WO1999023186A1 - Feuille adhesive sensible a la pression protectrice de surface et composition adhesive sensible a la pression pour ladite feuille - Google Patents
Feuille adhesive sensible a la pression protectrice de surface et composition adhesive sensible a la pression pour ladite feuille Download PDFInfo
- Publication number
- WO1999023186A1 WO1999023186A1 PCT/JP1998/004821 JP9804821W WO9923186A1 WO 1999023186 A1 WO1999023186 A1 WO 1999023186A1 JP 9804821 W JP9804821 W JP 9804821W WO 9923186 A1 WO9923186 A1 WO 9923186A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- weight
- adhesive sheet
- pressure
- ethylene
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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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
- 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
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- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
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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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2857—Adhesive compositions including metal or compound thereof or natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/31917—Next to polyene polymer
Definitions
- the present invention relates to a surface protective pressure-sensitive adhesive sheet and a pressure-sensitive adhesive composition for a surface protective pressure-sensitive adhesive sheet, and more particularly, to a surface protective pressure-sensitive adhesive sheet which protects a coating film and has excellent strength at low temperatures and excellent high-speed peelability.
- the present invention relates to a pressure-sensitive adhesive composition for a surface-protecting pressure-sensitive adhesive sheet having excellent low-temperature adhesion and high-speed peelability to a coating film.
- JP-A-6 7 3 3 5 2 JP as shown in JP-A 9-3 4 2 0 No. etc., there is a method of pasting a surface protective pressure sensitive adhesive sheet directly coated surface power?
- Adhesive sheets are poorly adherent to low-adhesion coatings with excellent water repellency and stain resistance, especially at low temperatures, and have low tear strength and low tensile elongation. peeling force s or occur, partially torn, peeled and torn suffer the fringe cormorant problem.
- a surface protection adhesive sheet having an adhesive layer mainly composed of a hydrogenated product of a random copolymer of styrene and a gen-based hydrocarbon has been proposed.
- Japanese Patent Application No. 6-1494963 Japanese Patent Application No. 6-1494963
- an adhesive containing at least one of polyisobutylene, butyl rubber and polybutene as a main component is used as a support.
- these films do not peel off during transportation of vehicles, when the protective sheet is peeled off after transportation, high-speed peeling has been proposed. There is a problem that it is easy to be torn or torn due to high peeling force.
- the present invention is applied to a hard-to-adhesive coating film having excellent water repellency and stain resistance, and in a wide temperature range where it is not easily torn, peeled or peeled even at a low temperature.
- An object of the present invention is to provide a surface protective adhesive sheet which has an excellent protection function and can be easily peeled at high speed without tearing or breaking when peeled off.
- the present invention also provides excellent adhesion to hard-to-adhesive coatings with excellent water repellency and stain resistance, especially at low temperatures, and leaves dirt and marks on the adhered surface when peeled off with force. It is an object of the present invention to provide an adhesive for a low-temperature surface protective adhesive sheet that can be easily peeled off at a high speed without any problem. Disclosure of the invention
- the present invention provides a surface protective adhesive comprising a substrate comprising an ethylene Z propylene copolymer and an ethylene Z 1 -butene copolymer in a weight ratio of 60:40 to 90:10.
- a sheet is provided.
- the present invention has a tensile strength at ⁇ 20 ° C. of 1.5 N / rise or more, a tensile elongation of 100% or more, and an Elmendorf tear strength at 5 ° C. in the film forming direction and the width direction. 0.5N or more, and an elastic modulus at 23 ° C in the film forming direction of 300 to 50 ON / thigh 2 is provided. .
- the present invention provides the surface protective pressure-sensitive adhesive sheet, wherein the light transmittance of the substrate at 200 to 400 nm is 0.5% or less.
- the present invention relates to polybutylene and / or butyl rubber 50 to 100
- a pressure-sensitive adhesive composition for a surface-protective pressure-sensitive adhesive sheet comprising 5 to 30 parts by weight of a gin-based tackifier resin with respect to 100 parts by weight of a blend comprising 100% by weight of polybutene and 50 to 0% by weight of polybutene.
- the substrate layer of the surface protective pressure-sensitive adhesive sheet of the present invention contains the ethylene / propylene copolymer and the ethylene Z1-butene copolymer in a weight ratio of 60:40 to 90:10, and is preferably used. 75: 25 to 85: 15. If the amount of the ethylene Z1-butene copolymer exceeds 40% by weight, it will be too soft, and the workability for sticking and peeling will be poor.
- the ethylene Z propylene copolymer used in the present invention is a block copolymer or a random copolymer, which is generally called block polypropylene or random polypropylene. It includes from.
- Such ethylene / propylene copolymers include melt flow rate
- ethylene Z propylene copolymers that can be used in the present invention include, for example, Noblene BJS-M (trade name, manufactured by Grand Polymer Co., Ltd.) and Grand Polypropylene J 702 L (trade name, manufactured by Grand Polymer Co., Ltd.) Is mentioned.
- the ethylene / 1-butene copolymer used in the present invention has an MFR (measured according to JIS K-7201) of 190 to 120 ° C and a load of 0.1 to 20 gZl O at a load of 2.16 kg. Is preferred.
- the weight ratio of ethylene to 1-butene is, for example, 75:25 to 8 5: 15
- Commercially available ethylene / 1-butene copolymers that can be used in the present invention include JSREBM 201 P (trade name, manufactured by Nippon Synthetic Rubber Co., Ltd.) Industrial Co., Ltd.).
- the surface protective adhesive sheet one bets of the substrate layer of the present invention, 2 0 0-4 0 0 ⁇ light transmittance of 0. It force is 5% or less?, From the viewpoint of weather resistance.
- a method of adding titanium oxide, an ultraviolet absorber, an ultraviolet stabilizer and the like can be mentioned.
- titanium oxide When titanium oxide is added to the base material layer, 3 to 15 parts by weight of titanium oxide may be added to the total amount of 100 parts by weight of ethylene Z propylene copolymer and ethylene Z 1 -butene copolymer. preferable.
- an ultraviolet absorber or an ultraviolet stabilizer When an ultraviolet absorber or an ultraviolet stabilizer is added to the substrate layer, examples thereof include benzotriazole-based, hinderedamine-based, and benzoate-based compounds. These UV absorbers or UV stabilizers should be added in an amount of 0.03-0.3 parts by weight based on 100 parts by weight of the ethylene Z propylene copolymer and the ethylene / 1-butene copolymer. Power preferred.
- various additives can be blended as needed within a range not to impair the purpose of the present invention.
- pigments such as Ripponbon Black and Bengala
- fillers such as talc and calcium carbonate
- lubricants such as stearic acid, stearic acid amide, calcium stearate, nordium stearate and zinc stearate
- phenolic antioxidants Agents antioxidants such as phosphite antioxidants and thioether antioxidants
- inorganic hollow particles such as glass balloons and silica balloons
- polymer microspheres such as high molecular weight polyolefin powders
- silicones A releasability-imparting agent such as a releasability-imparting agent and a long-chain alkyl-based releasability-imparting agent can be appropriately added.
- the base material layer of the present invention is formed by a general film forming method such as T-die film formation and inflation film formation. Can film.
- the pressure-sensitive adhesive layer of the surface protective pressure-sensitive adhesive sheet of the present invention is not particularly limited, but the above-mentioned pressure-sensitive adhesive composition for a surface protective pressure-sensitive adhesive sheet of the present invention is preferably used.
- the composition include polyisobutylene, butyl rubber, or a blend prepared by adding polybutene to the mixture, to which a gin-based tackifying resin is added because of its good low-temperature adhesiveness.
- composition More particularly, the composition, poly isobutylene, or butyl rubber 5 0 wt 0/0 or more, and polybutene to 5 0 wt 0/0 Purendo product 1 0 0 parts by weight of the following, tackifying resins 5-3 0 Parts by weight are added.
- the content of polybutene in a blend of polyisobutylene and / or butyl rubber and polybutene exceeds 50% by weight, the peeling force at the time of high-speed peeling is increased, and the peeling workability is increased. Deterioration or poor weather resistance.
- the polyisobutylene and butyl rubber used in the present invention preferably have a viscosity average molecular weight of from 400,000 to 150,000 as measured by the F10ry method. If the viscosity average molecular weight is less than 400,000, the peeling force at the time of high-speed peeling becomes heavy, and the peeling workability becomes poor. If it exceeds 150,000, the low-temperature adhesion to the poorly-adhesive coating film will be poor.
- the polybutene used in the present invention preferably has a number average molecular weight of 400 to 3,000. When the number average molecular weight is less than 400, the peeling force at the time of high-speed peeling increases, and the peeling workability deteriorates. If it exceeds 3,000, the low-temperature adhesion to the poorly-adhesive coating film will be poor.
- the addition amount of the rosin-based tackifying resin is less than 5 parts by weight based on 100 parts by weight of a blend of polyisobutylene and Z or butyl rubber and polybutene, the poor adhesion coating Poor low temperature adhesion to the film. If the amount of the rosin-based tackifying resin exceeds 30 parts by weight, low-temperature adhesion The weatherability is worsened and the adhered surface is contaminated.
- the mouth gin-based tackifying resin used in the present invention is preferably a mouth gin ester-based resin, and more preferably a hydrogenated or disproportionated rosin ester resin from the viewpoint of weather resistance.
- the surface-protective pressure-sensitive adhesive sheet using the adhesive composition of the present invention has a wettability (according to JISK 670) of less than 3 O dyn / cm.
- Adhesive strength in atmosphere 180 ° peeler, peeling speed 0.3 m / min, conforming to JISZ 237) is 0.4 NZ10 or more, high speed in atmosphere at 23 ° C It is preferable that the peeling force (180 ° piler, pretreatment at 70 ° C. for 24 hours, peeling speed of 40 mZ, conforming to JISZ0237) is less than 2 NZ10 bandages.
- the adhesive strength in an atmosphere at a temperature of 20 ° C is less than 0.4 N / 10
- the low-temperature adhesive strength is deteriorated, and the adhesive tends to peel off during low-temperature transportation.
- the high-speed peeling force in a 23 ° C atmosphere is higher than 2 ⁇ 10, peeling workability may be deteriorated.
- the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer for the surface protective pressure-sensitive adhesive sheet of the present invention may contain various additives as necessary, as long as the object of the present invention is not impaired. it can.
- softeners such as oil, paraffin wax, epoxy plasticizer, polyester plasticizer; pigments such as titanium oxide, black carbon black, red iron oxide; fillers such as talc, calcium carbonate; stearic acid, stearic acid Lubricants such as amides, calcium stearate, barium stearate, and zinc stearate; antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioether antioxidants; benzotriazo UV absorbers such as cellulose UV absorbers, hindered UV stabilizers, benzoate UV stabilizers, etc .; or inorganic hollow particles such as glass balloon, silica balloon, etc .; acryl Microspheres, polymer microspheres such as high molecular weight polyolefin powder; silicone-based release agent, long
- the surface protective adhesive sheet of the present invention has a tensile strength at 20 ° C of 1.5 N / or more, a tensile elongation of 100% or more, and an Elmendorf tear strength at 5 ° C in both the film forming direction and the width direction. Is 0.5N or more, and the elastic modulus at 23 ° C in the film forming direction is 300 to 50 ON. -If the tensile strength at 20 ° C is less than 1.5N /, or the tensile elongation is less than 10096, or the Elmendorf tear strength at 5 ° C is less than 0.5N, it will be torn or torn.
- the elastic modulus at 23 is less than 300 N / mm 2 , it is too soft and poor in sticking workability and peeling workability. If it exceeds 500 N, the ability to follow irregularities and curved portions of the adherend will be poor.
- the surface protective pressure-sensitive adhesive sheet of the present invention includes, for example, melt-coating, hot-melt extrusion-coating the pressure-sensitive adhesive layer after forming the substrate layer, or co-extrusion of the substrate layer and the pressure-sensitive adhesive layer. It can be manufactured by a known method.
- the thickness of the base material layer is preferably from 20 to 20 O / ym, more preferably from 30 to 100 m.
- the thickness of the pressure-sensitive adhesive layer is preferably from 2 to 80 m, more preferably from 5 to 30 / m.
- Ethylene / propylene copolymer (hereinafter abbreviated as " ⁇ ")
- HPP Polypropylene
- HPP-1 Idemitsu Polypro F-200 S (trade name, Idemitsu Petrochemical Polypropylene) Pyrene)
- EBM Ethylene Zl-butene copolymer
- Titanium oxide (hereinafter abbreviated as "TIO")
- ⁇ I 0-1 Thai base ⁇ 220 (trade name, Ishihara Sangyo's titanium oxide, anatas type)
- UV stabilizer (hereinafter abbreviated as “HL S”)
- H L S-1 Tinuvin 622 L D (trade name, Ciba Specialty 'Hindered amine UV stabilizer manufactured by Chemicals Co., Ltd.)
- AO-1 Irganox 100 (trade name, Ciba Specialty Chemical Chemicals Co., Ltd., hindered phenolic antioxidant)
- Irganox 56 5 (trade name, Hindered phenolic antioxidant manufactured by Ciba 'Specialty' Chemicals)
- PIB-1 Vistanex MML 80 (trade name, polyisobutylene manufactured by Exxon, viscosity average molecular weight 990,000)
- P B-1 Idemitsu Polybutene 300 R (trade name, polybutene manufactured by Idemitsu Petrochemical Co., number average molecular weight 1,330)
- Tackifying resin (hereinafter abbreviated as “AR”)
- AR-1 Pine Crystal KE-311 (Trade name, Arakawa Chemical Industries rosin ester resin) 9
- AR-2 Clearon P-85 (trade name, hydrogenated terpene resin manufactured by Yashara Chemical Co., Ltd.)
- AR-3 Archon P-100 (trade name, Arakawa Chemical Industries, Ltd., alicyclic saturated hydrocarbon resin)
- AR-4 YS Polystar T1 15 (trade name, terpene phenolic resin manufactured by Yashara Chemical Co., Ltd.)
- the base material layer was formed to a thickness of 60 m using a T-die extruder, but the adhesive layer was melted with a toluene solvent to a thickness of 10 m. Coated.
- High-speed peeling force against coating film 1 80 ° peel force, adherent Adhesion-resistant acrylic coating film, peeling speed 40 mZ min, pretreatment 70 ° C x 24 hours (based on JIS K 0237)
- Adhesion workability Evaluate workability when applying samples to finished vehicles coated with hard-to-adhesive acryl-based paint
- Peeling workability Evaluate the workability when peeling by hand after pre-treatment at 70 ° C X 24 hours after attaching the sample to a finished car coated with hard-to-adhesive acrylic paint
- Adhesion at low temperature Attached a sample to a completed car coated with hard-to-adhesive acrylic paint, conducted a running test at a speed of 100 km / h, and evaluated for peeling
- Substrate destruction at low temperature Attached sample to finished car coated with hard-to-adhesive acrylic paint, evaluated at 70 ° C x 24 hours after pretreatment, whether there was substrate destruction when peeled by hand
- Base layer light transmittance Measure the light transmittance of the base layer film from 200 to 40 Onm using an ultraviolet-visible spectrophotometer.
- Non-adhesive acrylic coating film of less than 30 dyn m (containing silicon)
- Table 2 shows the test results.
- the surface protective pressure-sensitive adhesive sheet of the present invention has a good protection function against a poorly adherent coating film at both normal temperature and low temperature, and tears or tears during transportation at low temperature. It does not peel off partially or completely, and has good sticking workability, peeling workability, and good weather resistance, and tears or tears even if it peels off after carbon arc irradiation. It can be easily peeled at high speed without performing.
- An adhesive composition having the composition shown in Table 3 was dissolved in a toluene solvent on one side of the same film used in Example 1, and then each was spread-coated to a thickness of 10 m.
- the surface protective pressure-sensitive adhesive sheets obtained in Examples 3 to 8 and Comparative Examples 4 to 11 were applied to an acrylic-based hard-to-adhesive coating film, and were adhered to the adherend at low temperature, high-speed peelability, and weather resistance. Were tested. The weather resistance was measured after irradiation with a carbon arc by Zomeometer. The removability, contamination of the adhered surface after peeling, and the presence or absence of sticking marks were evaluated.
- Hard-to-adhesive coating film wettability (according to JIS K 6760) Hard-to-adhesive acryl-based coating film with less than 3 Odyn / cin (containing silicone)
- High-speed peelability 23. (: 180 ° peeling force in atmosphere (substrate: hardly adherent acryl-based coating, peeling speed: 40 m / min, in accordance with JISZ0237), evaluation result: good 2 NZ Less than 10 bandits, bad 2 NZ 10 marauder or more (Set from the result of pasting a surface protection adhesive sheet sample to a finished car coated with hard-to-adhesive acrylic paint and evaluating the peeling workability)
- Table 4 shows the test results.
- the surface protective pressure-sensitive adhesive sheet of the present invention has a good protection function against hardly adherent coating film at both normal temperature and low temperature, and is capable of being partially peeled or partially peeled or completely peeled at low temperature transportation. Not something. Further, the surface protective pressure-sensitive adhesive sheet of the present invention has good sticking workability, peeling workability, and good weatherability, and can be easily peeled at a high speed without peeling or tearing even after peeling after carbon arc irradiation. It is possible.
- the pressure-sensitive adhesive composition of the present invention has a certain amount of polybutene and / or gin-based pressure-sensitive adhesive with respect to polyisobutylene and / or butyl rubber, which has a low peeling force at the time of high-speed peeling but has poor adhesion to a poorly adherent coating film.
- a surface protective pressure-sensitive adhesive sheet having a low-speed peeling force and improved low-temperature adhesion to a poorly-adhesive coating film by adding a resin to be applied.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US09/341,088 US6274235B1 (en) | 1997-10-31 | 1998-10-26 | Surface-protective pressure-sensitive adhesive sheet and pressure-sensitive adhesive composition for surface-protective pressure-sensitive adhesive sheet |
DE1998625145 DE69825145T2 (de) | 1997-10-31 | 1998-10-26 | Druckempfindliche klebefolie für oberflächenschutz, und druckempfindliche klebstoffzusammensetzung für oberflächenschutz |
EP19980950373 EP0955346B1 (en) | 1997-10-31 | 1998-10-26 | Surface-protective pressure-sensitive adhesive sheet and pressure-sensitive adhesive composition for surface-protective pressure-sensitive adhesive sheet |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30008197A JP3517341B2 (ja) | 1997-10-31 | 1997-10-31 | 表面保護粘着シート用の粘着剤組成物 |
JP9/300081 | 1997-10-31 | ||
JP9/322574 | 1997-11-25 | ||
JP32257497A JP3317663B2 (ja) | 1997-11-25 | 1997-11-25 | 表面保護粘着シート |
Publications (1)
Publication Number | Publication Date |
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WO1999023186A1 true WO1999023186A1 (fr) | 1999-05-14 |
Family
ID=26562204
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/004821 WO1999023186A1 (fr) | 1997-10-31 | 1998-10-26 | Feuille adhesive sensible a la pression protectrice de surface et composition adhesive sensible a la pression pour ladite feuille |
Country Status (4)
Country | Link |
---|---|
US (1) | US6274235B1 (ja) |
EP (2) | EP0955346B1 (ja) |
DE (2) | DE69829322T2 (ja) |
WO (1) | WO1999023186A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2012200484B2 (en) * | 2006-11-08 | 2014-05-29 | Frans Nooren Afdichtingssystemen B.V. | Process for providing an extended tubular article with a corrosion protection coating system having self-repairing properties |
US9297490B2 (en) | 2006-11-08 | 2016-03-29 | Frans Nooren Afdichtingssystemen B.V. | Process for providing an extended tubular article with a corrosion protection coating system having self-repairing properties |
US9926630B2 (en) | 2012-07-13 | 2018-03-27 | Frans Nooren Afdichtingssystemen B.V. | Process for the protection against corrosion of an article in a wet environment and composition therefore |
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US20040241434A1 (en) * | 2003-06-02 | 2004-12-02 | Tomoo Yamaguchi | Pressure-sensitive adhesive double-coated sheet |
EP1741743B1 (en) * | 2004-03-19 | 2009-10-07 | Lintec Corporation | Surface substrate film for automobile brake disc anti-rust film |
WO2006075383A1 (ja) * | 2005-01-14 | 2006-07-20 | Nichiban Company Limited | 表面保護シート |
KR101236140B1 (ko) | 2005-12-16 | 2013-02-22 | 니찌방 가부시기가이샤 | 내치핑성 필름 |
JP5038770B2 (ja) * | 2007-05-01 | 2012-10-03 | 日東電工株式会社 | 車両用塗膜面に対する粘着シートの接着方法 |
EP2337698A1 (en) * | 2008-10-21 | 2011-06-29 | E. I. du Pont de Nemours and Company | Cover for protecting a painted surface |
JP5558074B2 (ja) * | 2009-10-15 | 2014-07-23 | 日東電工株式会社 | 塗膜保護シート |
JP2011096988A (ja) * | 2009-11-02 | 2011-05-12 | Keiwa Inc | 太陽電池モジュール裏面保護用粘着シート及びこれを用いた太陽電池モジュール |
JP2013511410A (ja) * | 2009-11-18 | 2013-04-04 | スリーエム イノベイティブ プロパティズ カンパニー | 可撓性組立品並びにその製造及び使用方法 |
JP5719647B2 (ja) * | 2010-04-09 | 2015-05-20 | 日東電工株式会社 | シーリング組成物、複層ガラスおよび太陽電池パネル |
JP5480319B2 (ja) | 2012-03-13 | 2014-04-23 | 日東電工株式会社 | 粘着剤組成物、粘着シートおよび透湿防水粘着シート |
JP5989432B2 (ja) * | 2012-07-18 | 2016-09-07 | 日東電工株式会社 | 塗膜保護シート |
JP6473378B2 (ja) * | 2015-04-30 | 2019-02-20 | マクセルホールディングス株式会社 | 粘着テープ |
US20240149185A1 (en) * | 2022-11-04 | 2024-05-09 | Charlie-Kao Industry Co., Ltd. | Building block assembly |
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JPH06336577A (ja) * | 1993-05-28 | 1994-12-06 | Hitachi Chem Co Ltd | 表面保護フイルム |
JPH07233354A (ja) * | 1993-12-28 | 1995-09-05 | Mitsui Petrochem Ind Ltd | 表面保護フィルム |
JPH0994532A (ja) * | 1995-10-04 | 1997-04-08 | Hitachi Chem Co Ltd | 塗膜保護方法および該方法に用いる表面保護フィルム |
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JPH01275029A (ja) * | 1988-04-27 | 1989-11-02 | Showa Denko Kk | 多層バリヤー容器の製造方法 |
JP3154931B2 (ja) * | 1995-09-22 | 2001-04-09 | 凸版印刷株式会社 | エンボスシート、それを用いた積層体およびその製造法 |
-
1998
- 1998-10-26 EP EP19980950373 patent/EP0955346B1/en not_active Expired - Lifetime
- 1998-10-26 EP EP20030002225 patent/EP1323801B1/en not_active Expired - Lifetime
- 1998-10-26 DE DE1998629322 patent/DE69829322T2/de not_active Expired - Lifetime
- 1998-10-26 DE DE1998625145 patent/DE69825145T2/de not_active Expired - Lifetime
- 1998-10-26 WO PCT/JP1998/004821 patent/WO1999023186A1/ja active IP Right Grant
- 1998-10-26 US US09/341,088 patent/US6274235B1/en not_active Expired - Lifetime
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JPH06336577A (ja) * | 1993-05-28 | 1994-12-06 | Hitachi Chem Co Ltd | 表面保護フイルム |
JPH07233354A (ja) * | 1993-12-28 | 1995-09-05 | Mitsui Petrochem Ind Ltd | 表面保護フィルム |
JPH0994532A (ja) * | 1995-10-04 | 1997-04-08 | Hitachi Chem Co Ltd | 塗膜保護方法および該方法に用いる表面保護フィルム |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2012200484B2 (en) * | 2006-11-08 | 2014-05-29 | Frans Nooren Afdichtingssystemen B.V. | Process for providing an extended tubular article with a corrosion protection coating system having self-repairing properties |
US9297490B2 (en) | 2006-11-08 | 2016-03-29 | Frans Nooren Afdichtingssystemen B.V. | Process for providing an extended tubular article with a corrosion protection coating system having self-repairing properties |
US9926630B2 (en) | 2012-07-13 | 2018-03-27 | Frans Nooren Afdichtingssystemen B.V. | Process for the protection against corrosion of an article in a wet environment and composition therefore |
US10801114B2 (en) | 2012-07-13 | 2020-10-13 | Frans Nooren Afdichtingssystemen B.V. | Process for the protection against corrosion of an article in a wet environment and composition therefore |
Also Published As
Publication number | Publication date |
---|---|
EP0955346A1 (en) | 1999-11-10 |
DE69829322T2 (de) | 2006-04-06 |
EP0955346B1 (en) | 2004-07-21 |
EP0955346A4 (en) | 2001-01-31 |
DE69825145D1 (de) | 2004-08-26 |
EP1323801A1 (en) | 2003-07-02 |
US6274235B1 (en) | 2001-08-14 |
EP1323801B1 (en) | 2005-03-09 |
DE69829322D1 (de) | 2005-04-14 |
DE69825145T2 (de) | 2005-08-04 |
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