以上の多層にて共押出し成形する方法；基材上に樹脂組成物を単層で押出ラミネートする方法；接着層と樹脂組成物を二層で押出ラミネートする方法；粘着層とフィルムやラミネート層などの支持基材形成材とをサーマルラミネートする方法；などの公知の方法に準じておこなうことができる。 "Method for forming adhesive layer on substrate"
The method for forming an adhesive layer made of the resin composition of the present embodiment on a substrate is, for example, a solution coating method in which a solution of a resin composition or a hot melt is applied to the substrate; After the coating, the formed adhesive layer is transferred and transferred; the resin composition is extruded and coated on the substrate; and the substrate and the resin composition are combined in two or more layers. Extrusion molding method; Extrusion laminating resin composition on substrate; Extrusion laminating adhesive layer and resin composition in two layers; Adhesive layer and supporting substrate forming material such as film or laminate layer Can be carried out in accordance with a known method such as thermal lamination.
これらの中でも、熱可塑性樹脂からなる基材とともに樹脂組成物を、インフレーション法やＴダイ法による二層または三層以上の多層にて共押出し成形する方法が好ましい。
Among these, a method in which a resin composition is co-extruded in a multilayer of two layers or three or more layers by an inflation method or a T-die method together with a base material made of a thermoplastic resin is preferable.
本実施形態において、基材に形成する粘着層の厚さは粘着力などに応じて適宜に決定されるが、一般には１μｍ以上２５０μｍ以下、さらには５μｍ以上１００μｍ以下とするのが好ましい。
また基材を有しない単層フィルムまたはシートの場合は５μｍ以上３００μｍ以下、さらには１０μｍ以上２００μｍ以下とするのが好ましい。 In the present embodiment, the thickness of the pressure-sensitive adhesive layer formed on the substrate is appropriately determined according to the pressure-sensitive adhesive force and the like, but is generally 1 μm or more and 250 μm or less, more preferably 5 μm or more and 100 μm or less.
In the case of a single layer film or sheet having no substrate, it is preferably 5 μm or more and 300 μm or less, more preferably 10 μm or more and 200 μm or less.
また基材を有しない単層フィルムまたはシートの場合は５μｍ以上３００μｍ以下、さらには１０μｍ以上２００μｍ以下とするのが好ましい。 In the present embodiment, the thickness of the pressure-sensitive adhesive layer formed on the substrate is appropriately determined according to the pressure-sensitive adhesive force and the like, but is generally 1 μm or more and 250 μm or less, more preferably 5 μm or more and 100 μm or less.
In the case of a single layer film or sheet having no substrate, it is preferably 5 μm or more and 300 μm or less, more preferably 10 μm or more and 200 μm or less.
本実施形態における感圧型粘着フィルムまたはシートは、硬い（リジッドな）被着体の表面に粘着層が対向するように積極的に加熱することなく圧力だけで貼り付けられる。不要時には手で容易に引き剥がされて被着体の表面には汚染物が残らない。被着体として例えば、合成樹脂板、化粧板、金属板、塗装鋼板などの製品表面保護用などが挙げられる。
また、窓ガラス表面保護用、自動車の焼付塗装時やプリント基板のハンダ浸積時の表面保護用などが挙げられる。
さらには、液晶表示装置、プラズマ表示装置、有機薄膜ＥＬ装置などの構成部材である液晶パネル板；反射板、位相差板、プリズムシート、導光板、偏光板、プラズマ表示パネル板、有機蛍光体薄膜、透明電極、フレキシブルプリント基板、リジッドプリント基板などの精密電子部品が挙げられる。本実施形態における感圧型粘着フィルムまたはシートは、これらの表面保護用のフィルムまたはシートとしてとくに好適に用いられる。 The pressure-sensitive adhesive film or sheet in the present embodiment is attached only by pressure without positively heating so that the adhesive layer faces the surface of a hard (rigid) adherend. When not needed, it is easily peeled off by hand, leaving no contaminants on the surface of the adherend. Examples of the adherend include product surface protection such as a synthetic resin plate, a decorative plate, a metal plate, and a coated steel plate.
Further, for window glass surface protection, surface protection at the time of carving and painting of automobiles, and soldering of printed circuit boards.
Furthermore, liquid crystal panel plates which are constituent members of liquid crystal display devices, plasma display devices, organic thin film EL devices, etc .; reflectors, retardation plates, prism sheets, light guide plates, polarizing plates, plasma display panel plates, organic phosphor thin films And precision electronic components such as transparent electrodes, flexible printed circuit boards, and rigid printed circuit boards. The pressure-sensitive adhesive film or sheet in this embodiment is particularly suitably used as a film or sheet for protecting these surfaces.
また、窓ガラス表面保護用、自動車の焼付塗装時やプリント基板のハンダ浸積時の表面保護用などが挙げられる。
さらには、液晶表示装置、プラズマ表示装置、有機薄膜ＥＬ装置などの構成部材である液晶パネル板；反射板、位相差板、プリズムシート、導光板、偏光板、プラズマ表示パネル板、有機蛍光体薄膜、透明電極、フレキシブルプリント基板、リジッドプリント基板などの精密電子部品が挙げられる。本実施形態における感圧型粘着フィルムまたはシートは、これらの表面保護用のフィルムまたはシートとしてとくに好適に用いられる。 The pressure-sensitive adhesive film or sheet in the present embodiment is attached only by pressure without positively heating so that the adhesive layer faces the surface of a hard (rigid) adherend. When not needed, it is easily peeled off by hand, leaving no contaminants on the surface of the adherend. Examples of the adherend include product surface protection such as a synthetic resin plate, a decorative plate, a metal plate, and a coated steel plate.
Further, for window glass surface protection, surface protection at the time of carving and painting of automobiles, and soldering of printed circuit boards.
Furthermore, liquid crystal panel plates which are constituent members of liquid crystal display devices, plasma display devices, organic thin film EL devices, etc .; reflectors, retardation plates, prism sheets, light guide plates, polarizing plates, plasma display panel plates, organic phosphor thin films And precision electronic components such as transparent electrodes, flexible printed circuit boards, and rigid printed circuit boards. The pressure-sensitive adhesive film or sheet in this embodiment is particularly suitably used as a film or sheet for protecting these surfaces.
別の本実施形態としては、上記の感圧型粘着フィルムまたはシートを、物品の表面を保護するために使用する方法が提供できる。表面保護の対象となる物品は、例えば、上記の被着体が挙げられる。
As another embodiment, a method of using the pressure-sensitive adhesive film or sheet as described above for protecting the surface of an article can be provided. Examples of the article to be surface protected include the adherend described above.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。
As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above can also be employ | adopted.
以下に、本実施形態を実施例および比較例により説明するが、本実施形態はこれらに限定されるものではない。
Hereinafter, the present embodiment will be described with reference to examples and comparative examples, but the present embodiment is not limited thereto.
［原料］
実施例および比較例では以下の原料を使用した。
ＥＶＡ１：エチレン・酢酸ビニル共重合体（ＭＦＲ＝９ｇ／１０ｍｉｎ、エチレン含量＝９０質量％、酢酸ビニル含量＝１０質量％）
粘着付与剤１：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－９０、軟化温度９０℃、水素化率６０％以上７０％以下）
粘着付与剤２：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１００、軟化温度１００℃、水素化率６０％以上７０％以下）
粘着付与剤３：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１１５、軟化温度１１５℃、水素化率６０％以上７０％以下）
粘着付与剤４：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１３５、軟化温度１３５℃、水素化率６０％以上７０％以下）
粘着付与剤５：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＰ－１００、軟化温度１００℃、水素化率９０％以上）
・ＭＦＲ：ＪＩＳ Ｋ７２１０－１９９９（１９０℃、２１６０g荷重）
・軟化温度：ＪＩＳ Ｋ２２０７－１９９６（環球法） [material]
In the examples and comparative examples, the following raw materials were used.
EVA1: Ethylene / vinyl acetate copolymer (MFR = 9 g / 10 min, ethylene content = 90 mass%, vinyl acetate content = 10 mass%)
Tackifier 1: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-90, softening temperature 90 ° C, hydrogenation rate 60% to 70%)
Tackifier 2: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-100, softening temperature 100 ° C, hydrogenation rate 60% to 70%)
Tackifier 3: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-115, softening temperature 115 ° C., hydrogenation rate 60% to 70%)
Tackifier 4: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-135, softening temperature 135 ° C., hydrogenation rate 60% to 70%)
Tackifier 5: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon P-100, softening temperature 100 ° C, hydrogenation rate 90% or more)
MFR: JIS K7210-1999 (190 ° C, 2160 g load)
・ Softening temperature: JIS K2207-1996 (ring and ball method)
実施例および比較例では以下の原料を使用した。
ＥＶＡ１：エチレン・酢酸ビニル共重合体（ＭＦＲ＝９ｇ／１０ｍｉｎ、エチレン含量＝９０質量％、酢酸ビニル含量＝１０質量％）
粘着付与剤１：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－９０、軟化温度９０℃、水素化率６０％以上７０％以下）
粘着付与剤２：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１００、軟化温度１００℃、水素化率６０％以上７０％以下）
粘着付与剤３：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１１５、軟化温度１１５℃、水素化率６０％以上７０％以下）
粘着付与剤４：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＭ－１３５、軟化温度１３５℃、水素化率６０％以上７０％以下）
粘着付与剤５：脂環族飽和炭化水素樹脂（荒川化学工業社製、アルコンＰ－１００、軟化温度１００℃、水素化率９０％以上）
・ＭＦＲ：ＪＩＳ Ｋ７２１０－１９９９（１９０℃、２１６０g荷重）
・軟化温度：ＪＩＳ Ｋ２２０７－１９９６（環球法） [material]
In the examples and comparative examples, the following raw materials were used.
EVA1: Ethylene / vinyl acetate copolymer (MFR = 9 g / 10 min, ethylene content = 90 mass%, vinyl acetate content = 10 mass%)
Tackifier 1: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-90, softening temperature 90 ° C, hydrogenation rate 60% to 70%)
Tackifier 2: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-100, softening temperature 100 ° C, hydrogenation rate 60% to 70%)
Tackifier 3: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-115, softening temperature 115 ° C., hydrogenation rate 60% to 70%)
Tackifier 4: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon M-135, softening temperature 135 ° C., hydrogenation rate 60% to 70%)
Tackifier 5: Alicyclic saturated hydrocarbon resin (Arakawa Chemical Industries, Alcon P-100, softening temperature 100 ° C, hydrogenation rate 90% or more)
MFR: JIS K7210-1999 (190 ° C, 2160 g load)
・ Softening temperature: JIS K2207-1996 (ring and ball method)
［評価サンプル作製］
４０ｍｍφＴダイ成形機（ナカタニ機械社製）を用いて表１に記載の配合割合（質量部）の樹脂組成物を厚み９０μｍにて押出加工し、評価用フィルムを作製した。押出加工は、樹脂温度を約１８０℃、加工速度を１０ｍ／ｍｉｎの条件下でおこなった。 [Evaluation sample preparation]
A 40 mmφT die molding machine (manufactured by Nakatani Machinery Co., Ltd.) was used to extrude a resin composition having a blending ratio (parts by mass) shown in Table 1 at a thickness of 90 μm to produce an evaluation film. Extrusion was performed under conditions of a resin temperature of about 180 ° C. and a processing speed of 10 m / min.
４０ｍｍφＴダイ成形機（ナカタニ機械社製）を用いて表１に記載の配合割合（質量部）の樹脂組成物を厚み９０μｍにて押出加工し、評価用フィルムを作製した。押出加工は、樹脂温度を約１８０℃、加工速度を１０ｍ／ｍｉｎの条件下でおこなった。 [Evaluation sample preparation]
A 40 mmφT die molding machine (manufactured by Nakatani Machinery Co., Ltd.) was used to extrude a resin composition having a blending ratio (parts by mass) shown in Table 1 at a thickness of 90 μm to produce an evaluation film. Extrusion was performed under conditions of a resin temperature of about 180 ° C. and a processing speed of 10 m / min.
［評価方法］
（１）粘着力評価
ＪＩＳ Z０２３７に準拠し、評価用フィルム（２５ｍｍ幅）と被着体であるアクリル板（３０ｍｍ幅、１５０ｍｍ長、２ｍｍ厚）を重ねて、手動式ローラー（４５ｍｍ幅、重量２Ｋｇ）で２往復圧着し、評価用サンプルを得た。これを、２３℃×５０％ＲＨ雰囲気下で３０分間静置後、引取り速度＝３００ｍｍ／ｍｉｎ、１８０度の角度で剥がし、粘着力の評価をおこなった。なお、本評価においては、測定バラツキの影響を少なくするため、測定を各５回実施し、最大値と最小値を除外した３回分の測定値を平均した値を粘着力として用いた。 [Evaluation methods]
(1) Adhesive strength evaluation In accordance with JIS Z0237, an evaluation film (25 mm width) and an acrylic plate (30 mm width, 150 mm length, 2 mm thickness) as an adherence are stacked, and a manual roller (45 mm width, weight 2 kg) ) Was reciprocated twice to obtain a sample for evaluation. This was left to stand for 30 minutes in a 23 ° C. × 50% RH atmosphere, and then peeled off at an angle of 180 ° with a take-off speed = 300 mm / min, and the adhesive strength was evaluated. In this evaluation, in order to reduce the influence of measurement variation, the measurement was performed 5 times each, and a value obtained by averaging three measurement values excluding the maximum value and the minimum value was used as the adhesive force.
（１）粘着力評価
ＪＩＳ Z０２３７に準拠し、評価用フィルム（２５ｍｍ幅）と被着体であるアクリル板（３０ｍｍ幅、１５０ｍｍ長、２ｍｍ厚）を重ねて、手動式ローラー（４５ｍｍ幅、重量２Ｋｇ）で２往復圧着し、評価用サンプルを得た。これを、２３℃×５０％ＲＨ雰囲気下で３０分間静置後、引取り速度＝３００ｍｍ／ｍｉｎ、１８０度の角度で剥がし、粘着力の評価をおこなった。なお、本評価においては、測定バラツキの影響を少なくするため、測定を各５回実施し、最大値と最小値を除外した３回分の測定値を平均した値を粘着力として用いた。 [Evaluation methods]
(1) Adhesive strength evaluation In accordance with JIS Z0237, an evaluation film (25 mm width) and an acrylic plate (30 mm width, 150 mm length, 2 mm thickness) as an adherence are stacked, and a manual roller (45 mm width, weight 2 kg) ) Was reciprocated twice to obtain a sample for evaluation. This was left to stand for 30 minutes in a 23 ° C. × 50% RH atmosphere, and then peeled off at an angle of 180 ° with a take-off speed = 300 mm / min, and the adhesive strength was evaluated. In this evaluation, in order to reduce the influence of measurement variation, the measurement was performed 5 times each, and a value obtained by averaging three measurement values excluding the maximum value and the minimum value was used as the adhesive force.
[評価結果]
以上の評価結果を表１にまとめた。 [Evaluation results]
The above evaluation results are summarized in Table 1.
以上の評価結果を表１にまとめた。 [Evaluation results]
The above evaluation results are summarized in Table 1.
この出願は、２０１１年１１月１５日に出願された日本出願特願２０１１－２４９３１８号を基礎とする優先権を主張し、その開示の全てをここに取り込む。
This application claims priority based on Japanese Patent Application No. 2011-249318 filed on November 15, 2011, the entire disclosure of which is incorporated herein.
Claims (8)
- 酢酸ビニル含有量が７．５質量％以上２０質量％以下のエチレン・酢酸ビニル共重合体と、
水素化率が５０％以上９０％未満の範囲内にある粘着付与剤と
を含む粘着層を備える、感圧型粘着フィルムまたはシート。 An ethylene / vinyl acetate copolymer having a vinyl acetate content of 7.5 to 20% by mass;
A pressure-sensitive adhesive film or sheet comprising an adhesive layer comprising a tackifier having a hydrogenation rate in the range of 50% or more and less than 90%. - 請求項１に記載の感圧型粘着フィルムまたはシートにおいて、
前記エチレン・酢酸ビニル共重合体と前記粘着付与剤との合計量を１００質量部としたとき、
前記粘着付与剤の含有量が０．１質量部以上５．０質量部以下である、感圧型粘着フィルムまたはシート。 In the pressure-sensitive adhesive film or sheet according to claim 1,
When the total amount of the ethylene / vinyl acetate copolymer and the tackifier is 100 parts by mass,
A pressure-sensitive adhesive film or sheet, wherein the content of the tackifier is 0.1 part by mass or more and 5.0 parts by mass or less. - 請求項１または２に記載の感圧型粘着フィルムまたはシートにおいて、
前記粘着付与剤のＪＩＳ Ｋ２２０７－１９９６環球法に準拠して測定した軟化温度が８０℃以上１５０℃以下である、感圧型粘着フィルムまたはシート。 In the pressure-sensitive adhesive film or sheet according to claim 1 or 2,
A pressure-sensitive adhesive film or sheet having a softening temperature of 80 ° C. or higher and 150 ° C. or lower measured according to JIS K2207-1996 ring and ball method of the tackifier. - 請求項１乃至３いずれか一項に記載の感圧型粘着フィルムまたはシートにおいて、
前記エチレン・酢酸ビニル共重合体のＪＩＳ Ｋ７２１０－１９９９に準拠して測定したメルトフローレート（１９０℃、２１６０ｇ荷重）が、１ｇ／１０分以上５０ｇ／１０分以下である、感圧型粘着フィルムまたはシート。 In the pressure-sensitive adhesive film or sheet according to any one of claims 1 to 3,
Pressure-sensitive adhesive film or sheet having a melt flow rate (190 ° C., 2160 g load) of the ethylene / vinyl acetate copolymer measured in accordance with JIS K7210-1999 of 1 g / 10 min to 50 g / 10 min . - 請求項１乃至４いずれか一項に記載の感圧型粘着フィルムまたはシートにおいて、
前記粘着層が基材の少なくとも一方の面に形成された、感圧型粘着フィルムまたはシート。 In the pressure-sensitive adhesive film or sheet according to any one of claims 1 to 4,
A pressure-sensitive adhesive film or sheet in which the adhesive layer is formed on at least one surface of a substrate. - 請求項５に記載の感圧型粘着フィルムまたはシートにおいて、
前記基材がポリエチレンまたはポリプロピレンを含む、感圧型粘着フィルムまたはシート。 In the pressure-sensitive adhesive film or sheet according to claim 5,
A pressure-sensitive adhesive film or sheet, wherein the substrate comprises polyethylene or polypropylene. - 請求項１乃至６いずれか一項に記載の感圧型粘着フィルムまたはシートを含む、表面保護フィルムまたはシート。 A surface protective film or sheet comprising the pressure-sensitive adhesive film or sheet according to any one of claims 1 to 6.
- 請求項１乃至６いずれか一項に記載の感圧型粘着フィルムまたはシートを、物品の表面を保護するために使用する方法。 A method of using the pressure-sensitive adhesive film or sheet according to any one of claims 1 to 6 for protecting the surface of an article.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020147015289A KR102006365B1 (en) | 2011-11-15 | 2012-11-08 | Pressure-sensitive adhesive film or sheet, surface protecting film or sheet, and method for using pressure-sensitive adhesive film or sheet to protect surface of article |
| CN201280055859.1A CN103930500B (en) | 2011-11-15 | 2012-11-08 | Pressure-sensitive adhesive film or sheet material, surface protection film or sheet material and use pressure-sensitive adhesive film or sheet material for the method protecting article surface |
| JP2013544116A JP6016801B2 (en) | 2011-11-15 | 2012-11-08 | Pressure-sensitive adhesive film or sheet, surface protective film or sheet, and method of using pressure-sensitive adhesive film or sheet to protect the surface of an article |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011249318 | 2011-11-15 | ||
| JP2011-249318 | 2011-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013073142A1 true WO2013073142A1 (en) | 2013-05-23 |
Family
ID=48429240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/007185 WO2013073142A1 (en) | 2011-11-15 | 2012-11-08 | Pressure-sensitive adhesive film or sheet, surface protecting film or sheet, and method for using pressure-sensitive adhesive film or sheet to protect surface of article |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6016801B2 (en) |
| KR (1) | KR102006365B1 (en) |
| CN (1) | CN103930500B (en) |
| WO (1) | WO2013073142A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281085A (en) * | 2016-08-18 | 2017-01-04 | 宁波卓胜新材料有限公司 | A kind of auto-parts self-adhesion gas shielded adhesive tape and preparation method thereof |
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| JPH04170489A (en) * | 1990-05-12 | 1992-06-18 | Sekisui Chem Co Ltd | Heat-sensitive adhesive tape for sealing |
| JPH06145616A (en) * | 1992-11-10 | 1994-05-27 | Sekisui Chem Co Ltd | Surface-protection film |
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| JPH08216316A (en) * | 1995-02-14 | 1996-08-27 | Bridgestone Corp | Polarizing plate for liquid crystal display device |
| JPH08216315A (en) * | 1995-02-14 | 1996-08-27 | Bridgestone Corp | Polarizing plate for liquid crystal display device |
| JP2003186404A (en) * | 2001-12-21 | 2003-07-04 | Oji Paper Co Ltd | Label sticking method, label stuck body, and heat seal label |
| JP2004123939A (en) * | 2002-10-03 | 2004-04-22 | Tosoh Corp | Adhesive composition for laminating glass |
| WO2009098976A1 (en) * | 2008-02-05 | 2009-08-13 | Du Pont-Mitsui Polychemicals Co., Ltd. | Tacky resin composition and pressure-sensitive adhesive film or sheet |
| JP2010171419A (en) * | 2008-12-27 | 2010-08-05 | Arakawa Chem Ind Co Ltd | Sealing material sheet for solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SG42380A1 (en) * | 1995-06-08 | 1997-08-15 | Sekisui Chemical Co Ltd | An interlayer film and laminated glass using the same |
| JP2008255233A (en) | 2007-04-05 | 2008-10-23 | Du Pont Mitsui Polychem Co Ltd | Pressure-sensitive adhesive film or sheet |
-
2012
- 2012-11-08 KR KR1020147015289A patent/KR102006365B1/en active IP Right Grant
- 2012-11-08 CN CN201280055859.1A patent/CN103930500B/en not_active Expired - Fee Related
- 2012-11-08 WO PCT/JP2012/007185 patent/WO2013073142A1/en active Application Filing
- 2012-11-08 JP JP2013544116A patent/JP6016801B2/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516055A (en) * | 1978-07-21 | 1980-02-04 | Sanyo Chem Ind Ltd | Heat-sensitive adhesive, its preparation and adhesive sheet |
| JPH04170489A (en) * | 1990-05-12 | 1992-06-18 | Sekisui Chem Co Ltd | Heat-sensitive adhesive tape for sealing |
| JPH06145616A (en) * | 1992-11-10 | 1994-05-27 | Sekisui Chem Co Ltd | Surface-protection film |
| JPH06344043A (en) * | 1993-06-11 | 1994-12-20 | Sony Chem Corp | Molding method for metallic plate and adhesive sheet |
| JPH08216316A (en) * | 1995-02-14 | 1996-08-27 | Bridgestone Corp | Polarizing plate for liquid crystal display device |
| JPH08216315A (en) * | 1995-02-14 | 1996-08-27 | Bridgestone Corp | Polarizing plate for liquid crystal display device |
| JP2003186404A (en) * | 2001-12-21 | 2003-07-04 | Oji Paper Co Ltd | Label sticking method, label stuck body, and heat seal label |
| JP2004123939A (en) * | 2002-10-03 | 2004-04-22 | Tosoh Corp | Adhesive composition for laminating glass |
| WO2009098976A1 (en) * | 2008-02-05 | 2009-08-13 | Du Pont-Mitsui Polychemicals Co., Ltd. | Tacky resin composition and pressure-sensitive adhesive film or sheet |
| JP2010171419A (en) * | 2008-12-27 | 2010-08-05 | Arakawa Chem Ind Co Ltd | Sealing material sheet for solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102006365B1 (en) | 2019-08-02 |
| KR20140101343A (en) | 2014-08-19 |
| CN103930500B (en) | 2016-08-24 |
| JPWO2013073142A1 (en) | 2015-04-02 |
| CN103930500A (en) | 2014-07-16 |
| JP6016801B2 (en) | 2016-10-26 |
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