MXPA97002232A - A film covered with adhes - Google Patents
A film covered with adhesInfo
- Publication number
- MXPA97002232A MXPA97002232A MXPA/A/1997/002232A MX9702232A MXPA97002232A MX PA97002232 A MXPA97002232 A MX PA97002232A MX 9702232 A MX9702232 A MX 9702232A MX PA97002232 A MXPA97002232 A MX PA97002232A
- Authority
- MX
- Mexico
- Prior art keywords
- adhesive
- film
- microspheres
- elastic
- substrate
- Prior art date
Links
- 239000004005 microsphere Substances 0.000 claims abstract description 89
- 239000000853 adhesive Substances 0.000 claims abstract description 85
- 230000001070 adhesive Effects 0.000 claims abstract description 85
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000002313 adhesive film Substances 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 238000005034 decoration Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 8
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- 240000008528 Hevea brasiliensis Species 0.000 description 2
- 235000016247 Mentha requienii Nutrition 0.000 description 2
- 235000002899 Mentha suaveolens Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000006682 bigleaf mint Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 235000006679 mint Nutrition 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-Methyl-2,4-pentanediol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- NCTBYWFEJFTVEL-UHFFFAOYSA-N 2-methylbutyl prop-2-enoate Chemical compound CCC(C)COC(=O)C=C NCTBYWFEJFTVEL-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241001649081 Dina Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 210000000474 Heel Anatomy 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001225 Polyester resin Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000468 Polystyrene-block-polybutadiene-block-polystyrene Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920002803 Thermoplastic polyurethane Polymers 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000149 penetrating Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
Abstract
An adhesive film for decoration prepared by coating an adhesive on a surface of a film substrate is disclosed, characterized in that the adhesive has microspheres, the elastic modulus of the microspheres is from 1 × 10 4 to 1 × 10 7 dynes / cm 2 and its particle diameter is 10 100æm (average volume diameter
Description
A FILM COATED WITH ADHESIVE Technical Field This invention is related to an adhesive film and more particularly! i with a film coated with an adhesive in microspheres, which easily allow trapped air bubbles to escape.
BACKGROUND OF THE INVENTION When D an adhesive film for decoration, according to the prior art, adheres to a substrate article, the air is trapped between the adhesive and the substrate article and to prevent entrapment, a considerably high level of Experience is necessary. In addition, a lot of work and time are necessary for the work of adhesion. When the conventional adhesive film for decoration adheres to a substrate article and is used indoors and outdoors, the adhesion strength rises over time and it is extremely difficult to separate the adhesive film from the substrate article. Thus, a great amount of work and time are also necessary. An adhesive sheet material described in the Patent Publication
Examined Japanese (Kokoku) No. 44-17040 and a positionable adhesive tape, described in Japanese Unexamined Patent Publication (Kokai) No. 3-181578, form hollows in a support or a carrier fabric and arrange the non-adhesive elements or beads of glass in the holes. Because the adhesive does not come in contact directly with the substrate article this REF: 24340 tape and the fabric have sliding ability and the work becomes easier. However, the stage of the process of forming the holes in the support and the carrier fabric is necessary. After the film is pressed onto the substrate article, the adhesive no longer has protuberances and the substrate article and the adhesive no longer have a contact point. Therefore, when the air remains on the substrate article in the center of the film, this air can not be removed. Since surface contact is established when the film is pressurized to the article of the substrate, the contact area increases with time and the adhesion strength increases, so that the re-release is extremely difficult. A pressure sensitive adhesive composition described in Japanese Examined Patent Publication (Kokoku) No. 45-17074 is obtained by mixing lightweight brittle glass pellets having a thin wall with a liquid adhesive composition and coating and drying the mixture. The adhesive having protuberances obtained in this manner has sliding ability because the adhesive does not come into direct contact with the substrate article and work becomes easier. However, after the film is press-adhered onto the substrate article, the glass beads are broken and the substrate article and the adhesive no longer have the point of contact. Therefore, if air remains in the center of the film, this air can not be removed. In addition, when the film adheres under pressure to the article of the substrate, the contact area becomes larger with time and the resistance to adhesion increases, so that re-detachment is extremely difficult. An adhesive tape for packaging described in Japanese Unexamined Utility Model Publication (Kokai) No. 59-763 and an adhesive tape described in Japanese Unexamined Utility Model Publication (Kokai) No. 59-37343 prevents entrapment of air by partial disposal of an adhesive layer. However, these tapes involve the problem that because the additive must be dispersed in a dot system or a striped pattern, a specific coating machine for this purpose is necessary. Another problem is that the surface of the film becomes uneven due to the stitches or the striped pattern, which is partially arranged. An air-permeable adhesive element described in Japanese Unexamined Patent Publication (Kokai) No. 2-45582 has a structure wherein an air permeable adhesive rod containing hollow beads is disposed on an air-permeable porous substrate and a large air-permeable substrate. number of cue microspheres communicate with the pores in the substrate are arranged. According to this conventional technique, the substrate is limited because it must be porous and special equipment is necessary to partially remove an adhesive solution by means of a gas impelling system or an air suction system from the air permeable substrate side after the coating solution applies Another problem is that when a decoration ink is applied, it closes the pores of the air permeable substrate and initial operation can not be obtained. An exterior adhesive sheet described in Japanese Examination of the Japanese Examination Model No. Kokai No. 59-54547 has a structure in which a flat film is laminated on one of the surfaces of a film having a continuous foam layer formed on it and an adhesive layer is arranged on the other surface, in such a way that the gas generated from the substrate has the possibility of penetrating with time. However, this sheet is not free of the problem that air trapped at the time of adhesion can not be removed because the adhesive layer is not permeable to air. A removable protective sheet, described in Japanese Utility Model Publication, Not Examined (Kokai) No. 5-56938 has a structure wherein the microspherical adhesive components are deposited with intervals between them on one of the surfaces of a support. This sheet involves the problem that the resistance to adhesion to the adhered article is as low as 100 g / 25 and when it is used in the open it naturally comes off. A re-peelable adhesive sheet disclosed in the Japanese Unexamined Utility Model Publication (Kokai) No. 61-168146 has a structure wherein a layer of an adhesive composition comprising elastic microspheres and an adhesive is formed on a substrate. A solution for preparing the desired adhesive composition is obtained by dispersing the microspheres and the adhesive in a volatile organic solvent. However, the elastic microspheres are obtained by a suspension polymerization method when using water as a medium and in order to disperse them uniformly in the organic solvent, the water content must be removed. However, this stage of the process has a high level Extremely low productivity and another problem is that the elastic microspheres suffer deformation and degradation due to the influences of the organic solvent and the desired point contact can not be obtained after the sheet adheres to the adhered article. Still another problem is that the adhesion strength can not be controlled when the adhesive composition is applied to the entire surface of the substrate and the adhesive must be coated in a configuration such as a square or a circle, such that A specific coating machine is necessary for this purpose. A positionable adhesive having a high cutting force, which is described in reference W092 / 13924, has a structure wherein a layer of adhesive composition comprising elastic microspheres and an adhesive is formed on a substrate. Since the mixing ratio of the elastic microspheres to the adhesive is high, the elastic microspheres are packed in high density to the adhesive layer and since the passages or passages of air necessary for deformation are not formed, entrapped air bubbles enter the adhesive layer. Adhesive and the substrate article can not be removed. Because the adhesive film has a flat adhesive layer, the adhesion between the adhesive and the article of the substrate becomes adhesion by surface contact and because the adhesion strength rises with the passage of time the re-release is difficult.
BRIEF DESCRIPTION OF THE INVENTION The present invention provides an adhesive film that is free from the problems described in the art, can be produced extremely easily, can easily remove trapped air between the adhesive layer and the substrate article at the time of adhesion and it can be detached from the adhered article. In particular, to solve the problems described in the art, the present invention provides an adhesive film for decoration that is produced by applying an adhesive on a surface of a film substrate, the present invention provides an adhesive film which is characterized in that the adhesive has microspheres, where the elastic modulus of the microslips is in the range of 1 x 10 4 to 1 x 10 7 dynes / cm 2 and the average particle size is in the range of 10 to 100 μm (in terms of the average volumetric diameter) .
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of the section of a film according to the present invention. Figure 2 is a schematic view showing the section under a state where the film according to the present invention adheres to an adhered article.
Description of late) preferred embodiments The thickness of the film substrate used in the adhesive film of the present invention is not particularly limited, but is preferable from 10 μm to 1, 500 μm from the readily available point of view. The film substrate preferably has an elastic modulus of 1 x 109 to 1 x 10 12 dynes / cm 2. When this elastic modulus is less than 1 x 109 dynes / cm2, the film is so soft and flexible that irregularities are likely to occur on the surface of the film and the problem of appearance develops. When the elastic modulus is greater than 1012 dynes / cm2, the film is so hard that it can not be easily deformed and its property to follow a curved surface is very low. With reference in general to the drawings and in particular to the figures, Figure 1 is a schematic view showing the section of the film according to the present invention. In the drawings, the symbol (A) represents the case where hollow spheres are used as the elastic microspheres and (B) represents the case where solid spheres are used. In these drawings, the reference numbers 1, 2 and 3 denote a film substrate, an adhesive and hollow spheres, respectively and the reference number 4 denotes solid spheres. The adhesive film that satisfies the conditions described above, can easily allow the escape of air trapped between the film and the substrate at the time of adhesion and because the film and the substrate are out of surface contact, the re-detachment is easy and the adhesive of the film does not remain on the surface of the substrate at the time of peeling. Figure 2 shows the effect of the present invention described above and is a sectional view of Figure 2 of the film after it is adhered to a substrate article. In the drawing, (A) represents the case where the elastic modulus of the microspheres is from 1 x 104 to 1 x 107 dynes / cm2 and falls within the range of the present invention. In this case, spaces (6) are defined between the adhesive layer (2) and the article of the substrate (5) and entrapment of air at the time of adhesion can be prevented. In addition, since the microspheres have proper elasticity, the microspheres become appropriately planar and the surface of the film substrate becomes flat. Figure 2 (B) represents the case where the elastic modulus of the microspheres is greater than 1 x 107 dynes / cm2. In this case, the spaces (6) are defined between the adhesive layer (2) and the substrate article (5), and entrapment of air at the time of adhesion can be prevented. However, because the microspheres do not undergo deformation, the irregularity occurs on the surface of the substrate sheet. Figure 2 (C) represents the case where the elastic modulus of the microspheres is less than 1 x 104 dynes / cm2. Because the microspheres become extremely flat and no gaps are formed between the adhesive layer and the substrate article, the entrapment of air at the time of adhesion can not be prevented. Ejemolos of the material of the film substrate include a polyvinyl chloride resin, a polyester resin, a polyacrylic resin, a Teflon resin, a polyolefin resin and so on. successively. Concrete examples are polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyvinylidene fluoride, polyethylene, polypropylene, polymethacrylate, Teflon, and so on. Particularly, the polyvinyl chloride resin can be easily printed to the surface and is suitable as the film substrate. It is economical and has appropriate outdoor weathering, so that the weather can be used as well. It is possible in the present invention to use those film substrates to which the surface treatment such as embossing or protection or mold release treatment is applied on the backside. Next, the elastic microspheres used in the present invention will be explained. When the adhesive film is pressed under pressure by a molding press, etc., the pressure applied to the film is about 15 Kg / cm2 and the microspheres used in the present invention have a strength such that they are not easily broken by such pressure. An acrylic resin, a silicone resin, a urethane resin, a vinyl acetate resin, a Teflon resin, a polyamide resin, a vinyl chloride resin, a styrene resin, a phenolic resin, a resin epoxy, a styrene-butadiene-styrene block copolymer resin, a styrene-ethylene-butylene-styrene block copolymer resin, a styrene-isoprene-styrene block copolymer resin, NBR, chloroprene rubber, natural rubber, etc., can be used as the material of the elastic microspheres. Particularly preferred among them is the acrylic resin because it has excellent weathering ability, it is suitable as a decoration material for outdoor use and the elastic microspheres can be easily and economically provided by a suspension polymerization method or the similar. In addition, the Tg (vitreous transition temperature) and the elastic modulus can be easily controlled because the classes of monomers and crosslinking agents are versatile and an appropriate adhesion strength can be obtained at room temperature, while retaining the forms of the microspheres. In addition, there is the advantage that even when the elastic microspheres adhere to the adhesive, the decrease in adhesion resistance is small. The acrylic resin is used in most cases by the main agent of the adhesive because it is generally economical and has a high adhesion strength. Another advantage is that when the acrylic type elastic microspheres are used by such an adhesive, the specific gravity is uniform and the dispersion is extremely easy. Since the elastic microspheres can easily undergo elastic deformation, the microspheres can be of a hollow type or can have gaps or voids consisting of these resins. Examples of the acrylic resins suitable for the formation of the elastic microspheres are copolymers between an acrylate and acrylic acid as listed below: 2-ethylhexyl acrylate copolymer / acrylic acid (99/1 - 90/10) (Tg = 69 to -60 ° C) copolymer of n-butyl acrylate / acrylic acid (99/1 - 90/10) (Tg = 54 to -45 ° C) copolipher of isononyl acrylate / acrylic acid (99/1) - 90/10) (Tg = -81 to -72 ° C) ethyl acrylate / acrylic acid copolymer (99/1 - 90/10) (Tg = -21 to 13 ° C.
SSee can also use isol acrylate, isobutyl acrylate, 2-methylbutyl acrylate, etc., as the acrylic ester monomer that makes up the rylic resin and other alpha-olefincarboxylic acids, such as methacrylic acid can be used. use instead of acrylic acid. When these monomers are used, also the weight ratio between the acrylate and the alpha-olefincarbo acid < Illic is preferably within the range of 99/1 to 90/10. This crosslinking can be carried out by using a bifunctional acrylate such as 1,4-butyl-2-diacrylate, divinylbenzene, etc., as a component of the monomer, for example. When these cross-linking agents are added, the stiffness ratio in general becomes greater and the adhesion is inconsistent. Therefore, in order to provide an appropriate adhesion strength, the amount of the crosslinking agent is not greater than
0. 5 parts in weight, preferably not greater than 0.1 parts by weight, based on
100 parts per kiss of the monomer.
polymerization in suspension, polymerization in emulsion or polymerization of seeding. The average volume diameter of the elastic microspheres used in the present invention is 10 μm to 100 μm. When the diameter is less than 10 μm, the peel does not naturally come off and the operation and adhesion and separation resistance of the bubbles can not be satisfied simultaneously. When the diameter is greater than 100 μm, irregularity occurs on the surface of the substrate film and an ink layer can not be uniformly printed. Because the density of the ink can not be controlled, the film can not be used as a decoration film. The elastic compression module of the microspheres used in the present invention is from 1 x 104 to 1 x 107 dynes / cm2 at 20 ° C. When the adhesive film is adhered by a molding press, etc., the pressure applied to the film is about 15 kg / cm2 and because the elastic microspheres used in the present invention have a strength such that they are not broken by such pressure , the protuberances can be stopped after the adhesion of the film and consequently, because the passage of bubbles can be ensured. When the elastic compression modulus is less than 1 x 104 dynes / cm2, aggregation of the microspheres is not sufficient. Consequently, the microspheres can not easily retain the spherical shape and suffer deformation due to adhesion and the escape steps of the bubbles can not be sufficiently ensured. When the elastic compression modulus is greater than 1 x 107 dynes / cm2, the adhesiveness decreases and the film can not be used. The average volume diameter of the elastic microspheres is determined according to the following equations when measuring 1, 000 microspheres when using an image processor by an optical microscopic method:
average diameter in volume =? ni-di4 /? ni-di3
where n is the number of microspheres, d is the diameter of the measured microspheres (μm), and i is an index. In the present invention, the elastic compression module of the elastic spheres is measured to use a viscoelastic spectrometer ("RSA11", a product of Rheometric Co.). In the present invention, the elastic microspheres can be individually dispersed in the adhesive or two or more microspheres can form a cluster in aggregation. It is because when the microspheres take up the cluster structure, the escape of trapped air becomes better. Such a cluster can be formed by adding the microspheres in advance to the adhesive solution by means of a binder such as gelatin, gum arabic, alcohol, etc., and then coating the solution. The bunch may also be formed by using the reaggregation effect at the coating drying time when selecting an appropriate set condition.
The cluster size is preferably from 2 to 100 pieces in terms of numbers of the microspheres. When the number of microspheres is greater than
100, the variance of the adhesion resistance becomes greater or an area in which the microspheres do not exist becomes larger, in such a way that the escape performance of trapped air becomes low, on the contrary. In addition, the elastic microspheres may be of the hollow or non-hollow type or may have a large number of voids inside the surface or the particles. These particles can be formed by changing the production condition mentioned above and the classes of the monomers and more specifically, they can be produced by the method described in Japanese Unexamined Patent Publication (Kokai) No. 2-194079. Next, the adhesive used in the present invention will be further explained. The adhesive used in the present invention is not particularly limited and the known adhesives such as an acrylic resin, a rubber type resin, (a natural rubber type resin and synthetic rubber type resin), a resin of the Type of silicone, a resin of the type of vinyl acetate, etc., can be used. The mixing ratio of the elastic microspheres and the adhesive in the present invention is from 30: 100 to 900: 100 and preferably from 100: 100 to 900: 100 in terms of a solids content ratio. Then, the ratio of the elastic microspheres becomes small, the distribution of the microspheres becomes coarse, the surface of the adhesive becomes substantially flat and the escape steps of the bubbles can not be sufficiently assured, so that the operation of the Removal of bubbles descends noticeably. When the proportion of the microspheres is much higher, the microspheres are packaged and distributed, in such a way that the escape performance of the bubbles deteriorates. The weight of the coating of the mixture comprising the adhesive and the elastic microspheres is from 4 to 40 g / m2. When the weight of the coating is less than 4 g / m2, it becomes difficult to reliably bond the adhesive film to the substrate article and it is likely that the film naturally falls off. When the weight of the coating is greater than 40 g / m2 the performance of elimination of the bubbles is lost and at the same time, the adhesion resistance to the article of the substrate becomes high, in such a way that the redistribution becomes extremely difficult. The thickness of the adhesive is preferably 20 to 90% of the average volume diameter of the elastic microspheres. When the thickness is less than 20%, the adhesive can not reliably adhere to the adhered article and when the thickness is greater than 90%, on the other hand, the performance in the elimination of bubbles decreases. In the production of the adhesive film according to the present invention the adhesive and the elastic microspheres are mixed in a predetermined proportion and the mixing solution is coated onto the substrate sheet and dried in the customary manner. The coating is carried out by using a uchilla coater, an engraving coater, a roller coater and so on. Drying after coating is carried out at 80 to 100 ° C for 3 to 10 minutes. The most suitable adhesion strength for the adhesive film in the present invention is 200 to 1000 g / 25 mm and more preferably 250 to 450 g / 25 mm. In the adhesive film of the present invention, which satisfies the conditions described above, the adhesive layer exists on the surface of the film substrate and a large number of elastic microspheres are dispersed in the adhesive layer. Therefore, the surface of the adhesive layer is not flat and a large number of protuberances, due to the microspheres are formed. Therefore, when the adhesive film is placed on the surface of the adhered article, the bonded surface and the surface of the adhesive layer do not come into close contact on all the entire surfaces, but a large number of passages or passages of air are formed. Therefore, the air trapped between the adhesive film and the adhered surface when the adhesive film adheres to the adhered surface by the molding press, etc., can be easily removed by means of these air passages and the adhesion work of the adhesive film becomes extremely easy. It is suggested that the elastic microspheres deform to the right and left by the applied pressure of the molding press, which forms the air flow and effectively expels the trapped air to the outside. In the adhesive film of the present invention, since the elastic spheres are properly deformable, the relationship between the coating thickness of the adhesive and the diameter of the microspheres need not be strictly controlled. As a result, the production condition becomes moderate and the advantages of the production aspect become greater. In addition, because the adhesive layer is in point contact with the adhered article by means of the elastic microspheres that have high aggregation property, the contact area does not become larger with the passage of time, but the resistance to bending At the time of adhesion it can be maintained in a stable manner. Accordingly, the film has excellent re-detachability.
Examples Pre-determined amounts of the elastic microspheres and the adhesive were mixed and sufficiently stirred. The mixture was coated in such a manner to achieve a predetermined coating weight after drying and was dried at 100 ° C for 5 minutes, after which a release coating (separator) was laminated.
Test Methods: Bubble Disability After the separator was detached or separated, a 10 x 10 cm sample was placed on a flat, smooth acrylic plate and press molded into the center of the adhesive film by a molding press. , in such a way that bubbles could accumulate. A 2 kg roll was rolled over the air bubbles thus formed and the escape mode of the air bubbles was observed. This procedure was repeated four times. The sample in which the air bubbles were completely expelled was indicated by a mark or and the sample where the air bubbles persisted was partially indicated by the x mark.
Smoothness of the surface of the film A sample of 30 cm x 30 cm was applied to a flat and smooth acrylic plate and any irregularity of the surface of the film was visually inspected. The sample where the shapes of the elastic microspheres were recognized was indicated by the mark x and the sample where the shapes were not recognized was evaluated by the mark or.
Adhesion A sample was cut in 15 cm x 2.5 cm and adhered to an aluminum plate subjected to degreasing treatment by IPA under the condition of 20 ° C x 65% RH when using a roller as described in JIS Z0237. After the sample was allowed to stand under the same condition for 48 hours, a 90 ° peel strength at a 90 ° angle was measured at a peel rate of 30 cm / minute using a "Tensilon" apparatus.
Natural detachment A sample was adhered to an aluminum plate, placed in a thermal cycle test apparatus and subjected to aging for seven cycles. After this, any detachment of the substrate was examined. The sample without detachment was indicated by the mark or and the sample with detachment was indicated by the mark x.
Thermal cycle: 1 cycle (24 hours) -30 ° C x 0% RH (2 hours) - (1 hour) - 23 ° C x 65% RH (0.5 hours) - (0.5 hours) - 40 ° C x 95% RH (2 hours) - (0.5 hours) - 23 ° C x 65% RH (0.5 hours) - 30 ° C x 0% RH (2 hours) - (1 hour) - 23 ° C x 65% RH (0.5 hours) ) - (1 hour) - 80 ° C x 50% RH (11 hours) - (1 hour) - 23 ° C x 65% RH (0.5 hours).
Example 1
Microspheres Microspheres having several average particle diameters were used, which were obtained by the suspension polymerization of isooctyl acrylate and acrylic acid in a ratio of 94/6 as the monomers, using water as the medium. The elastic compression modulus of the elastic microspheres was 2.3 x 106 dynes / cm2 Adhesive AE 238B, a product of Nippon Gosei Gomu K.K.
Film Substrate A polyvinyl chloride film having a thickness of 100 μm and an elastic modulus of 2 × 10 10 dynes / cm 2 was used.
Film size evaluation test The production conditions and the characteristics of the adhesive film produced were as follows: Bubbility test of leakage: 10 cm x 10 cm Test of surface smoothness of the film: 30 cm x 30 cm Test of adhesion: 15 cm x 2.5 cm
The conditions for the preparation and properties of the adhesive film are as follows.
TABLE 1
Experiment Average Diameter Relation Weight Ratio- Disability Example Smoothness /
Volumetric no. Of the weight of the bubble layer the super- Example microsphere elas- microsphere (g / m2) elasticity of the com- pact (μm) elastic and the adhesive film
1-1 168 29/71 80.7 X X Comp. Example
1-2 d 17/83 54.0 0 X Comp. Ex.
1-3 50 20/80 18.0 X 0 Ex. Comp
1-4 50 90/10 20.3 0 0 Example
1-5 50 80/20 21.0 0 0 Example
1-6 50 54/46 25.0 0 0 Example
Experiment Average diameter Reagent Weight Ratio Adhesion Removed - Example /
Volumetric number of the weight of the bridle (gf / 25 mm) Example example micosphere of the microsphere (g m2) Compatibility (μm) elastic and adhesive ratios 1-7 50 80/20 3.0 50 X Comp.
1-8 50 44/56 56.2 1150 0 Ex. Comp
1-9 50 90/10 16.0 430 0 Example
1-10 50 80/20 14.5 380 0 Example In Experiment 1-1 (Comparative Example) the bubbles did not escape because the coating weight was too large, but in Experiments 1-4 through 1-6 (Examples) , the escape performance of the bubbles was excellent because the coating weight was appropriate. In Experiments 1 and 1-2 (Comparative Examples) irregularity occurred on the surface of the film because the diameter of the elastic microspheres was too large, but in Experiments 1-4 to 1-6 (Examples), the movie had excellent appearance. In Experiment 1-3 (Comparative Example), the escape performance of the bubbles could not be obtained because the weight ratio of the elastic microspheres and the adhesive was not adequate, but in Experiments 1-4 to 1- 6 (Examples), the films had excellent performance of escape bubbles. In Experiment 1-7 (Comparative Example) the coating weight was so low that the film naturally detached from the substrate article, but Experiments 1-9 and 1-10 (Examples) had excellent adhesion characteristics. In Experiment 1-8 (Comparative Example), the adhesion strength was so high that re-detachment of the adhered article was extremely difficult, but Experiments 1-19 and 1-10 had excellent re-detachibility.
Example 2 Elastic microspheres The same composition as described in Example 1 was used.
Adhesive The same adhesive was used as in Example 1.
Film Substrate A polyvinyl chloride substrate was made and had an elastic modulus of 2 x 1010 dynes / cm and a thickness of 100 μm.
Evaluation of the film size: Irregularity of the film surface 30 cm x 30 cm Test for the escape of air bubbles 10 cm x 10 cm Test for adhesion 15 cm x 2.5 cm.
TABLE 2 ExperiMicrosphere i elastic Microsphere Weight of Slip thickness of the Escapabi bility Example / mint Module Elastic diameter covering the bubble surface of the bubble Adhesion Example
No Elastic of parti- Parts by adhesion to the film Comparative d? Na / cm2 μm weight (g m2) (%) (gf / 25 mm). - "6 2- i tsrera i x l? du o? u 50? ? Ejtíipμi?
2-2 micro 1 x 103 50 500 20 50 O X 610 Comp. Ex.
2-3 elasti- 1 x 1010 50 500 20 50 X O 80 Comp.
2-4 ca (type 1 x 106 5 500 20 50 O X 820 Ej Comp.
2-5 solid) 1 x 106 150 500 20 50 X O 120 Comp.
2-6 1 x 106 50 10 20 50 O X 23 n Ex Comp.
2-7 1 x 106 50 1500 20 50 O X 170 Comp. Comp.
2-8 1x 106 50 500 2 10 O O v 40 Comp. Comp
2-9 1 x 106 50 500 50 100 O X 1200 Ej Comp.
ExperiMicroesfer. i Elastic Microsphere Weight of Heel Thickness of the Disability Example / mint Module Elastic diameter to cover the surface of the bubble Adhesion Example No. Elastic of parti- Parts by adhesion to the film The comparative dina / cm2 um weight (fl / m2) (%) (gf / 25 mm) 2-10 Sphere 1 x 104 50 500 20 50 OO 400 Example 2-11 micro 1 x 103 50 500 20 50 OX 680 Comp. 2-12 Elastic- 1 x 1010 50 500 20 50 X O 180 Ex. Comp. 2-13 ca (type 1 x 106 5 500 20 50 O X 800 Ex. Comp.I
2-14 hollow 1 x 106 150 500 20 50 X 0 230 Comp. Comp. I
2-15 1 x 106 50 10 20 50 O X 420 Ex. Comp. 2-16 1 x 106 50 1500 20 50 0 X 350 Ex Comp. 2-17 1x 106 50 500 2 10 0 0 50 Ex. Comp. 2-18 1 x 106 50 500 50 100 0 X 1250 Ex Comp. 2-19 Pearls - 70 20 20 50 X X 50 Comp. Comp. of glass 2-20 +++ _ _ 15 100 0 X 900 Ex. Comp.
In Table 2, the term "parts by weight of the elastic microspheres" is the value based on 100 parts by weight of the adhesive and the term "coating weight" is a value representing the thickness of the coated adhesive layer with respect to to the average diameter in volume of the elastic microspheres. The production condition of the adhesive film and the characteristics of the film thus produced were as follows. Since Experiments 2-1 and 2-10 were within the appropriate range of condition, an excellent surface smoothness of the film, bubble leakage and adhesion could be obtained. In Experiments 2-2 and 2-12, the elastic modulus of the elastic microspheres was so low that the bubbles could not escape. In Experiments 2-3 and 2-11, the elastic modulus of the elastic microspheres was so high that irregularity occurred on the surface of the film. In Experiments 2-4 and 2-13, the particle size of the elastic microspheres was so small that the bubbles could not escape and in Experiments 2-5 and 2-14, on the other hand, the particle size was so large irregularity was presented on the surface of the film. In Experiments 2-6 and 2-15, the ratio of the adhesive to the elastic microspheres was too great and in Experiments 2-7 and 2-16, it was too small, so that the escapeability of the bubbles could not be get in no case. In Experiments 2-8 and 2-17, the weight of the coating was so small that the adhesion was too low and Experiments 2-9 and 2-18, the weight of the coating was so large that the adhesion became too high. In experiment 2-19, since the glass beads did not easily undergo deformation, it was likely that the irregularity occurred and because the adhesive and the adhered article had point contact, the adhesion was low. In Experiment 2-20, the bubble leakage was low because the adhesive and the adhesive article were placed in surface contact.
EXAMPLE 3 Elastic microspheres Microspheres having an elastic modulus of 3 x 106 dynes / cm2 and an average particle diameter of 50 μm and made of isooctyl acrylate / acrylic acid in a ratio of 95/5 were used.
Adhesive 100 parts by weight of the adhesive described in Example 1 were used per 500 parts by weight of the elastic microspheres.
Film substrate An elaborate polyester film was used.
Coating weight 20 g / m: per film substrate Film size for the evaluation test: Irregularity of the film surface 30 cm x 30 cm Test for the escape of air bubbles 10 cm x 10 cm Test for adhesion 15 cm x 2.5 cm
The production condition and characteristics of the adhesive film thus produced are tabulated in the following Table 3. Table 3
Expep- Escapabilidad Lugas Example / ment the superde the bubble Adhesion Example No. Film of the Comparative EspeModulo film gf / 25 mm elastic s
3-1 100 μm i 5 106 O O 380 Example dynes / cm2 3-2 100 2 x 103 X X 360 Ex. Comp. 3-3 100 2 x 1013 1 O O 360 Ex. Comp
ExperiLisations of Disability Example / mento the superde the bubble Adhesion Example No Film of the Comparative Specimen module film gf / 25 mm elastic strip
3-4 10 2 x 109 O O 400 Example 3-5 1500 2 x 109 O O 410 Example 3-6 10 2 x 1012 O O 380 Example 3-7 1500 2 x 1012 0 0 390 Example
Since Experiments 3-1 and 3-4 to 3-7 were within the ranges of film thickness and elastic modulus, a flat and smooth film surface and sufficient air leakage could be obtained and it was confirmed that they could be obtained Extremely excellent features like a film for decoration. On the other hand, because the elastic modulus of the film was so low in Experiment 3-2 that irregularity occurred on the surface of the film, the escapeability of the bubbles could not be obtained. In Experiment 3-3, the film was so hard that its property to follow a curved surface was low and the film could not be used as a decoration film.
It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following
Claims (7)
- Claims 1. An adhesive film for decoration having a coated adhesive on a surface of a film substrate, characterized in that the adhesive has microspheres, the elastic modulus of the microspheres is from 1 x 104 to 1 x 107 dynes / cm2 and the diameter The average volumetric pore is 10 to 100 μm.
- 2. An adhesive film according to claim 1, characterized in that the elastic modulus of the film is from 1 x 109 to 1 x 10 12 dynes / cm 2 and the thickness is within the range of 10 μm to 1, 500 μm.
- 3. An adhesive film according to claim 2, characterized in that from 30 to 900 parts by weight of the elastic microspheres are added to 10 parts by weight to the adhesive.
- 4. An adhesive film according to claim 3, characterized in that the elastic microspheres form clusters.
- 5. An adhesive film according to claim 4, characterized in that the elastic microspheres have gaps or voids.
- 6. An adhesive film according to any of the preceding claims, characterized in that a mixture comprising the adhesive and the elastic microspheres is coated in a coating weight in the range of 4 to 40 g / m2.
- 7. An adhesive film according to claim 6, characterized in that the adhesive is coated in a thickness of 20 to 90% with respect to the average volumetric diameter of the elastic microspheres.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-243079 | 1994-10-06 | ||
| JP9/243079 | 1994-10-06 | ||
| JP24307994A JP3585962B2 (en) | 1994-10-06 | 1994-10-06 | Film with bubble removal performance |
| PCT/US1995/011767 WO1996011116A1 (en) | 1994-10-06 | 1995-09-15 | An adhesive-coated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA97002232A true MXPA97002232A (en) | 1997-06-01 |
| MX9702232A MX9702232A (en) | 1997-06-28 |
Family
ID=17098472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9702232A MX9702232A (en) | 1994-10-06 | 1995-09-15 | An adhesive-coated film. |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0784544B1 (en) |
| JP (1) | JP3585962B2 (en) |
| CN (1) | CN1160377A (en) |
| AU (1) | AU3633595A (en) |
| BR (1) | BR9509240A (en) |
| CA (1) | CA2200193A1 (en) |
| DE (1) | DE69511709T2 (en) |
| MX (1) | MX9702232A (en) |
| WO (1) | WO1996011116A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4442670C1 (en) * | 1994-11-30 | 1996-05-30 | Atlas Vertriebs Gmbh | Application of self adhesive film to vehicles |
| JP3612386B2 (en) * | 1996-08-28 | 2005-01-19 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesive film 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 |
| EP0839887B1 (en) * | 1996-10-30 | 2000-02-02 | Rikidyne Co., Ltd. | A permeable adhesive tape and a process for preparing the same |
| GB2344061B (en) * | 1998-11-26 | 2001-08-15 | William Britton | Repositionable and/or slippable self-adhesive articles |
| US6673419B1 (en) | 1999-03-12 | 2004-01-06 | 3M Innovative Properties Company | Marking film and composite marking film |
| JP2000265123A (en) * | 1999-03-12 | 2000-09-26 | Minnesota Mining & Mfg Co <3M> | Marking film and composite marking film |
| US6656567B1 (en) | 1999-04-30 | 2003-12-02 | 3M Innovative Properties Company | Adhesive sheet and adhesive sheet applied structure |
| US6524675B1 (en) | 1999-05-13 | 2003-02-25 | 3M Innovative Properties Company | Adhesive-back articles |
| JP2001262089A (en) * | 2000-03-15 | 2001-09-26 | Three M Innovative Properties Co | Pressure-sensitive adhesive article and pressure- sensitive adhesive sheet |
| KR100411188B1 (en) * | 2000-10-20 | 2003-12-18 | 한솔제지주식회사 | Process for preparing seed polymer for pore microsphere adhesive |
| US7709070B2 (en) * | 2001-12-20 | 2010-05-04 | The Procter & Gamble Company | Articles and methods for applying color on surfaces |
| CN101466540A (en) | 2006-06-02 | 2009-06-24 | 日东电工株式会社 | Polymer member having incompatible material maldistributed polymer layer and surface uneven tape or sheet made of the polymer member |
| JP2009249582A (en) * | 2008-04-10 | 2009-10-29 | Daiwa Kasei Shoji Kk | Pressure-sensitive adhesive film |
| JP5933957B2 (en) * | 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 | Graphics film precursor |
| JP6326780B2 (en) * | 2013-11-19 | 2018-05-23 | コニカミノルタ株式会社 | Window pasting film |
| CN104835409A (en) * | 2014-02-12 | 2015-08-12 | 鸿富锦精密工业（深圳）有限公司 | Label |
| JP6587883B2 (en) * | 2015-09-28 | 2019-10-09 | リンテック株式会社 | Adhesive sheet and method for producing adhesive sheet |
| WO2018189626A1 (en) | 2017-04-10 | 2018-10-18 | 3M Innovative Properties Company | Adhesive sheet and method of applying adhesive sheet to rough surface |
| JP7164307B2 (en) | 2017-04-10 | 2022-11-01 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive sheet and method of applying adhesive sheet to rough surface |
| CN109368025A (en) * | 2018-11-22 | 2019-02-22 | 南京讯飞智慧空间信息科技有限公司 | A kind of quickstick device and its package |
| JP7327934B2 (en) | 2018-12-21 | 2023-08-16 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive sheet and method of applying adhesive sheet to rough surface |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0414434Y2 (en) * | 1985-04-08 | 1992-03-31 | ||
| ZA876122B (en) * | 1986-08-21 | 1989-04-26 | Minnesota Mining & Mfg | Pressure-sensitive tape construction incorporating resilient polymeric microspheres |
| JP2657965B2 (en) * | 1987-10-31 | 1997-09-30 | 日本カーバイド工業 株式会社 | Pressure-sensitive adhesive layer |
| US5118750A (en) * | 1990-04-20 | 1992-06-02 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive comprising solid tacky microspheres and macromonomer-containing binder copolymer |
| JP3417596B2 (en) * | 1993-04-07 | 2003-06-16 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Adhesive film containing elastic microspheres |
| JP2804743B2 (en) * | 1996-05-24 | 1998-09-30 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive sheet-like structure |
-
1994
- 1994-10-06 JP JP24307994A patent/JP3585962B2/en not_active Expired - Fee Related
-
1995
- 1995-09-15 EP EP95933825A patent/EP0784544B1/en not_active Expired - Lifetime
- 1995-09-15 DE DE69511709T patent/DE69511709T2/en not_active Expired - Lifetime
- 1995-09-15 WO PCT/US1995/011767 patent/WO1996011116A1/en not_active Application Discontinuation
- 1995-09-15 MX MX9702232A patent/MX9702232A/en unknown
- 1995-09-15 CN CN95195532A patent/CN1160377A/en active Pending
- 1995-09-15 CA CA002200193A patent/CA2200193A1/en not_active Abandoned
- 1995-09-15 AU AU36335/95A patent/AU3633595A/en not_active Abandoned
- 1995-09-15 BR BR9509240A patent/BR9509240A/en not_active Application Discontinuation
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