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WO1998018878A1 - Feuille adhesive et procede de fabrication correspondant - Google Patents

Feuille adhesive et procede de fabrication correspondant Download PDF

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Publication number
WO1998018878A1
WO1998018878A1 PCT/US1997/018285 US9718285W WO9818878A1 WO 1998018878 A1 WO1998018878 A1 WO 1998018878A1 US 9718285 W US9718285 W US 9718285W WO 9818878 A1 WO9818878 A1 WO 9818878A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
elastic
adhesive
tacky polymer
microspheres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1997/018285
Other languages
English (en)
Inventor
Mamoru Kanno
Hidetoshi Abe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US09/284,573 priority Critical patent/US6217981B1/en
Priority to AU48980/97A priority patent/AU4898097A/en
Publication of WO1998018878A1 publication Critical patent/WO1998018878A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • 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
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive

Definitions

  • the present invention relates to an adhesive sheet comprising a flexible substrate and an adhesive layer formed on at least one of the main surfaces of the substrate and containing elastic microspheres. More particularly, the invention relates to an adhesive sheet which has a high peeling adhesion strength in a dry state, a high water-resistant adhesion strength and good bubble escapability.
  • the adhesive layer of an adhesive sheet is generally a single layer if it contains elastic microspheres.
  • Such an adhesive sheet is produced by applying a coating liquid containing elastic microspheres and a tacky polymer directly onto the surface of a substrate and drying the applied coating liquid to form a single layer adhesive film as disclosed in JP-A-6-287525.
  • a coating liquid containing elastic microspheres and a tacky polymer directly onto the surface of a substrate and drying the applied coating liquid to form a single layer adhesive film as disclosed in JP-A-6-287525.
  • Bubbles which have been trapped between the adhesive layer and the adherent can be easily removed when they are forced to escape by the application of a pressure from the back face of the support towards the adherent in the presence of those passages.
  • the adhesive layer tends to maintain the above spot contact state after the adhesion of the adhesive sheet to the adherent (finish pressing), and therefore the peeling adhesion strength is low.
  • a DINOCTM brand film commercially available from Sumitomo 3M Co. Ltd.
  • One of the reasons for the continuation of spot contact may be that the tacky polymer layer covering the elastic microspheres is in a single layer state having a small thickness in comparison to the diameter of the microspheres, has small flow during the press adhering of the sheet to the adherent and small flow over time (namely, cold flow), and therefore the contact areas of the adhesive layer do not increase readily.
  • JP-A-6-322325 discloses an example of adhesive sheets having a dual adhesive layer.
  • the used adhesive layer is prepared by laminating a primer layer containing hollow microparticles and a top adhesive layer on the primer layer.
  • the primer layer functions to compensate surface irregularity of the adherent such as a corrugated board, etc. after the adhesive sheet is adhered to the adherent, and thus good adhesion of the sheet to the irregular surface is achieved.
  • the contact between the adhesive sheet and adherent is plane contact since the top surface of the adhesive layer has no projections, and therefore the bubble escapability is not good.
  • JP-U-5 -72946 discloses an adhesive sheet or tape having a dual adhesive layer containing elastic microspheres.
  • the disclosed adhesive tape or sheet comprises a substrate, an adhesive layer containing elastic microspheres, and a layer of viscoelastic materials having a thickness of 20 pm inserted between the substrate and adhesive layer.
  • This structure improves the adhesion of the tape or sheet to adherents having irregular surfaces such as a corrugated board, etc. and achieves repositioning properties of the tape or sheet while preventing spontaneous peeling.
  • large cold flow cannot be expected with this structure, and the contact areas of adhesive layer do not readily increase.
  • the present invention provides an adhesive sheet comprising a flexible substrate, and an adhesive layer formed on at least one of the main surfaces of said flexible substrate and containing elastic microspheres, wherein said adhesive layer comprises a) an elastic microsphere layer which is in contact with the main surface of the flexible substrate, comprising said elastic microspheres and a first tacky polymer and having projections containing said elastic microspheres on a surface which is not in contact with said substrate, and b) a layer of a second tacky polymer which covers said projections containing the elastic microspheres so that raised portions are formed on an adhesion surface.
  • the invention also pertains to a method for producing an adhesive sheet, comprising the steps of (a) applying a coating liquid comprising a second tacky polymer on a releasing surface of a release liner, and drying the applied coating liquid to form a layer of tacky polymer, (b) applying a coating liquid comprising elastic microspheres and a tacky polymer on the layer of tacky polymer and drying the applied coating liquid to form an elastic microsphere layer having temporarily raised portions containing the microspheres on its surface, and (c) having a main surface of a flexible substrate in close contact with the surface of said elastic microsphere layer under a specific pressure so that the temporary projections are reversed to form projections having specific sizes on an adhesion surface of an adhesive layer which faces the release liner.
  • the adhesive layer of the adhesive sheet according to the present invention comprises an elastic microsphere layer and a layer of the second tacky polymer.
  • the elastic microsphere layer is formed so that it has the projections containing the elastic microspheres on the surface which is not in contact with the substrate and it functions as a primer layer for the formation of the raised portions having a specific size.
  • the thickness (or amount) of the tacky polymer which covers the microspheres is relatively small in the elastic microsphere layer which has been formed to provide the effective projections.
  • the elastic microsphere layer it is difficult for the elastic microsphere layer to improve the adhesion strength, in particular, the peeling adhesion strength (at a peeling angle of 90 degrees) in a dry state and to prevent a large decrease of the peeling adhesion strength (at a peeling angle of 90 degrees) caused by the penetration of water from the atmosphere.
  • the layer of the second tacky polymer is coated over the projection of the elastic microsphere layer to form the raised portions having a specific size on the adhesion surface.
  • the layer of the second tacky polymer improves the bubble escapability and achieves a high adhesion strength after press adhering the sheet to the adherent.
  • the raised portions on the adhesive layer should form passages which communicate with the atmosphere and through which bubbles trapped between the adherent and adhesive layer escape easily by the bubble removing procedures in the press adhering step for the adhesive layer.
  • the layer of the second tacky polymer flows easily since it covers the projections containing the elastic microspheres without being in direct contact with the microspheres.
  • the adhesive layer according to the present invention can lead to an improvement of the peeling adhesion strength and as such the water-resistant adhesion strength more effectively than the adhesive layer consisting of a single elastic microsphere layer.
  • the preferable compressive modulus of the microspheres is in the range between 1 X 10 4 and 1 X 10 7 dyne/cm 2 in view of the above flowability.
  • the compressive modulus exceeds 1 X 10 7 dyne/cm 2 , the layer of the second tacky polymer may not have sufficient flowability.
  • the compressive modulus is less than 1 X 10 4 dyne/cm 2 , the peeling adhesion strength as such the water- resistant adhesion strength may not increase.
  • the compressive modulus is measured using a RS A 1 1 viscoelastic spectrometer (manufactured by RHEOMETRIX) at 20°C.
  • the thickness of the layer of the second tacky polymer is preferably in the range between 1 and 100 g/m 2 , more preferably in the range between 5 and 80 g/m 2 in terms of a coating weight.
  • the coating weight is less than 1 g/m 2 , the improvement of the peeling adhesion strength in a dry state and the water-resistant adhesion strength tends to deteriorate.
  • the coating weight exceeds 100 g/m 2 , the bubble escapability tends to decrease.
  • the elastic microsphere layer comprises elastic microspheres and a tacky polymer (the first tacky polymer).
  • the first tacky polymer functions to bond the elastic microsphere layer to the substrate and to effectively form the projections containing the elastic microspheres.
  • the projections containing clusters which consist of a plurality of elastic microspheres can be formed when the elastic microsphere layer is formed by applying a coating liquid containing the elastic microspheres, the first tacky polymer and a solvent onto the layer of the second adhesive layer or the main surface of the substrate and drying the coated liquid. Furthermore, the adhesion properties of the adhesive layer on the adherent do not deteriorate, if the first and second tacky polymers are mixed up and the mixture flows.
  • the thickness of the elastic microsphere layer is preferably in the range between 5 and 150 g/m 2 , more preferably in the range between 10 and 100 g/m 2 in terms of a coating weight.
  • the coating weight is less than 5 g/m 2 , the adhesion properties may deteriorate.
  • the coating weight exceeds 150 g/m 2 , the projections having the sufficient size may not be formed.
  • the volume average diameter of elastic microspheres is preferably in the range between 10 and 300 pm. When the volume average diameter is less than 10 pm, the bubble escapability tends to decrease. When the volume average diameter exceeds 300 pm, a sufficient adhesion area cannot be achieved even if the second tacky polymer or the mixture of the first and second tacky polymers flows, and therefore the improvement of the peeling adhesion strength and as such the water- resistant adhesion strength is insufficient.
  • the amounts of the elastic microspheres and the first tacky polymer in the elastic microsphere layer are such that the elastic microspheres are contained preferably in an amount of between 10 and 900 wt. parts, more preferably between 20 and 100 wt. parts per 100 wt. parts of the tacky polymer. When the amount of the elastic microspheres is less than 10 wt. parts, the bubble escapability tends to decrease. When this amount exceeds 900 wt. parts, the adhesion strength of the elastic microsphere layer to the substrate decreases.
  • the flexible substrate allows the easy press adhering of the adhesive sheet to an adherent and bubble escaping, and also has the following functions.
  • the adhesive layer formed on a temporal releasable support is in close contact with the flexible substrate, and the raised portions having a specific size are easily shaped on the adhesion surface. Therefore, a plastic film having a thickness in the range between 10 and 1000 pm is preferably used as the flexible substrate.
  • Fig. 1 schematically shows the first subcombination of the adhesive sheet of the present invention.
  • Fig. la schematically shows the second subcombination of the adhesive sheet of the present invention.
  • Fig. lb schematically shows the final step to forming the adhesive sheet of the present invention.
  • Figs. 1, 1a, and lb show the construction of an adhesive sheet of the present invention.
  • the sheet comprises a layer 1 of a second tacky polymer, a plurality of microspheres 3, a layer 2 of a first tacky polymer, and a substrate 4.
  • the inversion of "first” and “second” concerns the view of layering of the two different tacky polymers from the perspective of the substrate 4.
  • any flexible sheets such as a paper sheet, metal film or plastic film can be used as the substrate.
  • “Plastics” include synthetic polymers such as polyvinyl chloride, polyester, polyurethane, polyacrylate, etc.
  • the surface of the substrate on which the adhesive layer is formed may be treated to increase the adhesion strength of the adhesive layer to the substrate.
  • the surface treatment can be performed by corona treatment, plasma treatment or treatment with chemical agents.
  • Aqueous emulsion type polymers are preferable as the first tacky polymer composition, since the lamination of the adhesive layer and the clusters of the elastic microspheres can easily be made.
  • Either solution type polymers or emulsion type polymers can be used as the second tacky polymer composition, while the solution type polymers are preferable since they have excellent properties for improving the water-resistant adhesion strength.
  • Any polymeric materials which are conventionally used as adhesive materials can be used as the first and second tacky polymers.
  • the tacky polymers are acrylic polymers, rubbery polymers, silicone polymers, polyurethanes, polyolefins, and so on. Among them, the acrylic polymers are preferable.
  • a preferred example of the acrylic polymer is a copolymer of at least one acrylic monomer which provides a homopolymer having a glass transition temperature between -50°C and less than 25°C (e.g. isooctyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, etc.) and at least one vinyl monomer which provides a homopolymer having a glass transition temperature between 25°C and 150°C (e.g. methyl methacrylate, acrylic acid, styrene, etc.).
  • the acrylic monomer increases the adhesion properties of the copolymer
  • the vinyl monomer increases the cohesive force of the copolymer.
  • the weight ratio of the acrylic monomer (A) to the vinyl monomer (V) (A:V) is usually in the range between 85:15 and 99:1, preferably in the range between 90:10 and 98:2.
  • the acrylic polymer are copolymers of isooctyl acrylate and acrylic acid, copolymers of n-butyl acrylate and acrylic acid, copolymers of 2-ethylhexyl acrylate and acrylic acid, and so on.
  • the molecular weight of the tacky polymer is in a range in which the polymer exhibits the desired adhesive properties. In general, the weight average molecular weight is in the range between 10,000 and 1 ,000,000.
  • the tacky polymer may contain any conventional additive such as a tackifier, crosslinking agent, and so on, insofar as the effects of the present invention do not deteriorate.
  • the elastic microspheres preferably exhibit tackiness.
  • the tacky elastic microspheres may be produced from a tacky polymer having a compressive modulus of between 1 X 10 4 and 1 x 10 7 dyne/cm 2 .
  • the volume average diameter of the microspheres is preferably in the range between 10 and 300 pm, more preferably in the range between 25 and 250 ⁇ m.
  • the volume average diameter is obtained by measuring diameters of 1000 microspheres with an optical microscope and an image analyzer, and calculating an average value according to the following equation:
  • volume average diameter ( ⁇ m) ⁇ (d, 4 x n,)/ ⁇ (d, 3 x n,) wherein d, is a measured diameter ( ⁇ m) of a microsphere having an i-th largest diameter, and n, is the number of microspheres having the diameter d,.
  • the elastic microspheres are produced preferably from acrylic polymers since the tackiness is effectively improved.
  • the acrylic polymers for the microspheres may be copolymers prepared from the same monomers as those used for the preparation of the adhesive copolymers.
  • the elastic microspheres are generally prepared by suspension polymerization. For example, a quantity of water, emulsifier, monomers, oil- soluble polymerization initiator, and other additive(s) are charged into a reactor equipped with a mechanical mixer and heated to a specific temperature while stirring to initiate the polymerization reaction. The stirring speed is generally between 10 and 700 rpm, and the heating temperature is generally between 30 and 120°C. The reaction time is generally between several hours to several tens of hours. For example, a production method for such acrylic polymeric microspheres is disclosed in US Patent No. 4,994,322.
  • the elastic microspheres may be solid or hollow ones having at least one pore.
  • the polymer for the elastic microspheres may be crosslinked. Formation of adhesive layer
  • the adhesive layer may be formed as follows: The elastic microspheres, tacky polymer, solvent, and optional additives are mixed with the mixing apparatus such as a homomixer to disperse or dissolve all the components uniformly, and a coating liquid for each layer is prepared.
  • the mixing apparatus such as a homomixer to disperse or dissolve all the components uniformly, and a coating liquid for each layer is prepared.
  • the prepared coating liquids are successively coated on a temporal support and dried to form the elastic microsphere layer and the layer of second tacky polymer.
  • the coating liquids can be coated by any of the conventional coating means such as a knife coater, bar coater, roll coater, die coater and so on.
  • a layer having a uniform thickness can be formed by adjusting the viscosity of the coating liquid in a suitable range.
  • the viscosities of the coating liquids for the elastic microsphere layer and the layer of the second tacky polymer are both in the range between 100 and 10,000 cps. When the viscosity is less than 100 cps, the layer may not be formed at the sufficient coating weight. When the viscosity exceeds 10,000 cps, it may be difficult to apply the coating liquid at a uniform thickness.
  • the lamination of the layers can be performed as follows:
  • a coating liquid comprising the second tacky polymer is applied on a releasing surface (51 ) of a release paper (5) at a specific coating weight in the above explained range and dried to form a layer (1) of the second tacky polymer.
  • the drying temperature is between 50 and 150°C.
  • a coating liquid comprising the first tacky polymer (2) and elastic microspheres (3) is applied on the surface of the layer (1) of the second tacky polymer and dried to form an elastic microsphere layer.
  • the above steps produce a laminate comprising the release paper (5), the layer (1) of the second tacky polymer, and the elastic microsphere layer having a plurality of temporal protrusions which contain the elastic microspheres in this order.
  • drying temperature in the coating step for the elastic microsphere layer is between 90 and 150°C.
  • a flexible substrate (4) is laminated onto the elastic microsphere layer and pressed under a specific pressure, as seen in Fig lb.
  • the elastic microsphere layer and the flexible substrate (4) are closely adhered so that the temporal protrusions are reversed to complete the adhesive sheet.
  • the elastic microsphere layer and the flexible substrate (4) are closely adhered so that the elastic microspheres in the protrusions are temporarily deformed. Then, the deformed elastic microspheres are recovered, and raised portions having a specific size are formed on the surface of adhesive layer (20) which faces the temporal support. The deformed microspheres do not recover just after the adhering of the substrate, but recover after a short time from the adhering of the substrate.
  • the above method can be used to form the raised portions having a specific size and containing the elastic microspheres which are covered with a layer of the second adhesive layer on the adhesion surface of adhesive layer.
  • the pressure in the step for adhering the substrate is usually between 10 and 50 kgf/cm 2 , preferably in the range between 15 and 30 kgf/cm 2 .
  • this pressure is too high, the projections containing the elastic microspheres are plastically deformed, and heights of the raised portions on the adhesive layer will be insufficient.
  • this pressure is too low, the adhesion between the elastic microsphere layer and the substrate is insufficient, and the projections may not be sufficiently reversed.
  • the adhesive layer may not be well adhered to the substrate and also raised portions having an effective size may not be formed.
  • the above laminate and the support are press adhered using a laminator having a pair of press rolls.
  • the material of the press rolls may be metals, rubbers, elastomers and so on.
  • the press rolls can be heated in the press adhering step.
  • the heating temperature for the rolls is usually in the range between 25 and 80°C.
  • the roll temperature is less than 25°C, bubbles remain between the flexible support and elastic microsphere layer, and the adhesion between them may decrease.
  • the roll temperature exceeds 80°C, the exposed surface of the flexible support may be raised due to pressing of the microspheres against the support.
  • the raised portions on the exposed surface of the flexible substrate are not preferable since the appearance of the adhesive sheet, in particular, decorative sheet deteriorates when the adhesive sheet is bonded to the adherent.
  • only a roll which is in contact with the temporal support, that is, the release paper is heated, since the formation of the raised portions on the exposed surface of the flexible support is easily prevented.
  • the release paper as the temporal support may be left on the adhesive layer so as to protect the adhesive layer.
  • the release paper as the temporal support may be removed and a new release paper may be provided on the adhesive layer.
  • the adhesive sheet can be produced by laminating the elastic microsphere layer and the layer of second adhesive polymer in this order on the substrate.
  • the solid content and coating weight of the coating liquid containing the second tacky polymer are adjusted adequately.
  • Preferable coating means are a knife coater and Mayor bar.
  • the solid content in the coating liquid containing the second tacky polymer is preferably in the range between 20 and 70 wt. %, and the coating weight is preferably in the range between 1 and 100 g/m 2 .
  • the raised portions of the adhesive layer which have been formed as described above have a sufficient size for providing good bubble escapability during the press bonding of the adhesive sheet.
  • the size of raised portions can be expressed in terms of a contact area percentage between the adhesive layer and a plate surface when the contact area percentage is measured by adhering the adhesive sheet onto a flat glass surface under the pressure of 2 kgf/25 cm 2 .
  • the contact area percentage is a ratio of an actually contacting area between the adhesive layer and the adherent to an apparent contact area.
  • the contact area percentage is measured as follows:
  • the adhesive layer of the adhesive sheet is adhered to a flat surface of glass plate such as a slide glass and pressed by a roller of 2 kg by reciprocating it over the adhesive sheet one time.
  • the contact area percentage measured as above is preferably in the range between 20 and 90 %, more preferably in the range between 30 and 70 %, in particular in the range between 40 to 60 %.
  • the contact area percentage in this range can improve the adhesive properties of the adhesive sheet such as the high peeling adhesion strength in a dry state, the high water-resistant adhesion strength, etc., while maintaining good bubble escapability.
  • the contact area percentage increases as the size of the microspheres decreases or the coating weight of the whole adhesive layer increases, while it decreases as the content of the microspheres in the tacky polymer increases. Accordingly, the contact area percentage can be controlled in the above range by adjusting these parameters in the desired ranges.
  • a silicone release paper (Product No.) RHC-11 (manufactured by SAN-EL CHEMICAL Co., Ltd.) was used as a release paper.
  • Ethyl acetate was used as a diluent for the coating liquid containing the second tacky polymer.
  • a crosslinking agent (COLONATE L55E (trade name) manufactured by NIPPON POLYURETHANE Co., Ltd.) were added to 100 wt. parts of the acrylic tackifier (solution) so that the viscosity of the coating liquid was about 1000 cps.
  • D) Application of layer of second tacky polymer The coating liquid for the layer of second adhesive polymer was coated with a knife coater on the release paper as the temporal support and dried to form the layer of second tacky polymer. Drying was carried out at about 65°C for 90 seconds and then at 95°C for 90 seconds. The coating weight of the layer of the second tacky polymer was 8 g/m 2 in this Example.
  • the monomer composition comprised isooctyl acrylate and acrylic acid in a molar ratio of 94:6.
  • This copolymer had the compressive modulus of 2.5 x lO 6 dyne/cm 2 .
  • composition of coating liquid for elastic microsphere layer The weight ratio of the elastic microspheres to the first tacky polymer was
  • the elastic microspheres, the first tacky polymer and a crosslinking agent for first tacky polymer were mixed with a homomixer to disperse them homogeneously. Then the mixture was thickened with an alkali, and a coating liquid was obtained.
  • the crosslinking agent was E- AX (manufactured by SOKEN CHEMICAL Co., Ltd.) in the amount of 1.8 wt. parts per 100 wt. parts of the solution of tacky polymer.
  • the coating liquid had the solid content of 50 wt. % and the viscosity of 1000 Cps.
  • the coating liquid for the elastic microsphere layer was applied onto the above formed layer of the second tacky polymer with a knife coater at a coating weight of 16 g/m 2 and dried at about 100°C for 5 minutes to form an elastic microsphere layer having a plurality of projections containing elastic microspheres, and a laminate consisting of the release paper, the layer of the second tacky polymer and the elastic microsphere layer in this order was obtained.
  • the produced adhesive sheet was subjected to the evaluation of the peeling adhesion strength in the dry state, water resistant peeling force and bubble escapability as follows: Peeling adhesion strength
  • a sample of an adhesive sheet having the size of 150 mm x 25 mm was adhered to a bonderized steel plate at 20°C, 65 %RH with a roller of 2 kg, and aged at 20°C, 65 %RH for 48 hours. Then, the peeling force of the sample was measured with a tensile tester at a peeling angle of 90°, at a peeling rate of 300 mm/min. Water Resistant Peeling Adhesion strength
  • a 150 mm x 25 mm sample of an adhesive sheet was prepared and adhered to a bonderized steel plate at 200°C, 65 %RH with a roller of 2 kg, and aged at 20°C, 65 %RH for 24 hours and further in warm water at 40°C for one week.
  • the sample was removed from water, water was wiped off from the surface of the sample and the sample was kept standing at 20°C, 65 %RH for 5 minutes. Then, the peeling force of the sample was measured with a tensile tester at a peeling angle of 90° at a peeling rate of 300 mm/min.
  • the adhesive sheets were produced in the same manner as in Example 1 except that the coating weight of the layer of second tacky polymer, the volume average diameter of the elastic microspheres and the coating weight of the elastic microsphere layer were changed as shown in Table 1.
  • the adhesive sheets were produced in the same manner as in Example 1 except that the volume average diameter of elastic microspheres and the coating weight of the elastic microsphere layer were changed as shown in Table 2, and the coating liquid for the elastic microsphere layer was coated directly on the substrate and dried to form a single layer adhesive layer.
  • each adhesive sheet was subjected to the same evaluation tests as in Example 1. The results are shown in Table 2.
  • the adhesive sheets produced in Comparative Examples A and B had very low water resistant peeling forces since no layer of second tacky polymer was provided.
  • the adhesive sheet was produced in the same manner as in Example 1 except that the coating liquid for the layer of the second adhesive polymer was coated directly onto the substrate and dried to form a single layer adhesive layer.
  • the adhesive sheet of Comparative Example D had low bubble escapability since no elastic microsphere layer was provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Cette invention se rapporte à une feuille adhésive comportant un substrat flexible (4) et une couche adhésive (20) formée sur au moins l'une des surfaces principales dudit substrat flexible et contenant des microsphères élastiques (3). Ladite couche adhésive comporte, d'une part, (a) une couche de microsphères élastiques qui est en contact avec la surface principale du substrat flexible, qui contient des microsphères élastiques (3) et un polymère collant (2) et qui présente des protubérances contenant lesdites microsphères élastiques sur une surface qui n'est pas celle en contact avec ledit substrat et, d'autre part, (b) une couche d'un polymère collant (1) qui recouvre lesdites protubérances contenant les microsphères élastiques de façon à ce que des parties en saillie soient formées sur une surface d'adhésion (11). Le fait que la surface d'adhésion possède un pourcentage d'aire d'adhésion compris entre 20 et 90 %, permet à des bulles d'air de s'échapper en cours d'application et d'utilisation. L'invention se rapporte également à un procédé de fabrication de cette feuille adhésive.
PCT/US1997/018285 1996-10-25 1997-10-13 Feuille adhesive et procede de fabrication correspondant Ceased WO1998018878A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/284,573 US6217981B1 (en) 1997-10-13 1997-10-13 Adhesive sheet and method for producing the same
AU48980/97A AU4898097A (en) 1996-10-25 1997-10-13 Adhesive sheet and method for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP28368396A JP3612394B2 (ja) 1996-10-25 1996-10-25 粘着シートおよびその製造方法
JP8/283683 1996-10-25

Publications (1)

Publication Number Publication Date
WO1998018878A1 true WO1998018878A1 (fr) 1998-05-07

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PCT/US1997/018285 Ceased WO1998018878A1 (fr) 1996-10-25 1997-10-13 Feuille adhesive et procede de fabrication correspondant

Country Status (3)

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JP (1) JP3612394B2 (fr)
AU (1) AU4898097A (fr)
WO (1) WO1998018878A1 (fr)

Cited By (25)

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WO1999058620A1 (fr) * 1998-05-14 1999-11-18 Minnesota Mining And Manufacturing Company Feuille adhesive et structure appliquee de feuille adhesive
WO2000022059A1 (fr) * 1998-10-14 2000-04-20 Minnesota Mining And Manufacturing Company Feuilles adhesives et structures adhesives
FR2787116A1 (fr) * 1998-12-10 2000-06-16 Guttaterna Matiere de collage d'un revetement sur une surface sensiblement plane et procede de pose d'un tel revetement
US6217981B1 (en) * 1997-10-13 2001-04-17 3M Innovative Properties Company Adhesive sheet and method for producing the same
US6294250B1 (en) 1996-08-28 2001-09-25 3M Innovative Properties Company Adhesive film and method for producing the same
WO2001078131A1 (fr) * 2000-04-06 2001-10-18 Cintech Ad Venture Pte Ltd Procede et ensemble permettant d'appliquer un adhesif sur un substrat
US6656567B1 (en) 1999-04-30 2003-12-02 3M Innovative Properties Company Adhesive sheet and adhesive sheet applied structure
WO2005063464A3 (fr) * 2003-12-29 2005-10-06 Mactac Europ S A Procede de formation d'une microstructure tridimensionnelle sur une surface, ses utilisations, et produits microstructures ainsi obtenus
DE102008004388A1 (de) 2008-01-14 2009-07-16 Tesa Ag Geschäumte, insbesondere druckempfindliche Klebemasse, Verfahren zur Herstellung sowie die Verwendung derselben
DE102008056980A1 (de) 2008-11-12 2010-05-20 Tesa Se Strahlenchemisch vernetzbare, geschäumte Selbstklebemasse basierend auf Vinylaromatenblockcopolymeren
WO2010112346A1 (fr) 2009-04-01 2010-10-07 Tesa Se Procédé de fabrication d'un système de masse expansé
EP2796490A1 (fr) 2013-04-24 2014-10-29 Tesa Se Masse polymère doublement expansée
EP2801461A2 (fr) 2013-05-08 2014-11-12 Tesa Se Procédé de fabrication d'une masse polymère expansée syntactique, de préférence d'une masse collante sensible à la pression, dispositif d'exécution du procédé, produit d'extrusion et ruban autocollant
US9085121B2 (en) 1999-05-13 2015-07-21 3M Innovative Properties Company Adhesive-backed articles
EP3075772A1 (fr) 2015-04-02 2016-10-05 tesa SE Bande adhésive amovible
WO2016156305A1 (fr) 2015-04-02 2016-10-06 Tesa Se Bande adhésive décollable
DE102016223852A1 (de) 2016-11-30 2018-05-30 Tesa Se Wiederablösbarer Haftklebestreifen
WO2018153618A1 (fr) 2017-02-24 2018-08-30 Tesa Se Bande adhésive repositionnable
WO2018189626A1 (fr) * 2017-04-10 2018-10-18 3M Innovative Properties Company Feuille adhésive et procédé d'application d'une feuille adhésive sur une surface rugueuse
DE202015009724U1 (de) 2015-04-02 2019-08-16 Tesa Se Wiederablösbarer Haftklebestreifen
DE202015009721U1 (de) 2015-04-02 2019-08-23 Tesa Se Wiederablösbarer Haftklebestreifen
DE202015009730U1 (de) 2015-04-02 2019-09-06 Tesa Se Wiederablösbarer Haftklebestreifen
CN110520494A (zh) * 2017-04-10 2019-11-29 3M创新有限公司 粘合剂片材和将粘合剂片材施加到粗糙表面的方法
WO2020193461A1 (fr) 2019-03-28 2020-10-01 Tesa Se Bande adhésive de contact détachable
WO2022207460A1 (fr) 2021-04-01 2022-10-06 Tesa Se Utilisation d'une bande adhésive en tant qu'élément de recouvrement d'une source de rayonnement de haute fréquence

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JP3838808B2 (ja) * 1999-03-30 2006-10-25 日本カーバイド工業株式会社 再剥離型感圧接着剤組成物
JP3591639B2 (ja) * 2000-10-05 2004-11-24 コニシ株式会社 リサイクル型水性接着剤組成物
JP3591640B2 (ja) * 2000-10-23 2004-11-24 コニシ株式会社 リサイクル型水性接着剤
JP2002129120A (ja) * 2000-10-23 2002-05-09 Konishi Co Ltd リサイクル型水性接着剤組成物
JP4781514B2 (ja) * 2000-11-02 2011-09-28 スリーエム イノベイティブ プロパティズ カンパニー 接着剤組成物および接着シート
JP5933957B2 (ja) * 2011-10-21 2016-06-15 スリーエム イノベイティブ プロパティズ カンパニー グラフィックスフィルム前駆体
JP6302330B2 (ja) * 2014-04-02 2018-03-28 リンテック株式会社 粘着シートの製造方法
JP6874993B2 (ja) * 2015-09-28 2021-05-19 リンテック株式会社 粘着シート、及び粘着シートの製造方法
WO2017057404A1 (fr) * 2015-09-28 2017-04-06 リンテック株式会社 Feuille adhésive et procédé de production d'une feuille adhésive
JP6725249B2 (ja) * 2015-12-28 2020-07-15 住友化学株式会社 樹脂フィルム付光学部材の製造方法
JP2020142530A (ja) * 2020-05-15 2020-09-10 住友化学株式会社 樹脂フィルム付光学部材の製造方法

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EP0708162A2 (fr) * 1994-10-17 1996-04-24 Minnesota Mining And Manufacturing Company Article adhésif thermo-activable

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US6294250B1 (en) 1996-08-28 2001-09-25 3M Innovative Properties Company Adhesive film and method for producing the same
US6217981B1 (en) * 1997-10-13 2001-04-17 3M Innovative Properties Company Adhesive sheet and method for producing the same
WO1999058620A1 (fr) * 1998-05-14 1999-11-18 Minnesota Mining And Manufacturing Company Feuille adhesive et structure appliquee de feuille adhesive
CN1097625C (zh) * 1998-05-14 2003-01-01 美国3M公司 粘合片和施加有粘合片的结构
WO2000022059A1 (fr) * 1998-10-14 2000-04-20 Minnesota Mining And Manufacturing Company Feuilles adhesives et structures adhesives
AU748253B2 (en) * 1998-10-14 2002-05-30 Minnesota Mining And Manufacturing Company Adhesive sheets and adhesive structures
FR2787116A1 (fr) * 1998-12-10 2000-06-16 Guttaterna Matiere de collage d'un revetement sur une surface sensiblement plane et procede de pose d'un tel revetement
US6656567B1 (en) 1999-04-30 2003-12-02 3M Innovative Properties Company Adhesive sheet and adhesive sheet applied structure
US9085121B2 (en) 1999-05-13 2015-07-21 3M Innovative Properties Company Adhesive-backed articles
WO2001078131A1 (fr) * 2000-04-06 2001-10-18 Cintech Ad Venture Pte Ltd Procede et ensemble permettant d'appliquer un adhesif sur un substrat
EA010748B1 (ru) * 2003-12-29 2008-10-30 Мактак Юроп С.А. Способ образования трехмерной микроструктуры на поверхности, его применение и полученные таким образом микроструктурированные продукты
WO2005063464A3 (fr) * 2003-12-29 2005-10-06 Mactac Europ S A Procede de formation d'une microstructure tridimensionnelle sur une surface, ses utilisations, et produits microstructures ainsi obtenus
EP2610289A2 (fr) 2008-01-14 2013-07-03 tesa AG Masse de collage expansée, notamment sensible à la pression, son procédé de fabrication et son utilisation
DE102008004388A1 (de) 2008-01-14 2009-07-16 Tesa Ag Geschäumte, insbesondere druckempfindliche Klebemasse, Verfahren zur Herstellung sowie die Verwendung derselben
DE102008056980A1 (de) 2008-11-12 2010-05-20 Tesa Se Strahlenchemisch vernetzbare, geschäumte Selbstklebemasse basierend auf Vinylaromatenblockcopolymeren
WO2010112346A1 (fr) 2009-04-01 2010-10-07 Tesa Se Procédé de fabrication d'un système de masse expansé
DE102009015233A1 (de) 2009-04-01 2010-10-14 Tesa Se Verfahren zur Herstellung eines geschäumten Massesystems
US10457791B2 (en) 2009-04-01 2019-10-29 Tesa Se Method for producing a self-adhesive
EP2796490A1 (fr) 2013-04-24 2014-10-29 Tesa Se Masse polymère doublement expansée
DE102013207467A1 (de) 2013-04-24 2014-10-30 Tesa Se Dual geschäumte Polymermasse
US9499676B2 (en) 2013-05-08 2016-11-22 Tesa Se Process for producing a syntactically foamed polymer composition, preferably a pressure-sensitive adhesive composition, apparatus for carrying out the process, extrudate and self-adhesive tape
DE102013208445A1 (de) 2013-05-08 2014-11-13 Tesa Se Verfahren zum Herstellen einer syntaktisch geschäumten Polymermasse, vorzugsweise einer druckempfindlichen Klebemasse, Vorrichtung zur Durchführung des Verfahrens, Extrudat und Selbstklebeband
EP2801461A2 (fr) 2013-05-08 2014-11-12 Tesa Se Procédé de fabrication d'une masse polymère expansée syntactique, de préférence d'une masse collante sensible à la pression, dispositif d'exécution du procédé, produit d'extrusion et ruban autocollant
US10759974B2 (en) 2015-04-02 2020-09-01 Tesa Se Removable pressure-sensitive adhesive strip
EP3075772A1 (fr) 2015-04-02 2016-10-05 tesa SE Bande adhésive amovible
WO2016156305A1 (fr) 2015-04-02 2016-10-06 Tesa Se Bande adhésive décollable
DE102015206076A1 (de) 2015-04-02 2016-10-06 Tesa Se Wiederablösbarer Haftklebestreifen
EP3581630A1 (fr) 2015-04-02 2019-12-18 tesa SE Bande adhésive pouvant être fixée de manière démontable
WO2016156307A1 (fr) 2015-04-02 2016-10-06 Tesa Se Bande adhésive décollable
DE202015009730U1 (de) 2015-04-02 2019-09-06 Tesa Se Wiederablösbarer Haftklebestreifen
DE202015009724U1 (de) 2015-04-02 2019-08-16 Tesa Se Wiederablösbarer Haftklebestreifen
DE202015009721U1 (de) 2015-04-02 2019-08-23 Tesa Se Wiederablösbarer Haftklebestreifen
US10351740B2 (en) 2016-11-30 2019-07-16 Tesa Se Redetachable adhesive strip
DE102016223852A1 (de) 2016-11-30 2018-05-30 Tesa Se Wiederablösbarer Haftklebestreifen
WO2018153618A1 (fr) 2017-02-24 2018-08-30 Tesa Se Bande adhésive repositionnable
WO2018189626A1 (fr) * 2017-04-10 2018-10-18 3M Innovative Properties Company Feuille adhésive et procédé d'application d'une feuille adhésive sur une surface rugueuse
CN110520494A (zh) * 2017-04-10 2019-11-29 3M创新有限公司 粘合剂片材和将粘合剂片材施加到粗糙表面的方法
US11407925B2 (en) 2017-04-10 2022-08-09 3M Innovative Properties Company Adhesive sheet and method of applying adhesive sheet to rough surface
WO2020193461A1 (fr) 2019-03-28 2020-10-01 Tesa Se Bande adhésive de contact détachable
US12077695B2 (en) 2019-03-28 2024-09-03 Tesa Se Detachable adhesive strip
WO2022207460A1 (fr) 2021-04-01 2022-10-06 Tesa Se Utilisation d'une bande adhésive en tant qu'élément de recouvrement d'une source de rayonnement de haute fréquence
DE102021203370A1 (de) 2021-04-01 2022-10-06 Tesa Se Verwendung eines Haftklebstreifens als Abdeckung einer Hochfrequenzstrahlungsquelle

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AU4898097A (en) 1998-05-22
JP3612394B2 (ja) 2005-01-19

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