AQUEOUS ADHESIVE COMPOSITION, ADHESIVE FILM AND PROCESS FOR PRODUCING IT

Abstract: An adhesive layer having minimal coating failure and little thickness variation is diclosed. An aqueous adhesive composition comprises a mixed solvent of water and a co-solvent, and an adhesive component dissolved or dispersed in the mixed solvent, the co-solvent containing a compound (A) represented by formula (1) wherein R1 is a methyl group or an ethyl group; and R2 is an alkylene group having 3 to 5 carbon atoms.

Description: AQUEOUS ADHESIVE COMPOSITION, ADHESIVE FI LM AND PROCESS FOR PRODUCING IT. FIELD OF THE INVENTION The present invention relates to an aqueous adhesive composition More particularly, it relates to an aqueous adhesive composition which is suitable for producing products having an adhesive layer, such as adhesive film, etc Furthermore, the present invention relates to an adhesive film having an adhesive layer formed from the above aqueous adhesive composition, and a process for producing the same BACKGROUND OF THE INVENTION In the production of products, wherein an adhesive layer is provided on at least one surface ofa substrate (hereinafter referred to as an "adhesive film", sometimes), such as adhesive film (e g , graphic film, etc ), adhesive tape (e.g , mending tape, etc ), marking material, etc , an aqueous adhesive composition containing a water-soluble or water-dispersible polymer as an adhesive component has hitherto been used as a coating solution for forming the adhesive layer thereof Examples ofthe process for producing these products include the following (i) a process comprising providing an adhesive layer on a substrate (e g , film, etc ) and laminating a base having a mold release layer such as silicon layer, etc (hereinafter referred to as a "liner") to protect the adhesive layer, and (ii) a process comprising providing an adhesive layer on a mold release layer of a liner and laminating a substrate thereon However, it is normally difficult to provide the adhesive layer on the liner by applying the aqueous adhesive composition according to the above process (ii) because the surface ofthe mold release layer (sometimes referred to as a "mold release surface") has water repellency That is, regarding a conventional aqueous adhesive composition, wetting to the surface having a water repellency to be coated is insufficient and a coating failure (e.g., cissing, recess, etc.) is generated. Therefore, it is impossible to form a coating which has a sufficient thickness and has no thickness variation In order to prevent the above coating failure, it is effective to add a thickening agent. For example, an aqueous adhesive composition containing such a thickening agent is disclosed in Japanese Laid-open Patent Publication No. 61 -101555 This composition contains a thickening agent such as a slurry obtained by dissolving xanthanegum in a non-solvent such as alcohol, glycol, glycol monoether, etc However, the thickening agent increases a viscosity ofthe composition to deteriorate a fluidity ofthe composition Therefore, it becomes difficult to form a coating having no thickness variation to obtain well-balanced coating characteristics Furthermore, in order to prevent the coating failure, it is also effective to add a nonionic surfactant For example, an aqueous adhesive composition containing such a nonionic surfactant is disclosed in Japanese Laid- Open Patent Publication No 55-30967 This publication discloses a water-soluble sizing agent containing an nonionic surfactant for adhering a surface protective sheet on a synthetic resin plate The useful nonionic surfactant disclosed in the publication contains a comparatively high molecular weight hydrophobic group such as alkyl or aralkyl group having not less than 12 carbon atoms Therefore, it is inferior in hydrophilic nature and compatibility with the polymer component so that the polymer component is liable to separate in the adhesive layer. The separation causes deterioration of adhesive force with time On the other hand, it has been known that a hydroxy-substituted compound is used as the additive ofthe adhesive composition to control the adhesive force ofthe adhesive For example, a water-soluble adhesive containing such a compound is disclosed in Japanese Laid-Open Patent Publication Nos 3-149280 and 3-149281 Furthermore, in Japanese Laid-Open Patent Publication No 57-186, there is disclosed that a curing agent for a water-soluble phenol resin such as ethylene glycol diacetate can be used as the other additive. However, such an additive is not used to prevent generation ofthe coating failure and, therefore, it is inferior in function for preventing the coating failure. Furthermore, it has also been known to use a water-miscible organic solvent which is miscible with water as a co-solvent. For example, in Japanese Laid- Open Patent Publication No. 4-337381, there is disclosed a solid adhesive composition comprising an adhesive resin, water, a water-miscible organic solvent, a gelatinizing agent and an alkyl glycoxide, which can be applied on the surface to be adhered, smoothly and uniformly, with a small pressure. Examples of he useful water-miscible organic solvent disclosed in this publication include hydroxy group- containing compounds such as cellosolve (ethylene glycol monoethyl ether), butyl carbitol (diethylene glycol monobutyl ether), glycerin, etc. The water-miscible organic solvent is also used for paint, such as industrial high gloss lacquer. However, these solvents have no sufficient performances for improving a wettability to the surface ofthe material such as silicone having a water repellency to form a coating having a sufficient thickness and no thickness variation on the surface to be coated. It is also known that an aqueous acrylic pressure sensitive adhesive contains such a thickening agent as mentioned above and a surfactant. For example "AROSET resins" which is commercially available from Ashland Co. is an emulsion based acrylic pressure sensitive adhesive using an acrylic latex thickening agent Also, the article, "SURFACTANT IN PRESSURE SENSITIVE ADHESIVE" by William R. Dougherty (Air Products and Chemicals, Inc., ) suggests that a glycol based nonionic surfactant reduces surface energy of an aqueous coating composition of acrylic pressure sensitive adhesive and effectively improves wettability and generation of bubble. However, as mentioned above, the addition ofthe thickening agent and the surfactant does not always dissolve the problems mentioned above 84 PC17US96/12869 SUMMARY OF THE INVENTION In the light ofthe above problems ofthe prior art, the present invention provides an aqueous adhesive composition having the following characteristics ( 1 ) It has a sufficient fluidity (e.g., a viscosity within a suitable range, etc ) at the time of applying operation. (2) It can be applied on the surface of an object having a water repellency (e.g , liner etc.) in a sufficient thickness (dry thickness, for example, a weight after drying of 4 to 100 g/m 2 ). (3) It can form an adhesive layer having minimal coating failure (e.g., cissing, recess, etc ) and little thickness variation by a normal applying operation (4) It can form an adhesive layer having an adhesive force which is stable with time The present invention provides an aqueous adhesive composition comprising a mixed solvent of water and a co-solvent, and an adhesive component dissolved or dispersed in the mixed solvent, the co-solvent containing a compound A represented by the formula ( 1 ) Ri — O— R 2 — OC— H 3 (1 ) 0 wherein Ri is a methyl group or an ethyl group, and R 2 is an alkylene group having 3 to 5 carbon atoms Another aspect of the present invention also provides an adhesive film having the improved adhesive layer as described above Another aspect of the present invention is to provide a process for producing an adhesive film having the improved adhesive layer as described above Further aspects and features ofthe invention are disclosed in the following description ofthe embodiments EMBODIMENTS OF THE INVENTION As described above, the aqueous adhesive composition comprises a mixed solvent of water and a co-solvent, and an adhesive component dissolved or dispersed in the mixed solvent, the co-solvent containing a compound A represented by the formula ( 1 ) wherein Ri is a methyl group or an ethyl group; and R 2 is an alkylene group having 3 to 5 carbon atoms The compound A is contained in the mixed solvent to improve solubility or dispersion properties ofthe adhesive component in the mixed solvent, thereby acting on the fluidity and drying rate ofthe adhesive composition to control them within a suitable range As a result, the above-described application properties ofthe aqueous adhesive composition as well as stability with time ofthe adhesive force ofthe adhesive layer formed from the adhesive-composition can be improved These properties ofthe compound A manifest from its chemical structure, that is, the fact that it contains no hydroxyl group but contains a methoxy group (or ethoxy group) and an acetoxy group and an alkylene group exists between these functional groups has 3 to 5 carbon atoms One preferred embodiment ofthe present invention is characterized by the fact that the amount ofthe compound A to be contained is within a range of 20 to 100 parts by weight, based on 100 parts by weight of water When the amount is smaller than 20 parts by weight, it is likely to impossible to impart a fluidity enough to facilitate the applying operation On the contrary, when the amount is larger than 100 parts by weight, it takes a long time to dry and, therefore, the productivity is liable to become inferior When the fluidity of the adhesive composition is represented by the viscosity ofthe adhesive composition, it is preferred that the viscosity is within a range of 500 to 10,000 cps When the viscosity is smaller than 500 cps, it is liable to become difficult to obtain a coating having a sufficient thickness and no thickness variation On the contrary, when the viscosity is larger than 10,000 cps, the fluidity is inferior and, therefore, it is likely to become difficult to conduct the applying operation and to supply the adhesive composition to the applying apparatus. Furthermore, when the viscosity is too large, air bubbles entrapped at the time of dispersing are not easily escaped and crater, pinhole, etc. are easily generated in the coat In another embodiment, the present invention provides an adhesive film comprising a film-like substrate and an adhesive layer formed on the substrate, the adhesive layer being formed by vaporizing a mixed solvent from the aqueous adhesive composition of claim 1 Since this adhesive film is formed from the above adhesive composition, it has no coating failure such as cissing, recess, etc., which are generated in the applying operation Furthermore, it has an adhesive layer having thickness variation within a stated range and the adhesive layer has an adhesive force which is stable with time It is preferred that such an adhesive layer has a compression modulus which is a value measured at 20°C and is within a range of 1 x IO 4 to I O 7 dyne/cm 2 When the compression modulus is smaller than 10 4 dyne/cm 2 , the cohesiveness becomes small and adhesion performances such as retention are liable to become insufficient On the contrary, when the compression modulus is larger than 10 dynecm 2 , the tackiness is deteriorated and it is likely to become difficult to apply the adhesive film at normal temperature In still another embodiment, the present invention provides a process for producing an adhesive film consisting ofa film-like substrate, an adhesive layer and a liner, which are mutually laminated in this order, comprising the steps of (a) applying the aqueous adhesive composition of claim 1 on a mold release surface ofthe liner, at least one surface of which is the mold release surface, and removing a mixed solvent in the composition to form an adhesive layer, and (b) laminating the film-like substrate on the adhesive layer to seal This production process facilitates the production ofthe above-described adhesive film to improve the productivity In the adhesive film, the form of the substrate (e g , decorative motif, etc.) varies depending upon products when the material of the substrate, thickness or substrate is decorated However, a common liner can be used for different products Accordingly, if a liner with an adhesive layer is previously mass produced to stock the resulting liners and then a substrate corresponding to the ordered product is prepared to produce an adhesive film using the substrate and the above liner with an adhesive layer, the service efficiency ofthe applying apparatus is enhanced As a result, the productivity ofthe adhesive film can be enhanced The compound A is different from the water-miscible organic solvent containing a hydroxyl group in the molecule (e g , cellosolve, etc ) in the fact that the compound A has not a large solubility to water That is, the compound A may have a predetermined solubility to water within a range that it is contained in the mixed solvent to improve the solubility or dispersion properties ofthe adhesive component in the mixed solvent, thereby acting on the fluidity and drying rate ofthe adhesive composition to control them within a suitable range The solubility ofthe compound A to water is normally within a range of 1 to 30 ml/1 00 ml of water, preferably 5 to 20 ml/100 ml of water In the formula ( 1), the number of carbon atoms of R 2 is within a range of 3 to 5 When the number of carbon atoms is smaller than 3, the above- described application properties ofthe aqueous adhesive composition can not be improved On the contrary, when the number of carbon atoms is larger than 5, it takes a long time to dry and, therefore, the productivity becomes inferior An alkylene group of R 2 can take a straight-chain structure or a branched structure Furthermore, Ri is a methyl group, preferably Because the solubility to water becomes comparatively good, which facilitates the improvement of application properties ofthe adhesive composition The vaporization rate ofthe compound A when that of butyl acetate is 100 is preferably within a range of 5 to 50, particularly 8 to 40 Furthermore, the solubility parameter ofthe compound A is preferably within a range of 8 0 to 10 0, particularly 8 2 to 9 5 Nonlimiting examples ofthe compound A include the following Propylene glycol monomethyl ether acetate (PGM-AC manufactured by Kuraray Co., Ltd;) Ri = methyl group, number of carbon atoms of R 2 = 3, solubility parameter = 9.2, vaporization rate (when that of butyl acetate is 100) = 34, solubility to water = 18.5 ml/ 100 ml Propylene glycol monoethyl ether acetate (PE-AC: manufactured by Kuraray Co., Ltd; ) Ri = ethyl group, number of carbon atoms of R 2 = 3, vaporization rate (when that of butyl acetate is 100) = 19, solubility to water = 9.5 ml/100 ml 3-Methyl-3-methoxybutyl acetate (Sorfit™-AC manufactured by Kuraray Co., Ltd;) Ri = methyl group, number of carbon atoms of R 2 = 5, solubility parameter = 8 4, vaporization rate (when that of butyl acetate is 100) 10, solubility to water = 6 8 ml/1 00 ml 3-Methoxybutyl acetate Rι= methyl group, number of carbon atoms of R 2 = 4, solubility parameter = 8.5 Furthermore, these compounds can be used alone or in combination thereof The adhesive component and additive to be optionally added are dissolved or dispersed in the mixed solvent of water and a co-solvent containing the compound A to form an aqueous adhesive composition solution which can be applied with an applying means In addition to the compound A, the co-solvent can contain a water- miscible organic solvent unless the effect ofthe present invention is damaged In this case, the amount of the water-miscible organic solvent to be contained is preferably not more than 20 parts by weight based on 100 parts by weight of water The polymer to be contained in the adhesive component is not specifically limited, and a normal water-soluble or water-dispersible adhesive polymer can be used Examples thereof include polyacrylate, polyvinyl acetate, polyvinyl alcohol, polyurethane, urea, melamine, silicone, natural rubber, synthetic rubber, etc Such a polymer is used after dissolving or dispersing in a mixed solvent. Furthermore, when the polymer is contained after dispersing, it can be contained as an elastic microsphere ofthe polymer Such an elastic microsphere is described in Japanese Laid-Open Patent Publication No 2-194079 Additives such as crosslinking agents, tackifiers, plasticizers, etc can be contained in the adhesive component for the purpose of improving performances ofthe adhesive The adhesive composition can contain additives such as thickening agents, surfactants, etc unless the object ofthe present invention is damaged The thickening agent is added to control the viscosity ofthe adhesive composition An alkaline thickening type acrylic emulsion is preferred, for example, there can be used Primal ASE-60 and Primal TT-615 (manufactured by Rohm and Haas (R & H) Co ) It is preferred that the amount ofthe solid content thereof to be added is 0 2 to 3 0 parts by weight, based on 100 parts by weight ofthe adhesive polymer When the amount is smaller than 0 2 part by weight, it is liable to be difficult to obtain a coating having no thickness variation because of insufficient thickening effect On the contrary, when the amount is larger than 3 0 parts by weight, it takes a long time to dry and, therefore, the productivity is likely to become inferior The surfactant is added to adjust the surface tension ofthe adhesive composition The amount ofthe surfactant to be added is normally within a range of 0 005 to 0 5 parts by weight For example, there can be used Tryton X-100 (polyethylene glycol surfactant, manufactured by R & H Co ), Tryton GR-5M (sulfonate surfactant, manufactured by R & H Co ) and FC-129 (fluorine surfactant, manufactured by 3M Co ) In addition, defoamers, wettability improvers, leveling agents, ultraviolet absorbers, antioxidants, pigments, etc can be added to the adhesive composition The adhesive composition ofthe present invention is produced by introducing a predetermined amount of water, a compound A, an adhesive component and, if necessary, various additives into a mixing apparatus or dispersing apparatus which has hitherto been known and then uniformly dissolving or dispersing the respective materials. Examples ofthe apparatus include high-speed mixer, planetary mixer, extruder, homogenizer, sand mill, etc. When using an alkaline thickening type thickening agent, an intermediate composition wherein a material other than an alkaline reagent (e.g , ammonia, etc.) is uniformly dissolved or dispersed is formed and the intermediate composition is thickened by adding the alkaline reagent The aqueous adhesive composition ofthe present invention can be used for forming the adhesive layer of the adhesive film as described hereinafter and is also used as the solvent vaporization type adhesive The aqueous adhesive composition of the present invention is applied on a mold release surface of a substrate or a liner, followed, by drying, to form an adhesive layer The application is conducted, for example, using normal applying apparatuses such as knife coater, gravure coater, roll coater, die coater, etc The drying after application is normally conducted at 80 to 120°C for 3 to 10 minutes The coating weight (weight after drying) ofthe adhesive is 4 to 1 00 g/m 2 when the adhesive film is produced, and it can be optionally selected depending upon the uses The adhesive film of the present invention is formed by laminating an adhesive layer on one or both surfaces of a film-like substrate of materials such as polyethylene, polypropylene, polyester, polyvinyl chloride, polymethyl methacrylate, polycarbonate, paper, metal foil, ceramic thin film, etc and then sealing the adhesive layer to the substrate When the adhesive layer is not easily adhered to the substrate, the adhesive force can be improved by subjecting the surface ofthe substrate, on which the adhesive layer is laminated, to a primer treatment The thickness of the substrate is normally within a range of 5 to 500 μm, preferably 20 to 200 μm In the normal production, regarding the adhesive film having an adhesive layer obtained by applying an adhesive composition directly on a substrate, followed by drying, the surface ofthe adhesive layer formed is covered with a liner, or the surface ofthe substrate which is opposite the surface having the adhesive layer is subjected to a mold release treatment and stored after coiling in the roll form Furthermore, in the production ofthe liner having an adhesive layer obtained by applying an adhesive composition directly on a liner, followed by drying, the surface ofthe adhesive layer formed is covered with another liner, or the surface ofthe liner which is opposite the surface having the adhesive layer is subjected to a mold release treatment and stored after coiling in the roll form The mold release treatment ofthe liner is normally conducted by providing a mold release layer comprising a silicon compound on the liner EXAMPLES The following Examples and Comparative Examples further illustrate the present invention in detail Examples 1 to 3 and Comparative Examples 1 to 3 Adhesive As the adhesive, a pressure-sensitive adhesive was used This is prepared-by using a polymer ofa monomer mixture having a monomer composition of IOA B A AA (90 7 3) as an adhesive polymer and adding an epoxy compound (manufactured by Soken Kagaku Co , Ltd ) as the crosslinking agent, provided that IOA, BA and AA means isooctyl acrylate, butyl acrylate and acrylic acid, respectively Compound A 3-Methyl-3-methoxybutyl acetate (Sorfit™AC) manufactured by Kuraray Co , Ltd was used Process for preparing sample A predetermined amount of an adhesive, a thickening agent, a surfactant and a compound A as shown in Table 1 were mixed and dispersed, and the mixture was stirred and thickened using ammonia to give an adhesive composition The amount of the respective materials to be formulated are shown in Table 1 The resulting adhesive composition was applied on a silicon-treated liner (RHC1 IT, manufactured by Sanei Kagaku Co., Ltd.) so that the coating weight after drying became 10 g/m 2 , followed by drying to form an adhesive layer. The drying was conducted at 105°C for 5 minutes. This liner with the adhesive layer and the above adhesive composition were used as a sample and subjected to the following tests Detailed explanation of test method Solution fluidity A polyethylene container containing the adhesive composition was allowed to incline at an angle of 45 degrees to evaluate according to the following criteria O The solution flows X The solution does not flow Cissing Immediately after the adhesive composition was applied on the liner, the surface of the resulting coating was visually observed whether a recess, a hole or a cissing is present or not to evaluate according to the following criteria O No failure arises X A failure arises Viscosity It was measured at 23°C using a spindle SA7 according to JIS K71 17 Compression modulus The compression modulus at 20°C was measured using a viscoelasticity spectrometer RSA II manufactured by Rheometrix Co. An adhesive to be tested was molded in a cylinder having a diameter of 5 mm and a thickness of 7 mm and the cylinder was attached to a parallel plate jig. Then, the temperature dependence of the elastic modulus was measured by changing the temperature within a range between -80 to 150°C while providing a compression strain having a frequency of 1 rad/second. The test results are shown in Table 1 below. In Table 1 , ASE-60, TT-615 and FC-129 means an acrylic emulsion thickening agent available from Rohm and Haas Co , an acrylic emulsion thickening agent available from Rohm and Haas Co. and an fluorine surfactant available from Sumitomo 3M, respectively As is apparent from Table 1, the adhesive of Comparative Example 1 has a problem in fluidity ofthe solution but those of Examples 1 to 3 have a good fluidity imparted by the addition effect ofthe co-solvent. The adhesives of Comparative Examples 2 and 3 caused a failure such as cissing on the liner but those of Examples 1 to 3 could form a good coating having a improved wettability. It seems that the defects of Comparative Examples are brought about by the reason that they had relatively low viscosity and its drying speed was too fast because the compound A was not contained, and that the dispersibility ofthe adhesive component was poor and agglomeration of the adhesive component would occur Examples 1 -3 showed mild drying speed because of change of viscosity, and also shows good dispersibility ofthe adhesive components which, in turn, reduces the generation of cissing Using a liner with the adhesive prepared in Example 1 and Comparative Examples 1 to 3 and a polyvinyl chloride film having a thickness of 50 μm, the substrate was adhered with the adhesive layer by a conventional method to form an adhesive film The adhering process was conducted by placing the substrate on the liner with adhesive, and then passing between the two rollers with pressuring This adhesive film was applied to an alkyd melamine coated plate (manufactured by NTP Co., Ltd.) and, after standing in an oven at 80°C for one day, a peel adhesive force before and after curing test was measured and compared, respectively As a result, any adhesive film showed a retention of an adhesive force after test of about 70 to 85% The peel adhesive force was determined according to JIS Z 0237 (1980) wherein a peeling degree was 90° and a peeling speed was 300 mm/sec The measurement results are shown in Table 1 Furthermore, a commercially available adhesive film as the control sample was subjected to the curing test to measure the retention ofthe adhesive force. As a result, the value was 85% This commercially available film was Scotchcal™ "Model No 3650" manufactured by 3 M Co The substrate was a polyvinyl chloride film having a thickness of 50 μm and adhesive was an acrylic pressure-sensitive adhesive It could be confirmed from these results that the adhesive layer to be formed by the present invention has a stable adhesive force with time, which has a high retention of a peel adhesive force USEFULNESS OF THE INVENTION According to the present invention, there can be provided an aqueous adhesive composition, which are characterized by the following (1 ) It has a sufficient fluidity (e g , a viscosity within a suitable range, etc ) at the time of applying operation (2) It can be applied on the surface of an object having a water repellency (e g , liner etc ) in a sufficient thickness (dry thickness, for example, a weight after drying of 4 to 100 g/m 2 ) (3) It can form an adhesive layer having minimal coating failure (e g , cissing, recess, etc ) and little thickness variation by a normal applying operation (4) It can form an adhesive layer having an adhesive force which is stable with time Furthermore, an adhesive film to be formed from such a adhesive composition has the adhesive layer having minimal coating failure and thickness variation as described above, and it can exhibit an adhesive force which is stable with time Furthermore, the above adhesive composition can be applied on the surface of an object having a water repellency, uniformly and easily Therefore, an adhesive film can be produced by a process comprising the steps of applying the above adhesive composition on a mold release surface of a liner, removing a mixed solvent to provide an adhesive layer, laminating a substrate on the adhesive layer and sealing the substrate to the adhesive layer, thereby making it possible to improve the productivity Embodiments have been described The claims follow

Claims: What is claimed is 1 An aqueous adhesive composition comprising a mixed solvent of water and a co-solvent, and an adhesive component dissolved or dispersed in the mixed solvent, the co-solvent containing a compound A represented by the formula Ri— O— R 2 — OC— CHi A wherein Ri is a methyl group or an ethyl group, and R 2 is an alkylene group having 3 to 5 carbon atoms 2 The aqueous adhesive composition according to claim 1 , wherein the amount ofthe compound A to be contained is within a range of 20 to 100 parts by weight, based on 100 parts by weight of water 3 The aqueous adhesive composition according to claim 1, wherein the viscosity of the adhesive composition is within a range of 500 to 10,000 cps 4 An adhesive film comprising a film-like substrate and an adhesive layer formed on the substrate, the adhesive layer being formed by vaporizing a mixed solvent from the aqueous adhesive composition of claim 1 5 The adhesive film according to claim 4, wherein the compression modulus ofthe adhesive layer measured at 20°C is within a range of 1 x 10 4 to 10 7 dyne/cm 2 6 A process for producing an adhesive film consisting ofa film- like substrate, an adhesive layer and a liner, which are mutually laminated in this order, comprising the steps of (a) applying the aqueous adhesive composition of claim 1 on a mold release surface ofthe liner, at least one surface of which is the mold release surface, and removing a mixed solvent in the composition to form an adhesive layer; and (b) laminating the film-like substrate on the above adhesive layer to seal

Inventors: ABE HIDETOSHI, ABE, HIDETOSHI
Applicants: ABE HIDETOSHI, MINNESOTA MINING & MFG, ABE, HIDETOSHI, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1996
Main classification: C08J3
IPC codes: C08J3, C09J7, C09J11, C09J201