Pressure sensitive adhesive film with barrier layer

The present invention relates to a pressure sensitive adhesive which is substantially reducible in the adhesive force by application thereto of ultraviolet light, and a pressure sensitive adhesive film having thereon a layer of such a pressure sensitive adhesive suitable for use, for instance, in dicing a semiconductor wafer to dice.
As the use of pressure sensitive adhesive films is spreading over a variety of industries, the adhesive film in turn has come to be required to meet a diversity of requirements and to possess more extended functions depending upon individual uses.
For example, a dicing process is included in the production of integrated circuits, as is well known. In the process, a semiconductor wafer is placed and fixed on a pressure sensitive adhesive film called a dicing film, cut to small pieces or dice of a predetermined size, and then the dice are removed or picked up from the film. Therefore, it is desirable that the semiconductor wafer, for instance, a silicon wafer, is initially adhered onto the dicing film with a relatively strong adhesive force so as to be precisely diced to dice of a predetermined size, whereas after the dicing the resultant dice are loosely adhered onto the film so as to be ready removable therefrom.
For exemplification only, it is desired that the dicing film initially has an adhesive force of about 100-1000 grams/mm so that the wafer is precisely diced to dice, but after the dicing the film has a reduced adhesive force of several tens grams/25 mm or less for the ready removal of the resultant dice. However, no such pressure sensitive adhesive which has a substantially reducible adhesive force so as to be suitably and practically usable for dicing a semiconductor wafer has been known to date.
On the other hand, a photocurable adhesive is already known which is curable by the application thereto of ultraviolet light to develop the adhesive force desired. The photocurable adhesive is usually composed of a photopolymerizable oligomer, a photopolymerizable monomer, a photopolymerization initiator and other additives, and is rapidly cured by the application thereto of the ultraviolet light. It must be noted, however, that the ultraviolet light is applied to the adhesive to complete the adhesion.
The present inventors have made an intensive investigation of a pressure sensitive adhesive for use in dicing a semiconductor wafer, and found unexpectedly that a photosensitive adhesive mainly composed of a certain elastic polymer as a base resin, a photopolymerizable acrylic acid ester and a photopolymerization initiator is substantially reducible in adhesive force by the application thereto of ultraviolet light. After a further investigation based on the above finding, the inventors have found that a pressure sensitive adhesive film composed of a photopermeable base film having on one side thereof a layer of such a pressure sensitive adhesive as above mentioned is suitably usable in dicing a semiconductor wafer, since the film is capable of fixing thereon a semiconductor wafer with an adhesive force sufficient to make it possible for the wafer to be precisely diced, but loses its adhesive force by irradiation with ultraviolet light to the other side of the film so that the dice may be readily removed therefrom.
It is, therefore, an object of the invention to provide a pressure sensitive adhesive which is substantially reducible in adhesive force by the application thereto of ultraviolet light.
It is a further and important object of the invention to provide a pressure sensitive adhesive film or sheet which is substantially reducible in the adhesive force by irradiation thereto with ultraviolet light.
It is still an object of the invention to provide a dicing film for use in a dicing process in which the wafer is initially fixed on the dicing film so that the wafer is precisely diced to small pieces or dice, and after the dicing, the film is substantially reduced in the adhesive force by the application thereto of the ultraviolet light so that the resultant dice are readily removed therefrom.
The pressure sensitive adhesive reducible in the adhesive force by the application thereto of the ultraviolet light of the invention comprises:
(i) at least one elastic polymer selected from the group consisting of a polymer mainly composed of acrylic acid ester copolymers and a saturated copolyester mainly composed of dibasic carboxylic acids and dihydroxy alcohols;
(ii) an ultraviolet light polymerizable acrylic acid ester having not less than two acryloyl or methacryloyl groups in the molecule and having a molecular weight of not more than about 1000, in amounts of about 15-200 parts by weight in relation to 100 parts by weight of the elastic polymer; and
(iii) a photopolymerization initiator in amounts sufficient to induce the photopolymerization of the ultraviolet light polymerizable acrylic acid ester.
The pressure sensitive adhesive film reducible in the adhesive force by the application thereto of the ultraviolet light of the invention comprises:
(a) a base film permeable to the ultraviolet light;
(b) a layer of a pressure sensitive sensitive adhesive formed on one side of the base film, the adhesive comprising:
(i) at least one elastic polymer selected from the group consisting of a polymer comprising acrylic acid ester copolymers, and a saturated copolyester comprising a dibasic carboxylic acid and a dihydroxy alcohol;
(ii) an ultraviolet light polymerizable acrylic acid ester having not less than two acryloyl or methacryloyl groups in the molecule in amounts of about 15-200 parts by weight in relation to 100 parts by weight of the elastic polymer;
(iii) a tackifier in amounts of about 10-200 parts by weight in relation to 100 parts by weight of the elastic polymer; and
(iv) a photopolymerization initiator in a sufficient amount to induce the photopolymerization of the ultraviolet light polymerizable acrylic acid ester; and
(c) a barrier layer interposed between the base film and the layer of the adhesive, the barrier comprising a resin permeable to the ultraviolet light but impermeable both to the ultraviolet light polymerizable acrylic acid ester and the plasticizer.
Other and further objects and features of the invention will be more apparent from the following description.
The photosensitive pressure adhesive of the invention includes an elastic polymer as a main component, a photopolymerizable acrylic acid ester polymerizable by the application thereto of the ultraviolet light and a photopolymerization initiator.
The photosensitive pressure adhesive film of the invention has a base film or a supporting film which is permeable to the ultraviolet light and a layer of a pressure sensitive adhesive formed on one side of the base film in which the pressure sensitive adhesive used is such that it is specified as above.
A variety of pressure sensitive adhesives are already known, as is described, for instance, in "Adhesive Handbook," 2nd ed., edited by Japan Adhesives Association, pp. 398-414 (1980), Nikkan Kogyo Shinbunsha. A typical pressure sensitive adhesive is composed of an elastic polymer as a main component, a tackifier and a plasticizer in which the elastic polymersoluble, and when desired, additional components such as an antioxidant, a filler and a colorant. According to the invention, however, the pressure sensitive adhesive includes at least one specified polymer as the elastic polymer selected from the group consisting of a polymer mainly composed of acrylic acid ester copolymers and a saturated copolyester mainly composed of dibasic carboxylic acids and dihydroxy alcohols.
The acrylic acid ester polymer as the elastic polymer in the pressure sensitive adhesive of the invention is already well known in the art, and is normally a copolymer of acrylic acid ester components as main monomer components such as ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate to form adhesive soft segments of a low glass transition temperature in the polymer chain, and comonomer components such as vinyl acetate, acrylonitrile, styrene, methyl acrylate or methyl methacrylate to form cohesive hard segments of a high glass transition temperature in the polymer chain.
The elastic polymer may further include a third comonomer component having a functional group therein such as a carboxyl, a hydroxyl, an amide, a glycidyl or a hydroxyalkyl to improve the curability and/or the adhesion of the resultant polymer. Examples of the third comonomer are acrylic acid, methacrylic acid, itaconic acid, hydroxymethyl methacrylate, hydroxypropyl methacrylate, acryl amide or glycidyl methacrylate.
The saturated copolyester preferably usable as the elastic polymer in the invention is per se also known, as described, for instance, in "Kogyo Zairyo (Industrial Materials)," Vol. 25, No. 11, pp. 101-106 (1977), and is a copolyester composed of a saturated dibasic carboxylic acid component and a saturated dihydroxy alcohol component, i.e., a glycol component. Hence, the copolyester has a low glass transition temperature. A mixture of an aromatic dibasic carboxylic acid and an aliphatic dibasic carboxylic acid is, for example, preferably used as the dibasic carboxylic acid component, while an aliphatic and/or an alicyclic glycol is preferably used as the glycol component.
In the invention, a copolyester is preferred which is composed of a dibasic carboxylic acid component of an aromatic dibasic carboxylic acid and an aliphatic dibasic carboxylic acid in a molar ratio of the former to the latter of about 80/20 to 20/80, more preferably of about 70/30 to 50/50, and a glycol component, substantially in an equimolar ratio. In particular, terephthalic acid is preferred as the aromatic dibasic carboxylic acid, whereas sebacic acid and adipic acid are preferred as the aliphatic dibasic carboxylic acid, meanwhile ethylene glycol, 1,4-butanediol and propylene glycol are, for instance, preferred as the glycol component, for the copolyester suitable for use in the invention. However, the dibasic carboxylic acid component may be in part displaced by a tribasic carboxylic acid, and the glycol may be replaced by a trihydroxy alcohol.
Preferably the pressure sensitive adhesive according to the invention includes a tackifier therein in amounts not more than about 200 parts by weight in relation to 100 parts by weight of the elastic polymer. The tackifier usable in the adhesive of the invention is not restricted to a specified one, but any tackifier is usable which is known in the production of a conventional pressure sensitive adhesive.
As examples only, there are mentioned as such a tackifier, for instance, xylene resins, rosins, polymerized rosins, hydrogenated rosins, rosin esters, terpene resins, terpene-phenol resins, petroleum resins, coumarone resins, styrene resins, alkylphenol resins and the like. The tackifier is preferably included in the adhesive in amounts of about 10-200 parts by weight, more preferably 50-150 parts by weight, in relation to 100 parts by weight of the elastic polymer.
The use of the tackifier is especially useful when the copolyester is used as the elastic polymer in the adhesive. When the amount of the tackifier is less than about 10 parts by weight in relation to 100 parts by weight of the elastic polymer, the resultant adhesive tends to have an adhesive force which is, for example, insufficient to fix a semiconductor wafer for the precise dicing, whereas when the amount of the tackifier is more than about 200 parts by weight, the resultant adhesive is reducible in the adhesive force only to an insufficient extent so that, for example, in dicing a wafer, the resultant dice are not readily removable from the dicing film after the dicing, but also the tackifier undesirably tends to remain on the dice.
In connection with the tackiness of the adhesive, it is preferable to incorporate both the acrylic acid ester copolymer and the saturated copolyester into an adhesive composition as elastic polymer copmponents, since such an adhesive has a pronouncedly large tackiness, but has substantially no tendency of migration. This pressure sensitive adhesive film is especially suitable for industrial use in dicing.
The ultraviolet light polymerizable acrylic acid ester usable in the invention has two or more acryloyl or methacryloyl groups in the molecule and a molecular weight of not more than about 5000, preferably not more than about 1000. Therefore, the acrylic acid ester usable in the invention includes, for instance, acrylates of polyhydroxy alcohols, such as ethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate and dipentaerythritol hexaacrylate, and methacrylates of polyhydroxy alcohols, such as ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate and dipentaerythritol pentamethacrylate.
The ultraviolet light photopolymerizable acrylic acid ester is included in the pressure sensitive adhesive in amounts of about 15-200 parts by weight in relation to 100 parts by weight of the elastic polymer. When the photopolymerizable acrylic acid ester is included in amounts less than about 15 parts by weight in relation to 100 parts by weight of the elastic polymer, the resultant adhesive is not substantially reducible in the adhesive force by the application of the ultraviolet light thereto. Meanwhile when the photopolymerizable acrylic acid ester is included in amounts more than about 200 parts by weight, the adhesive undesirably tends to migrate to a substance adhered to the layer of the adhesive, although the resultant adhesive is substantially reducible in the adhesive force by the application of the ultraviolet light.
The pressure sensitive adhesive of the invention further includes a photopolymerization initiator or photosensitizer, and in addition, may include, when desired, a polymerization inhibitor. The initiator is included in the adhesive to accerelate the polymerization of the photopolymerizable acrylic acid ester, as is well known in the field of the photopolymerization. Any known initiator is usable in the invention, for instance, benzoin alkylethers such as benzoin methylether and benzoin isopropylether, aromatic ketones and aromatic hydroxy ketones such as benzoin, benzil and benzophenone.
The polymerization inhibitor may be included in the adhesive of the invention, when desired, to prevent the polymerization of the photopolymerizable acrylic acid ester induced by an energy source other than the ultraviolet light, for instance, thermal polymerization. The inhibitor usable in the invention is not specifically limited, and as an exemplification, picric acid, phenol, hydroquinone, hydroquinone monomethylether and the like are usable.
The amount of the initiator and the inhibitor used may be in accordance with the amount in the conventional photopolymerization technology, respecitively, and hence the initiator is incorporated in the adhesive in amounts of about 0.1-30 parts by weight, and the inhibitor in amounts of about 0.1-1 parts by weight, respectively, in relation to 100 parts by weight of the photopolymerizable acrylic acid ester, although not limited to these exemplified ranges.
The pressure sensitive adhesive of the invention may further contain therein a plasticizer such as a polybutene polymer and a mineral oil.
The pressure sensitive adhesive film of the invention is composed of a base film and a layer of the pressure sensitive adhesive in solid as set forth above formed on the base film. In the production of the pressure sensitive adhesive film of the invention, the pressure sensitive adhesive as stated above is applied prefeably in a form of a liquid composition onto one side of a base film, followed by drying the liquid composition to form a solid layer of the pressure sensitive adhesive on the base film.
The liquid composition may be prepared, in principle, by dissolving in an organic solvent such as an aromatic hydrocarbon, an aliphatic ketone or a mixture of these, the above mentioned elastic polymer, photopolymerizable acrylic acid ester, a photopolymerization initiator, and when needed, further additives such as a tackifier, an inhibitor, a filler, an antioxidant and a colorant, each in amounts as stated hereinbefore, respectively. As the organic solvent is preferred in particular a mixture of toluene and methyl ethyl ketone, although not limited thereto. The liquid composition contains the elastic polymer preferably in amounts of about 10-50% by weight based on the liquid composition so as to be easy in coating on a base film and drying to form a solid layer of the adhesive on the base film.
The liquid composition may be prepared in any manner which is known in a conventional adhesive. The elastic polymer and the tackifier are usually available in the form of solution in organic solvents. Therefore, it is convenient to prepare the liquid composition, for example, by admixing the solutions of the elastic polymer and the tackifier together, adding to the resultant solution the photopolymerizable acrylic acid ester and the initiator, and when neccessary, other additives such as an inhibitor, an antioxidant, afiller or an additional amount of an organic solvent.
As apparent, a liquid composition on the market which includes polyacrylic acid esters as the elastic polymer is also usable for preparing a pressure sensitive adhesive of the invention, since such a liquid resin composition is in many cases a mixture of the elastic polymer with other additives such as a tackifier and a plasticizer dissolved in an organic solvent, although some of the liquid acrylic acid ester polymer composition are found not to contain a tackifier and a plasticizer.
When the liquid resin composition on the market is used for the preparation of photopolymerizable pressure sensitive adhesive of the invention, the liquid composition is mixed with the photopolymerizable acrylic acid ester and the initiator, and when desired, together with other additional components such as a polymerization inhibitor and an organic solvent, in amounts as stated hereinbefore, depending upon the amount of the elastic polmer in the liquid composition. However, it is preferred that the photopolymerizable acrylic acid ester is admixed in amounts of about 3-60 parts by weight, preferably about 5-20 parts by weight, with 100 parts by weight of the liquid composition.
The pressure sensitive adhesive film according to the invention may be prepared by forming a layer of the pressure sensitive adhesive as set forth hereinbefore on a base film permeable to the ultraviolet light, which will be now described.
Any resin film may be usable as the base film provided that the film is permeable or transparent to the ultraviolet light as well as the film has a strength sufficient to form an adherend. The base film usable in the invention, therefore, includes films of polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chlorid-vinyl acetate copolymer, vinyl chloride-acrylic acid copolymer, polyvinylidene chloride, polyolefin such as polyethylene or polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyamide, polyimide, polyamideimide, polyester such as polyethylene terephthalate, polycarbonate and cellulose acetate.
Among the above base films, however, films of homopolymers and copolymers of vinyl chloride and vinylidene chloride, respectively, are especially preferred in the invention, since these films are soft and less expensive than the others. These films, in particular, a polyvinyl chloride film, however, contain therein a plasticizer, although greatly advantageous in prices over the other films.
A variety of such plasticizers are known, among which are, for instance, diphthalates such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, di(tricresyl) phthalate and butyl benzyl phthalate; phosphates such as tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate and cresyl diphenyl phosphate; aliphatic dicarboxylic acid diesters such as dioctyl adipate, dioctyl sebacate, dioctyl azelate and tris(2-ethylhexyl)acetyl citrate; polyester plasticizers such as polypropylene adipate and polypropylene sebacate; epoxidized plasticizers such as epoxidized soybean oils; and chlorinated plasticizers such as chlorinated paraffins and chlorinated fatty acid esters.
Furthermore, these films, in particular, a polyvinyl chloride film, are preferred as a base film since it is readily expandable. It is desired in the dicing of semiconductor wafers that the dicing film can be expanded at least in one direction by about 5-50%, preferably 10-25%, after placing and fixing a wafer on the dicing film and irradiation of the film by ultraviolet light so that the resultant dice are readily separated from the dicing film. The base films which contain plasiticizers therein as described as above are readily expandable in this way, and accordingly they are usable in preference to the other base films which contain no plasiticizers therein.
However, it has been found out by the inventors that when a layer of the pressure sensitive adhesive is formed directly on a base film which contains the plasticizer therein, the plasticizer migrates into the adhesive, but also the photopolymerizable acrylic acid ester migrates into the base film since the plasticizer has usually a good miscibility with or solubility with respect to the low molecular weight photopolymerizable acrylic acid esters used in the invention.
This bidirectional migration of the plasticizer and the photopolymerizable acrylic acid ester in the pressure sensitive adhesive film has been found to remarkably decrease the degree of the reduction in the adhesive force of the pressure sensitive adhesive by the application thereto of the ultraviolet light, but also the adhesive force of the adhesive itself has been found to gradually decrease with time.
Furthermore, depending upon the base films used, it has been observed that there often takes place a remarkable decrease in the adhesive force without the irradiation of ultraviolet light even when the base film contains no plasiticizers therein. The reason has not yet been clarified, but it is likely that the reduction in the adhesive force is caused when the photopolymerizable acrylic acid esters have affinity to the resins that form base films.
Therefore, when a resin film which contains a plasticizer is used as the base film of the pressure sensitive adhesive film, it is desired in the invention that a barrier layer to the bidirectional migration is interposed between the base film and the layer of the pressure sensitive adhesive. The barrier layer is composed of a resin, either in the form of a film or a coating, which is impermeable both to the plasticizer and the photopolymerizable acrylic acid ester but permeable to the ultraviolet light, so that the barrier layer prevents the migration of the plasticizer in the base film into the layer of the adhesive but also the migration of the photopolymerizable acrylic acid ester in the adhesive into the base film. Thus, the barrier layer retains the photopolymerizable acrylic acid ester in the layer of the adhesive as well as retains the plasticizer in the base film, thereby in particular, to retain the function of the film reducible in the adhesive force by the application thereto of the ultraviolet light after a long standing as well as to prevent the reduction in the adhesive force of the adhesive with time before the application thereto of the ultraviolet light.
As the barrier layer mentioned above, a film or a coating of a resin such as polyolefin, e.g., polyethylene or polypropylene, polyalkylene terephthalate, e.g., polyethylene terephthalate, or polymethyl methacrylate, is preferred. The barrier layer is formed, for example, by laminating a film of the resin as specified above on the base film, or by coating a melt or a solution of the barrier resin on the film. Many of the alkyd modified acrylic resins and thermosetting acrylic resins including an acid, a hydroxyl, an epoxy or an amide type thermosetting acrylic resin are also suitable for the barrier coating. However, depending upon the photopolymerizable acrylic acid ester and the plasticizer used, some of the acrylic resins are often found to be soluble therein or swellable therewith, and therefore, when an acrylic resin is used as a barrier resin, it is necessary to choose such an acrylic resin which is neither soluble in nor swellable with the photopolymerizable acrylic acid ester and the plasticizer used.
However, it will be understood that the barrier layer is not limited to those exemplified above, since any layer of a resin may function as the barrier layer if it is impermeable both to the plasticizer and the photopolymerizable acrylic acid ester, but permeable to the ultraviolet light.
According to the invention, there is provided a pressure sensitive adhesive film which has an especially useful barrier layer interposed between the base film and the layer of the pressure sensitive adhesive composition. The barrier layer comprises resins which comprises a copolymer of
(a) aminoalkyl acrylate or aminoalkyl methacrylate components, and
(b) ethylenically unsaturated monomer components.
The barrier layer may be formed by coating a solution of the copolymers in organic solvents on a base film, and then drying the solution, thereby to form a layer of the copolymers on the base film.
Such copolymers as above described are already known as disclosed in Japanese Patent Publications Nos. 38-26763 and 43-6235. The copolymers preferably usable in the invention is specifically composed of aminoalkyl acrylate or aminoalkyl methacrylate components, and ethylenically unsaturated monomer components.
The aminoalkyl acrylates or aminoalkyl methacrylates usable in the invention include, for example, acrylates such as aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, aminohexyl acrylate, aminohydroxypropyl acrylate, and methacrylates such as aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, amino-n-butyl methacrylate, aminohexyl methacrylate, or aminohydroxypropyl methacrylate. These acrylates and methacrylates may be singly or jointly included in the copolymers, and included in the copolymers usually in amounts of about 1-40% by weight, preferably in amounts of about 2-20% by weight, based on the copolymers.
Meanwhile, the ethylenically unsaturated monomers usable in the invention includes, for example, acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or 2-ethylhexyl methacrylate; vinyl esters of aliphatic carboxylic acids such as vinyl acetate or vinyl propionate, aliphatic monoolefins such as ethylene, propylene or isobutene; aromatic monoolefins such as styrene or vinyltoluene; and others including acrylonitrile, vinyl chloride or vinyl fluoride. These ethylenically unsaturated monomers also may be singly or combinedly included in the copolymers, and included in the copolymers usually in amounts of about 60-90% by weight, preferably in amounts of about 80-98% by weight, based on the copolymers.
The copolymer has a weight average molecular weight usually of about 1,000-1,000,000, preferably of 5,000-500,000, and most preferably of 5,000-50,000 so as to form effective barrier layers.
The copolymer is obtained by, for example, reacting the aminoalkyl acrylates or aminoalkyl methacrylates with the ethylenically unsaturated monomers in organic solvents such as aromatic hydrocarbons exemplified by toluene, alcohols exemplified by isopropanol, carboxylic acid esters exemplified by ethyl acetate or mixtures of these, by use of peroxides as radical polymerization initiators such as azobisisobutyronitrile, if necessary together with chain transfers such as mercaptans, in conventional manners. The copolymer is obtained usually as solutions.
The abovementioned copolymer is available usually as solutions in organic solvents. The solutions are coated on a base film and dried, to provide the barrier layer. The organic solvents used in the solutions are, for example, ketones such as acetone or methyl ethyl ketone, although the solvents are not limited thereto. The solutions preferably contain solids usually in amounts of not less than about 70% by weight, but are not specifically limited to the above exemplified. The means to apply the solutions on the base films are not specifically limited, but any means are adoptable, such as brushes, roll brushes, spray guns, flow coaters or roll coaters. The amount of the copolymer solutions coated on the base films may be usually in the range of about 1-50 g/m.sup.2.
The copolymer solutions may contain small amounts of oligomers as cross-linking agents such as epoxy resins or prepolymers of polyisocyanates usually known per se, if desired.
Further according to the invention, the pressure sensitive adhesive preferably includes either an anhydrous silica powder or a polyisocyanate or a mixture of these, which causes the reduction to a greater extent in the adhesive force of the adhesive by the application thereto of the ultraviolet light than the adhesive which contained neither the silica nor the polyisocyanate, but otherwise is the same as above.
The silica powder is incorporated into the adhesive in amounts of about 1-30 parts by weight in relation to 100 parts by weight of the elastic polymer. The use of the silica powder in amounts of less than about 1 part by weight in relation to 100 parts by weight of the elastic polymer is insufficient to cause a further extended reduction in the adhesive force by the application thereto of the ultraviolet light, compared with the same adhesive except that it contains no silica powder. However, the use of the silica powder in amounts of more than about 30 parts by weight makes the resultant liquid composition for forming a layer of the pressure sensitive adhesive layer excessively viscous to form a gel-like substance, and as a result, for instance, it makes the application of the liquid composition onto the base film difficult. The preferred amount of the silica is about 3-15 parts by weight in relation to 100 parts by weight of the elastic polymer. The silica powder used in the invention is preferably a finely divided powder, and for example, "Aerosil" by Degussa, West Germany, is suitable for use.
A polyisocyanate is also usable for causing a further extended reduction in the adhesive force of the pressure sensitive adhesive by the application thereto of the ultraviolet light when the polyisocyanate is included in the adhesive in amounts of about 1-100 parts by weight in relation to 100 parts by weight of the elastic polymer in the adhesive. When the amount of the polyisocyanate used is less than about 1 part by weight in relation to 100 parts by weight of the elastic polymer, the resultant adhesive is not substantially reduced to an increased extent, whereas when the amount of the polyisocyanate is more than about 100 parts by weight, the resultant adhesive is gradually reduced in the adhesive force with time without the application thereto of the ultraviolet light. The preferred amount of the polyisocyanate is about 3-40 parts by weight in relation to 100 parts by weight of the elastic polymer in the adhesive.
The polyisocyanate usable in the invention is not specifically limited, but a diisocyanate and a triisocyanate are preferably used. The diisocyanate usable includes, for instance, 2,4-tolylene diisocyanate, m-phenylene diisocyanate, m-xylylen diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dianisidine diisocyanate and hexamethylene diisocyanate, and the triisocyanate usable includes, for instance, trimethylolpropane-tolylene diisocyanate adduct.
A urethane prepolymer prepared by the reaction of a diisocyanate in an excess amount with a dihydroxy alcohol so as to have isocyanate groups at the terminals of the polymer is also usable as a polyisocyanate in the invention.
The combined incorporation of the silica and the polyisocyanate results in a synergetic reduction in the adhesive force of the adhesive by the application thereto of the ultraviolet light. As stated hereinbefore, the combined use of the silica and the polyisocyanate in amounts of about 1-30 parts by weight and about 1-100 parts by weight, respectively, in relation to 100 parts by weight of the elastic polymer in the adhesive is allowed in the invention. However, smaller amounts of both of the two are sufficient to bring about the substantial reduction in the adhesive force to an increased extent due to the synergy of the combined use of the two additives. When the two are used in combination, the silica and the polyisocyanate are incorporated usually in amounts of about 1-20 parts by weight, preferably about 1-15 parts by weight, and 1-50 parts by weight, preferably about 1-20 parts by weight, respectively, in relation to 100 parts by weight of the elastic polymer in the adhesive.
The pressure sensitive adhesive and the adhesive film having a layer of such a pressure sensitive adhesive on one side of the base film as fully set forth as above according to the invention is especially suitable for use where it is needed that the adhesive has initially a relatively large adhesive force and thereafter is substantially reduced in the adhesive force.
Therefore, the pressure sensitive adhesive film is suitably usable as a dicing film in dicing a semiconductor wafer, as is stated hereinbefore. That is, the pressure sensitive adhesive film of the invention has initially a relatively large adhesive force, e.g., about 100-1,000 grams/25 mm, sufficient to fix the wafer thereon so that the wafer may be diced to dice of a precise size predetermined. Then when the film is irradiated by the ultraviolet light from the other side thereof after the dicing of the wafer, the substantial reduction in the adhesive force of the film takes place, that is, the adhesive force is reduced to several grams/25 mm to several tens grams/25 mm, and as a result, the dice on the film are readily picked up therefrom.
A means and a method for applying the ultraviolet light to the pressure sensitive adhesive or the film of the invention is not specifically limited, but any means and method may be used which are known in the field of photopolymerization technology. As an exemplification only, a xenon lamp, a low pressure, a medium pressure or a high pressure mercury lamp is used as a source of the ultraviolet light, and the ultraviolet light is applied to the film for a few seconds to a few minutes from the exposed back side of the film when the reduction in the adhesive force is needed, thereby to bring about the substantial reduction in the adhesive force of the film.
The pressure sensitive adhesive of the invention may include therein no photopolymerization initiator. As will be apparent, when the adhesive includes no initiator, an electromagnetic wave other than the ultraviolet light is applied thereto so that the polymerization of the beforesaid photopolymerizable acrylic acid ester takes place in the absence of the initiator, thereby to reduce substantially the adhesive force of the adhesive. As such an electromagnetic wave, for example, the electron beam is preferred. When the film having on one side such an adhesive is used as a dicing film, the film is irradiated by the electron beam from the back of the film after the dicing of a semiconductor wafer so that the pressure sensitive adhesive is substantially reduced in the adhesive force. Then the dice is readily removed from the dicing film.
The invention will be more fully understood with reference to the following examples; however these examples are intended to illustrate the invention only, and are not to be construed as limits to the scope of the invention.

EXAMPLE 1
A liquid acrylic resin composition on the market which mainly includes polyacrylic acid esters as the elastic polymer and a tackifier was mixed with a photopolymerizable acrylic acid ester and a photopolymerization initiator to provide a liquid composition having the formation as shown in Table 1. The thus prepared liquid composition was coated on a mold-releasing paper and dried at 120.degree. C. for one minute to form a layer of pressure sensitive adhesive in solid of 10 .mu.m in thickness.
A base film of 0.1 mm in thickness and composed of 100 parts by weight of polyvinyl chloride of an average polymerization degree of about 1,300, 35 parts by weight of dioctyl dioctylphthalate and a small amount of an stabilizer was placed on and adhered to the layer of the adhesive, and then the mold-releasing paper was removed, to provide a pressure sensitive adhesive film of the invention which had on one side thereof a pressure sensitive adhesive including the photopolymerizable acrylic acid ester and the photopolymerization initiator.
The adhesive force of the pressure sensitive adhesive film was measured in a manner as follows. The film was cut to a test piece of 25 mm in width and 100 mm in length, and the test piece was placed on a stainless steel plate.
TABLE 1__________________________________________________________________________ References Examples References 1 2 1 2 3 4 5 6 7 8 9 10 3 4 5__________________________________________________________________________Formation of Adhesive.sup.1Polythick 1001S.sup.2 100 100 100 100 100 100 100 100 100 100 100Polythick 401SA.sup.3 100 100TRP-1.sup.4 100 100TMPTA.sup.5 3 6 9 9 12 12 20 40 70 12DPEHA.sup.6 9 12 10Benzoin 1 0.5 1 1 1 1 1 1 1Benzoin isopropylether 0.5 1 2 2Adhesive Force (g/25 mm)Before UV Irradiation 750 950 500 480 450 450 500 400 550 350 380 250 --.sup.7 100 50After UV Irradiation 700 900 300 205 60 20 1 2 6 0 5 2 0 120 60__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Liquid acrylic adhesive (Sanyo Kasei Kogyo K. K.) .sup.3 Liquid acrylic adhesive (Sanyo Kasei Kogyo K. K.) .sup.4 Liquid rubber adhesive (Saiden Kagaku K. K.) .sup.5 Trimethylolpropane triacrylate .sup.6 Dipentaerythritol hexaacrylate .sup.7 The adhesive was found to migrate onto the stainless steel plate.
The test piece was then pressed against the stainless steel plate by having a 3 kg roll go and return on the adheseve film five times, and the 180.degree. adhesive force was measured at a pulling rate of 300 mm/min. with a Schopper's tester.
The adhesive force of the film before the application thereto of the ultraviolet light is presented in Table 1. Then the ultraviolet light (365 m.mu., 120 W/cm) is applied to the film from the other side thereof for 7 seconds, and the adhesive force was measured, which is presented in Table 1.
The pressure sensitive adhesive film according to the invention was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light.
As a reference, a pressure sensitive adhesive film was prepared which contained no photopolymerizable acrylic acid ester, but was otherwise the same as above. The film was found to be reduced only slightly in the adhesive force by the application thereto of the ultraviolet light, as presented in Reference Examples 1 and 2 in Table 1.
For a further reference, a pressure sensitive adhesive film was prepared in the same manner as above except the use of a liquid composition on the market including rubbers as the elastic polymer in place of polyacrylic acid ester coplymers. This film, including the photopolymerizable acrylic acid ester and the initiator, was found to increase in the adhesive force by the application thereto of the ultraviolet light, as presented in Reference Examples 4 and 5.
The pressure sensitive adhesive film of Reference Example 3 contained the photopolymerizable acrylic acid ester in an excess amount, so that the adhesive was found to remain on the stainless steel plate after the irradiation of the ultraviolet light.
EXAMPLE 2
A mixture of a saturated copolyester, a tackifier, a photopolymerizable acrylic acid ester and an initiator was prepared in a mixed solvent composed of 80% by weight of toluene and 20% by weight of methyl ethyl ketone (the same in the following when a solvent is referred to), each in amounts specified in Table 2, to provide a liquid composition for a pressure sensitive adhesive.
The saturated copolyester used was a condensation product of a saturated dibasic carboxylic acid component consisting of terephthalic acid and sebacic acid in a molar ratio of the former to the latter of 70/30 and ethylene glycol component, in an equimolar ratio, and had a glass transition temperature of about 10.degree. C.
The liquid composition was coated on a mold-releasing paper, and was then dried at 120.degree. C. for one minute to form a layer of a pressure sensitive adhesive in solid of 10 .mu.m in thickness. The same polyvinyl chloride film as used in Example 1 was placed on the layer of the adhesive on the base film, and then the mold-releasing paper was separated therefrom to provide a pressure sensitive adhesive film according to the invention.
As the adhesive force of the film before and after the appication thereto of the ultraviolet light is presented in Table 2, the substantial reduction in the adhesive force took place by the appication of the ultraviolet light.
As a reference, a pressure sensitive adhesive film was prepared in the same manner as above which contained no photopolymerizable acrylic acid ester, but was otherwise the same as above. The film was found to be reduced only slightly in the adhesive force by the application thereto of the ultraviolet light, as illustrated in Reference Examples 1 to 3 in Table 2.
EXAMPLE 3
By the use of the same saturated copolyester as used in Example 2, a liquid composition was prepared which had the formation shown in Table 3. This liquid composition was coated on a mold-releasing paper, and then dried at 120.degree. C. for one minute to form a layer of a pressure sesitive adhesive in solid of 10 .mu.m in thickness.
A synthetic resin film of 0.1 mm in thickness as a base film other than polyvinyl chloride film was placed on the layer of the adhesive, and then the mold-releasing paper was separated therefrom to provide a pressure sesitive adhesive film according to the invention.
TABLE 2__________________________________________________________________________ Examples References 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3__________________________________________________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30Xylene resin 30 40 40 40 60 20 25 20 10 5 5 5 5 20 40 5Other tackifiers.sup.2 10 15 15 15 15 15Solvent 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70TMPTA.sup.3 10DPEHA.sup.4 20 25 30 30 20 20TMPTMA.sup.5 10 10 20 12 30 20Benzoin 2 2Benzoin isopropylether 2 2 2 4 4 6 6 6 4 4 4Adsesive Force (g/25 mm)Before UV Irradiation 525 450 610 600 750 670 630 515 550 650 350 300 290 450 750 800After UV Irradiation 90 100 85 100 94 86 60 35 45 50 95 80 88 400 700 700__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Synthetic hydrocarbon oil in Example 9, terpenephenol resin in Exmple 10, aliphatic petroleum resin in Example 11, styrene resin in Example 12, aliphatic petroleum resin in Example 13, and terpenephenol resin in Reference 3. .sup.3 Trimethylolpropane triacrylate .sup.4 Dipentaerythritol hexaacrylate .sup.5 Trimethylolpropane trimethacrylate
TABLE 3______________________________________ Examples 1 2 3 4______________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30Xylene resin 30 20 30 20Solvent 70 70 70 70TMPTA.sup.2 30DPEHA.sup.3 30 30 30Benzoin isopropylether 4 4 6 6Base Film.sup.4 PET PP PA PMMAAdsesive Force (g/25 mm)Before UV Irradiation 450 400 300 250After UV Irradiation 45 40 33 48______________________________________ Notes: .sup.1 Parts by weight .sup.2 Trimethylolpropane triacrylate .sup.3 Dipentaerythritol hexaacrylate .sup.4 PET: Polyethylene terephthalate PP: Polypropylene PA: Polyamide, PMMA: Polymethyl methacrylate
As the adhesive force of the film before and after the appication thereto of the ultraviolet light is presented in Table 3, the substantial reduction in the adhesive force was found to take place by the application of the ultraviolet light.
EXAMPLE 4
A mixture of the same saturated copolyester as used in Example 2, a tackifier, a photopolymerizable acrylic acid ester, an initiator and the same solvent as used in Example 2, each in amounts specified in Table 4, was prepared to provide a liquid composition for forming on the base film a layer of the pressure sensitive adhesive. The formation of the liquid composition is presented in Table 4. The liquid composition was coated on a mold-releasing paper, and was then dried at 120.degree. C. for one minute to form a layer of a pressure sensitive adhesive in solid of 10 .mu.m in thickness.
A polyvinyl chloride film of 0.1 mm in thickness was prepared by a calendering process by the use of a composition composed of 100 parts by weight of polyvinyl chloride of an average polymerization degree of about 1300, 35 parts by weight of a plasticizer, either dioctyl phthalate or a polyester plasticizer, and a small amount of a stabilizer.
A barrier layer was then formed which was composed of a resin as shown in Table 4 on the polyvinyl chloride film. The polyvinyl chloride film was placed on the layer of the adhesive so that the barrier layer was in contact with the adhesive, to provide a pressure sensitive adhesive film of the invention having the barrier layer interposed between the base film and the layer of the adhesive.
After standing at a predetermined temperature for a predetermined period of time, the mold-releasing paper was removed, and the adhesive force of the film was measured. Then the film was irradiated by the ultraviolet light from the back side thereof in the same manner as in Example 1, and the adhesive force was measured. The change in the adhesive force before and after the irradiation of the ultraviolet light is presented in Table 4.
The pressure sensitive adhesive film of the invention was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing.
As a reference, a pressure sensitive adhesive film was prepared which contained no barrier layer, but was otherwise the same as above. As presented in Reference Example 1 in Table 4, the film of reference, immediately after the preparation, was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light, but after a long standing the film was found to have a tendency of being reduced irregularly in the adhesive force with time without the application thereto of the ultraviolet light.
TABLE 4__________________________________________________________________________ Examples References 1 2 3 4 1 2__________________________________________________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30 30 30Xylene resin 20 20 15 15 20 20Solvent 70 70 70 70 70 70TMPTA.sup.2 30 30DPEHA.sup.3 30 20 30Benzoin isopropylether 6 6 6 6 6Barrier Layer.sup.4 Ac Ac PP PE None NoneAdsesive Force (g/25 mm)InitialBefore UV Irradiation 510 470 350 300 560 450After UV Irradiation 62 40 56 45 35 400After standing at 80.degree. C. for 1 dayBefore UV Irradiation 530 435 300 280 20After UV Irradiation 50 42 50 55 100After standing at 80.degree. C. for 3 daysBefore UV Irradiation 450 450 310 285 0After UV Irradiation 52 45 40 38 25After standing at 80.degree. C. for 5 daysBefore UV Irradiation 480 425 290 275After UV Irradiation 38 50 45 40After standing at normal temperaturefor 1 monthBefore UV Irradiation 500 400 300 280 325After UV Irradiation 55 45 48 56 25After standing at normal temperaturefor 3 monthsBefore UV Irradiation 450 420 310 250 0After UV Irradiation 45 50 42 32 15__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Trimethylolpropane triacrylate .sup.3 Dipentaerythritol hexaacrylate .sup.4 Ac: Coating of modified acrylic resin PP: Polypropylene film PE: Polyethylene film
Further, the film of reference was often found to increase in the adhesive force by the application thereto of the ultraviolet light after a long standing, contrary to the film of the invention.
As a further reference, a pressure sensitive adhesive film was prepared which contained no photopolymerizable acrylic acid ester, but was otherwise the same as above. This film was found to be substantially unchanged in the adhesive force by the application thereto of the ultraviolet light even immediately after the preparation.
EXAMPLE 5
A liquid acrylic resin composition on the market (Polythick 610SA, Sanyo Kasei Kogyo K. K.) including polyacrylic acid ester copolymers in amounts of about 40% by weight based on the composition as the elastic polymer was mixed with a photopolymerizable acrylic acid ester and an initiator, each in amounts specified in Table 5, and then the resulting liquid composition was coated on a mold-releasing paper, dried at 120.degree. C. for one minute to form a layer of a pressure sensitive adhesive in solid of 10 .mu.m in thickness.
In the same manner as in Example 4, a barrier layer was formed on the same polyvinyl chloride film as used in Example 4, and a pressure sensitive adhesive film having the barrier layer between the base film and the layer of the adhesive was prepared.
The pressure sensitive adhesive film of the invention was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing, as illustrated in Table 5.
As a reference, a pressure sensitive adhesive film was prepared which contained no photopolymerizable acrylic acid ester, but was otherwise the same as above. The film was found to be substantially unchanged in the adhesive force by the application thereto of the ultraviolet light even immediately after the preparation, as illustrated in Reference Example 1 in Table 5.
EXAMPLE 6
A mixture of the same saturated copolyester as used in Example 2, a tackifier, a photopolymerizable acrylic acid ester, an initiator, the same solvent as used in Example 2 and anhydrous silica powder ("Aerosil" (Trademark), Degussa, West Germany, the same in the following), each in amounts specified in Table 6, was prepared to provide a liquid composition having the formation as shown in Table 6. The liquid composition was coated on a mold-releasing paper, and then was dried at 120.degree. C. for one minute to form a layer of a pressure sensitive adhesive in solid of 10 .mu.m in thickness.
TABLE 5______________________________________ Examples Reference 1 2 3 1______________________________________Formation of Adhesive.sup.(1)Liquid acrylic adhesive 100 100 100 100TMPTA.sup.(2) 30 20DPEHA.sup.(3) 30Benzoin isopropylether 6 6 6Barrier Layer.sup.(4) Ac Ac Ac AcAdsesive Force (g/25 mm)InitialBefore UV Irradiation 690 700 720 710After UV Irradiation 58 68 50 690After standing at 80.degree. C. for 1dayBefore UV Irradiation 650 700 710After UV Irradiation 54 60 50After standing at 80.degree. C. for 3daysBefore UV Irradiation 700 720 600After UV Irradiation 56 62 48After standing at 80.degree. C. for 5daysBefore UV Irradiation 650 690 650After UV Irradiation 60 68 52After standing at normal temper-ature for 1 monthBefore UV Irradiation 660 650 620After UV Irradiation 60 70 65After standing at normal temper-ature for 3 monthsBefore UV Irradiation 620 680 600After UV Irradiation 54 58 60______________________________________ Notes: .sup.(1) Parts by weight .sup.(2) Trimethylolpropane triacrylate .sup.(3) Dipentaerythritol hexaacrylate .sup.(4) Ac: Coating of modified acrylic resin
TABLE 6__________________________________________________________________________ Examples References 1 2 3 4 5 1 2__________________________________________________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30 30 30 30Xylene resin 15 15 15 15 15 15 15Solvent 70 70 70 70 70 70 70TMPTA.sup.2 20 20 20 30 20 30DPEHA.sup.3 30Benzoin 6 6 6 6Benzoin isopropylether 6 6 6Silica.sup.4 1 3 5 3 3 0 0Adsesive Force (g/25 mm)InitialBefore UV Irradiation 530 480 610 300 525 470 520After UV Irradiation 40 25 20 45 42 75 60After standing at 80.degree. C. for 1 dayBefore UV Irradiation 525 480 570 280 500 490 515After UV Irradiation 38 30 18 55 34 80 58After standing at 80.degree. C. for 3 daysBefore UV Irradiation 535 510 550 285 495 500 500After UV Irradiation 35 30 25 38 30 78 70After standing at 80.degree. C. for 5 daysBefore UV Irradiation 540 450 545 275 500 485 524After UV Irradiation 35 28 20 40 32 68 66After standing at normal temperaturefor 1 monthBefore UV Irradiation 540 500 580 280 520 500 510After UV Irradiation 35 35 30 56 38 70 60After standing at normal temperaturefor 3 monthsBefore UV Irradiation 500 470 550 250 525 492 498After UV Irradiation 33 20 25 32 35 68 72__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Trimethylolpropane triacrylate .sup.3 Dipentaerythritol hexaacrylate .sup.4 "Aerosil," Degussa, West Germany
A barrier layer was formed on the same polyvinyl chloride film as used in Example 4 by coating a solution of modified acrylic resin on the market followed by drying, and the polyvinyl chloride film was then placed on the layer of the adhesive so that the barrier layer was in contact with the adhesive, to provide a pressure sensitive adhesive film of the invention having the barrier layer interposed between the base film and the layer of the adhesive.
After standing at a predetermined temperature for a predetermined period of time, the mold-releasing paper was removed, and the adhesive force of the film was measured. Then the film was irradiated by the ultraviolet light from the back side thereof in the same manner as in Example 1, followed by the measurement of the adhesive force. The change in the adhesive force is presented in Table 6.
As a reference, a pressure sensitive adhesive film was prepared which contained no silica powder but was otherwise the same as above.
First the film containing the silica powder was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing. Second the film containing the silica powder was found to be reduced in the adhesive force to a greater extent than the film containing no silica powder therein, but was otherwise the same, as apparent from the comparison with Reference Examples 1 and 2 in Table 6.
However, it is to be noted that the pressure sensitive adhesive films of Reference Examples 1 and 2 are still within the scope of the invention.
EXAMPLE 7
The same liquid acrylic resin composition as used in Example 5 was mixed with a photopolymerizable acrylic acid ester, an initiator and the same anhydrous silica powder used in Example 6, each in amounts specified in Table 7, to provide a liquid composition having the formation as shown in Table 7. The liquid composition was coated on a mold-releasing paper, and then was dried at 120.degree. C. for one minute to form a layer of a pressure sensitive adhesive in solid of 10 .mu.m in thickness.
A barrier layer was then formed in the same manner as in Example 6 on the same polyvinyl chloride film as used in Example 4, and the polyvinyl chloride film was then placed on the layer of the adhesive, to provide a pressure sensitive adhesive of the invention having the barrier layer between the base film and the layer of the adhesive.
The film containing the silica powder was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing.
TABLE 7______________________________________ Examples 1 2______________________________________Formation of Adhesive.sup.1Liquid acrylic adhesive 100 100DPEHA.sup.2 30 30Benzoin isopropylether 6 6Silica.sup.3 5 10Adsesive Force (g/25 mm)InitialBefore UV Irradiation 700 800After UV Irradiation 30 28After standing at 80.degree. C. for 1 dayBefore UV Irradiation 720 780After UV Irradiation 25 25After standing at 80.degree. C. for 3 daysBefore UV Irradiation 700 750After UV Irradiation 28 25After standing at 80.degree. C. for 5 daysBefore UV Irradiation 690 700After UV Irradiation 30 20After standing at normal temperaturefor 1 monthBefore UV Irradiation 685 725After UV IrradiationAfter standing at normal temperaturefor 3 monthsBefore UV Irradiation 654 700After UV Irradiation 26 24______________________________________ Notes: .sup.1 Parts by weight .sup.2 Dipentaerythritol hexaacrylate .sup.3 "Aerosil," Degussa, West Germany
EXAMPLE 8
In the same manner as in Example 6 except the use of a polyisocyanate in place of the silica powder, a pressure sensitive adhesive film having the same barrier coating of modified acrylic resin as the beforementioned was prepared. The formation of the liquid composition used for forming the layer of the pressure sensitive adhesive is shown in Table 8.
As a reference, a pressure sensitive adhesive film was prepared in the same manner as in Example 6 except that the film contained no polyisocyanate.
The film containing the polyisocyanate according to the invention was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing, but also was found to be reduced in the adhesive force to a greater extent than the film containing no polyisocyanate therein, as illustrated in comparison with Reference Examples 1 and 2 in Table 8.
EXAMPLE 9
The same liquid acrylic resin composition as used in Exaple 5 was mixed with a photopolymerizable acrylic acid ester, an initiator and a polyisocyanate, each in amounts specified in Table 9, to provide a liquid composition having the formation as shown in Table 9.
By the use of the liquid composition thus prepared, a pressure sensitive adhesive film was prepared in the same manner as in Example 6 having the same barrier coating of modified acrylic resin as beforementioned between the base film and the pressure sensitive adhesive.
TABLE 8__________________________________________________________________________ Examples References 1 2 3 4 5 1 2__________________________________________________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30 30 30 30Xylene resin 20 20 20 20 15 15 25Solvent 70 70 70 70 70 70 70TMPTA.sup.2 20 20DPEHA.sup.3 30 30 30 30 30Benzoin 6Benzoin isopropylether 6 6 6 4 6 4Polyisocyanate.sup.4 2 5 10 20 5 0 0Adsesive Force (g/25 mm)InitialBefore UV Irradiation 500 495 350 350 550 525 525After UV Irradiation 35 32 25 18 30 60 85After standing at 80.degree. C. for 1 dayBefore UV Irradiation 480 510 300 250 500 515 530After UV Irradiation 40 30 28 15 45 55 78After standing at 80.degree. C. for 3 daysBefore UV Irradiation 520 500 325 200 480 500 550After UV Irradiation 32 28 25 20 40 60 80After standing at 80.degree. C. for 5 daysBefore UV Irradiation 490 515 350 200 490 505 525After UV Irradiation 20 26 24 12 35 62 75After standing at normal temperaturefor 1 monthBefore UV Irradiation 490 500 392 300 510 525 530After UV Irradiation 40 30 28 20 38 55 80After standing at normal temperaturefor 3 monthsBefore UV Irradiation 510 510 350 200 500 510 530After UV Irradiation 38 32 30 16 36 58 70__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Trimethylolpropane triacrylate .sup.3 Dipentaerythritol hexaacrylate .sup.4 Triisocyanate "Sumidule," Sumitomo Kagaku Kogyo K. K.
TABLE 9______________________________________ Examples 1 2______________________________________Formation of Adhesive.sup.(1)Liquid acrylic adhesive 100 100DPEHA.sup.(2) 30 30Benzoin isopropylether 6 6Polyisocyanate.sup.(3) 5 10Adsesive Force (g/25 mm)InitialBefore UV Irradiation 620 670After UV Irradiation 35 25After standing at 80.degree. C. for 1 dayBefore UV Irradiation 570 580After UV Irradiation 28 14After standing at 80.degree. C. for 3 daysBefore UV Irradiation 590 610After UV Irradiation 30 20After standing at 80.degree. C. for 5 daysBefore UV Irradiation 600 595After UV Irradiation 30 18After standing at normal temperaturefor 1 monthBefore UV Irradiation 600 650After UV Irradiation 30 20After standing at normal temperaturefor 3 monthsBefore UV Irradiation 570 580After UV Irradiation 28 22______________________________________ Notes: .sup.(1) Parts by weight .sup.(2) Dipentaerythritol hexaacrylate .sup.(3) Triisocyanate "Sumidule," Sumitomo Kagaku Kogyo K.K.
The film containing the polyisocyanate was found to be substantially reduced in the adhesive force by the application thereto of the ultraviolet light even after a long standing, as illustrated in Table 9.
EXAMPLE 10
In the same manner as in Example 6 except the combined use of silica powder and the polyisocyanate, a pressure sensitive adhesive film having the same barrier coating of modified acrylic resin as beforementioned was prepared. The formation of the liquid composition used is shown in Table 10.
As a reference, a pressure sensitive adhesive film was prepared which contained only one of silica powder and the polyisocyanate.
The film containing both the polyisocyanate and the silica was found to be reduced in the adhesive force to a greater extend by the application thereto of the ultraviolet light than the film containing only one of the polyisocyanate and the silica, as illustrated in comparison with Reference Examples 1 and 2 in Table 10.
However, the pressure sensitive adhesive films of Reference Examples 1 and 2 are still greater in the degree of reduction in the adhesive force by the application thereto of the ultraviolet light than the films of Reference Examples 3 and 4 which contained neither the silica nor the polyisocyanate.
TABLE 10__________________________________________________________________________ Examples References 1 2 3 4 5 1 2 3 4__________________________________________________________________________Formation of Adhesive.sup.1Saturated copolyester 30 30 30 30 30 30 30 30 30Xylene resin 15 20 30 30 20 20 15 20 15Solvent 70 70 70 70 70 70 70 70 70TMPTA.sup.2 30 20DPEHA.sup.3 30 30 30 30 30 30 30Benzoin 6 4Benzoin isopropylether 4 6 6 6 6 6 6Polyisocyanate.sup.4 2 3 3 2 2 5 0 0 0Silica.sup.5 2 5 5 5 2 0 3 0 0Adsesive Force (g/25 mm)InitialBefore UV Irradiation 492 550 480 510 610 495 525 510 350After UV Irradiation 8 6 5 10 20 32 42 62 56After standing at 80.degree. C. for 1 dayBefore UV Irradiation 510 545 450 525 600 510 500 530 300After UV Irradiation 10 14 4 8 18 30 34 50 50After standing at 80.degree. C. for 3 daysBefore UV Irradiation 460 500 465 514 570 500 495 450 310After UV Irradiation 4 4 10 12 12 28 30 52 40After standing at 80.degree. C. for 5 daysBefore UV Irradiation 500 525 485 520 550 515 500 485 290After UV Irradiation 2 2 8 10 14 26 32 38 45After standing at normal temperaturefor 1 monthBefore UV Irradiation 472 550 480 500 540 500 520 500 300After UV Irradiation 10 5 4 13 18 30 38 55 48After standing at normal temperaturefor 3 monthsBefore UV Irradiation 514 500 470 498 520 510 525 450 310After UV Irradiation 17 14 6 10 13 32 35 45 42__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Trimethylolpropane triacrylate .sup.3 Dipentaerythritol hexaacrylate .sup.4 Triisocyanate "Sumidule," Sumitomo Kagaku Kogyo K. K. .sup.5 "Aerosil," Degussa, West Germany
It is also to be noted that these films of Reference Examples 1 to 4 are all substantially reducible in the adhesive by the ultraviolet irradiation and are within the scope of the present invention.
EXAMPLE 11
the same acrylic liquid composition for a pressure sensitive adhesive as used in Exaple 5 was mixed with a photopolymerizable acrylic acid ester, an initiator, the polyisocyanate and the silica powder, each in amounts specified in Table 11, to provide a liquid composition for the pressure sensitive adhesive. The formation of the liquid composition is shown in Table 11.
By the use of the liquid composition thus prepared, a pressure sensitive adhesive film was prepared in the same manner as in Example 6 having the same barrier coating of modified acrylic resin.
The film containing the polyisocyanate and the silica powder was found to be rduced in the adhesive force to a greater extent than the film containing only one of the polyisocyanate and the silica powder, as illustrated in comparison with Reference Examples 1 and 2 in Table 11.
TABLE 11__________________________________________________________________________ Examples References 1 2 3 4 5 1 2 3__________________________________________________________________________Formation of Adhesive.sup.1Liquid acrylic adhesive 100 100 100 100 100 100 100 100DPEHA.sup.2 20 30 30 30 20 30 30 30Benzoin isopropylether 6 6 6 6 6 6 6 6Polyisocyanate.sup.3 1 2 3 5 10 5 0 0Silica.sup.4 2 2 5 3 2 0 3 0Adsesive Force (g/25 mm)InitialBefore UV Irradiation 700 600 605 620 700 620 600 510After UV Irradiation 20 8 6 6 12 35 50 70After standing at 80.degree. C. for 1 dayBefore UV Irradiation 680 625 630 620 600 570 588 500After UV Irradiation 18 10 4 6 2 28 42 68After standing at 80.degree. C. for 3 daysBefore UV Irradiation 720 650 610 650 549 590 602 508After UV Irradiation 12 4 4 4 12 30 38 75After standing at 80.degree. C. for 5 daysBefore UV Irradiation 800 700 600 600 550 600 598 512After UV Irradiation 18 4 12 12 4 30 40 78After standing at normal temperaturefor 1 monthBefore UV Irradiation 650 650 625 600 680 600 590 520After UV Irradiation 22 15 5 12 4 30 42 80After standing at normal temperaturefor 3 monthsBefore UV Irradiation 600 595 580 570 600 570 600 500After UV Irradiation 20 6 4 4 2 28 44 82__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Dipentaerythritol hexaacrylate .sup.3 Triisocyanate "Sumidule," Sumitomo Kagaku Kogyo K. K. .sup.4 "Aerosil," Degussa, West Germany
The films of Examples 1 and 2 are, however, still greater in the degree of reduction in the adhesive force when being irradiated by the ultraviolet light than the film of Reference Example 3, and are in accordance with the invention. The film of Example 3 is also a pressure sensitive adhesive film of the invention.
EXAMPLE 12
The same liquid acrylic acid ester copolymer compostion as used in Example 5 and the same saturated copolyester as used in Example 2 were both incorporated into a liquid composition together with a solvent, a tackifier, dipentaerythritol hexaacrylate, benzoin isopropylether, silica and a polyisocyanate. The formation of the resultant liquid composition is presented in Table 12.
By the use of the liquid composition, a pressure sensitive adhesive film was prepared in the same manner as in Example 6 having the same barrier coating of modified acrylic resin as beforesaid between the polyvinyl chloride base film and the pressure sensitive adhesive.
The tackiness and adhesive migration were measured as follows.
Tackiness:
A pressure sensitive adhesive film was fixed on a horizontal plane at 21.degree. C. with the layer of adhesive exposed, and a stainless steel plate was supported on the plane so that the plate intersected at the lower end with the plane at an angle of 30.degree..
TABLE 12__________________________________________________________________________ Examples References 1 2 3 4 1 2__________________________________________________________________________Formation of Adhesive.sup.1Polythick 610SA.sup.2 20 40 60 80Saturated coplyester 24 18 12 6 30 30Xylene resin 15 15 15 15 15 15Solvent 56 42 28 14 70 70DPEHA.sup.3 30 30 30 30 30 30Benzoin isopropyl ether 6 6 6 6 6 6Silica.sup.4 4 4 4 6 2 4Polyisocyanate.sup.5 7 7 7 9 5 7Adsesive Force (g/25 mm)InitialBefore UV Irradiation 500 610 650 625 620 585After UV Irradiation 18 17 14 20 12 10After standing at 80.degree. C. for 7 daysBefore UV Irradiation 520 550 650 600 600 550After UV Irradiation 15 13 12 18 13 12After standing at normal temperaturefor 3 monthsBefore UV Irradiation 550 590 620 630 625 590After UV Irradiation 12 15 18 20 10Tackiness at 21.degree. C. (cm) 1.2 1.0 0.5 0.7 6.5 5.3Initial (Before UV Irradiation)Adhesive Migration (21.degree. C.).sup.6After 1 day 1 1 1 1 4 3After 4 days 1 1 1 1 5 5After 7 days 1 1 2 1 5 5__________________________________________________________________________ Notes: .sup.1 Parts by weight .sup.2 Liquid acrylic adhesive (Sanyo Kasei Kogyo K. K. .sup.3 Dipentaerythritol hexaacrylate .sup.4 "Aerosil," Degussa, West Germany .sup.5 Triisocyanate "Sumidule," Sumitomo Kagaku Kogyo K. K. .sup.6 Five grade estimation; the more the figure, the more the migration
A stainless steel ball of 8.0 mm in diameter and 2.0 g in weight was placed on the steel plate at a position 50 mm apart from the lower end of the plate, and then was allowed to roll down on the slope. The tackiness was estimated in terms of the distance between the lower end of the steel plate and the position at which the ball stopped.
Adhesive migration:
A pressure sensitive adhesive film of 25 mm in width and 100 mm in length was adhered onto a stainless steel plate and was left standing at a predetermined period of time at 21.degree. C. Thereafter the film was separated from the plate at a pulling rate of 300 mm/min. by a Schopper's tester, and the plate was examined whether the adhesive was migrated thereonto.
The above pressure sensitive adhesive film was found to have a pronouncedly large tackiness, but substantially no adhesive was found on the plate even after a long standing of seven days, as shown in Table 12.
As a reference example, an adhesive film was prepared which included only the saturated copolyester as an elastic polymer. The formation of the liquid composition used is presented in Table 12.
The reference adhesive film was found to have a smaller tackiness, and at the same time the adhesive was found to migrate onto the plate. However, it is to be noted that the adhesive films of Reference Examples 1 and 2 are in accordance with the invention.
EXAMPLE 13
Pressure sensitive adhesive compositions I, II and III which had the formulations as shown in Table 13 were coated, repectively, on a mold-releasing paper, and then dried at 120.degree. C. for one minute to form a solid layer of a pressure sensitive adhesive of 10 .mu.m in thickness.
When polyacrylic esters or copolymers of acrylic esters were used as elastic polymers, the pressure sensitive adhesive compositions were prepared by mixing the marketed acrylic adhesiveve solutions with photopolymerizable acrylic esters, photopolymerization initiator and other additives. When saturated copolyesters were used as elastic polymers, the saturated copolyester used was a condensation product of a saturated dibasic carboxylic acid component consisting of terephthalic acid and sebacic acid in a molar ratio of the former to the latter of 70/30 and ethylene glycol component, in an equimolar ratio, and had a glass transition temperature of about 10.degree. C.
TABLE 13______________________________________ Adhesive Compositions.sup.(1) I II III______________________________________Liquid acrylic resin composition.sup.(2) 100 20Saturated copolyester 24 30Tackifier (Xylene resin) 15 10Solvent 56 70Photopolymerizable acrylic esterDPEHA.sup.(3) 30 30TMPTA.sup.(4) 30Benzoin isopropyl ether 6 6 6Polyisocyanate.sup.(5) 7 7 5Anhydrous silica.sup.(6) 2 4 4______________________________________ Notes: .sup.(1) Parts by weight .sup.(2) Polythick 610SA (Sanyo Kasei Kogyo K.K.) .sup.(3) Dipentaerythritol hexaacrylate .sup.(4) Trimethylolpropane triacrylate .sup.(5) Triisocyanate "Sumidule", Sumitomo Kagaku Kogyo K.K. .sup.(6) "Aerosil" Degussa, West Germany
Then the solutions of copolymers which had monomer compositions as shown in Table 14 and had solids in amounts of 30% by weight were coated on base films of 0.1 mm in thickness and composed of 100 parts by weight of polyvinyl chloride of an average polymerization degree of about 1300, 35 parts by weight of dioctyl phthalate or polyester plasticizers and a small amount of an stabilizer, and dried at 120.degree. C. for 30 seconds, to form barrier layers on the base films. Thereafter, the films were placed on the mold releasing paper so that the barrier layers and adhesive layers contact and adhere to each other, thereby to provide pressure sensitive adhesive films of the invention. The combination of the pressure sensitive adhesive compositions and the barrier layers used are shown in Table 16.
TABLE 14______________________________________Monomer Compositions of Copolymers Copolymers(% by weight) 1 2 3______________________________________Aminoethyl acrylate 5Aminoethyl methacrylate 15 15Methyl methacrylate 85 75 50Butyl acrylate 10 45Ethyl methacrylate 4______________________________________
As described hereinbefore, it is necessary that the barrier layers are not dissolvable or soluble in the photopolymerizable acrylic acid esters contained in the pressure sensitive adhesive compositions and in the plasticizers contained in the base films. Table 15 shows solubilities of the copolymers used as the barrier layers according to the invention and other polymers in the photopolymerizable acrylic esters and plasticizers. It is understood that the copolymers used as the barrier layers according to the invention are soluble neither in the law molecular weight photopolymerizable acrylic acid esters not in the plasticizers after immersion for three days therein.
The solubilities of the barrier layers in the photopolymerizable acrylic acid esters and plasticizers were evaluated as follows. Films of the copolymers of about 50 .mu.m in thickness and having the monomer compositions as shown in Table 14 were prepared, and then the films were immersed in 100 ml of the liquid photopolymerizable acrylic acid esters and plasticers, respectively, at themperatures of 80.degree. C. and the films were visually examined.
As references, pressure sensitive adhesive films were prepared which contained no barrier layers as described before, but otherwise was the same as above. The combination of the pressure sensitive adhesive compositions and the barrier layers used are shown in Table 16.
For further references, pressure sensitive adhesive films were prepared in the same manner as above except that the pressure sensitive adhesive layers contained neither silica powders nor polyisocyanates. The formations of the adhesive compositions were shown in Table 17.
TABLE 15__________________________________________________________________________ Ultraviolet light Polymerizable Acrylic Acid Esters.sup.4 * DOP.sup.3 * DPEHA TMPTA TMPTMA After Immersion For 1 day 3 days 1 day 3 days 1 day 3 days 1 day 3 days__________________________________________________________________________Copolymer 1 O O O O O O O OCopolymer 2 O O O O O .DELTA. O OCopolymer 3 O O O O O O O OPolyester polyurethane resin.sup.1 a O O x x x x x xMethacrylic resin.sup.2 b O O x x x x x x__________________________________________________________________________ Notes: .sup.1 Honeycemen 991 by Honey Kasei K. K. (Japan) .sup.2 Honeytan 638 by Honey Kasei K. K. (Japan) .sup.3 Dioctyl phthalate .sup.4 DPEHA = Dipentaerythritol hexaacrylate; TMPTA = Trimethylolpropane triacrylate; TMPTMA = Trimethylolpropane trimethacrylate. *O: no change occured; .DELTA.: swelled; x: dissolved.
TABLE 16__________________________________________________________________________ Examples* References* 1 2 3 4 5 1 2 3 4__________________________________________________________________________Adhesive Compositions.sup.1I OII OIII O O O O O O OBarrier Layers.sup.21 O2 O O O3 OOthers.sup.3 Oa ObAdsesive Force (g/25 mm)InitialBefore UV Irradiation 650 420 380 395 387 412 398 550 600After UV Irradiation 28 24 15 17 21 31 39 45 20After standing at 80.degree. C. for 1 dayBefore UV Irradiation 720 450 350 375 370 30 45 200 370After UV Irradiation 22 17 21 18 30 120 92 350 500After standing at 80.degree. C. for 3 daysBefore UV Irradiation 680 390 300 412 372 0 10 300 250After UV Irradiation 15 10 20 16 72 15 25 450 500After standing at 80.degree. C. for 5 daysBefore UV Irradiation 650 415 310 400 295 -- -- -- --After UV Irradiation 18 13 15 13 100 -- -- -- --After standing at normal temperaturefor 1 monthBefore UV Irradiation 625 465 395 405 395 305 293 500 550After UV Irradiation 12 15 17 12 17 78 52 50 50After standing at normal temperaturefor 3 monthsBefore UV Irradiation 570 405 370 402 352 0 5 250 200After UV Irradiation 13 14 13 12 51 20 13 500 550__________________________________________________________________________ Notes: .sup.1 Compositions shown in Table 1. .sup.2 Compositions of copolymers shown in Table 2. .sup.3 a and b represent the polyester polyurethane resin and methacrylic resin respectively in Table 3. *Adhesive compositions and barriers marked by O were used.
TABLE 17______________________________________ Examples References 6 7 8 5 6______________________________________Formation of Adhesive.sup.1Polythick 610SA.sup.2 100 20Saturated copolyester 30 30 24 30Xylene resin 10 10 15 10Solvent.sup.3 70 70 56 10DPEHA.sup.3 30 30 30 30 30Benzoin isopropylester 6 6 6 6 6Polyisicyanate.sup.4 7 5Silica.sup.5 4Adhesive Force (g/25 mm)InitialBefore UV Irradiation 625 435 423 455 405After UV Irradiation 42 51 72 120 98After standing at 80.degree. C. for 1 dayBefore UV Irradiation 620 400 431 472 390After UV Irradiation 35 50 80 112 100After standing at 80.degree. C.for 3 daysBefore UV Irradiation 623 395 425 437 375After UV Irradiation 45 47 78 109 102After standing at 80.degree. C.for 5 daysBefore UV Irradiation 651 380 390 428 385After UV Irradiation 48 52 78 112 100After standing at normaltemperature for 1 monthBefore UV Irradiation 675 412 398 452 412After UV Irradiation 37 55 69 113 195After standing at normaltemperature for 3 monthsBefore UV Irradiation 663 395 415 443 402After UV Irradiation 35 48 72 115 101______________________________________ Notes: .sup.1 Parts by weight .sup.2 Liquid acrylic adhesive by Sanyo Kasei Kogyo K. K., Japan .sup.3 Dipentaerythritol hexaacrylate .sup.4 Triisocyanate "Sumidule" by Sumitomo Kagaku Kogyo K. K., Japan .sup.5 "Aerosil" by Degussa, West Germany
The films prepared in this way were cut to test pieces of 25 mm in width and 100 mm in length, and the adhesive force of the films before and after the application thereto of the ultraviolet light was measured in the same manner as in Example 1.
To measure the adhesive force before the application thereto of the ultraviolet light, the mold releasing paper was removed from the film, and the film was placed on a stainless plate in the same manner as in Example 1. After standing at 21.degree. C. for 30 minutes, the adhesive force was measured.
To measure the adhesive force after the application thereto of the ultraviolet light, the films were left standing at 21.degree. C. for a predetermined period of time, and then the mold releasing paper was removed from the film, and the ultraviolet light was applied to the film from the back side of the base film for 7 seconds in the same manner as in Example 1. Thereafter, the adhesive force was measured. The results are shown in Tables 16 and 17.
As seen in Example Nos. 1-5 in Table 16, the pressure sensitive adhesive films according to the invention were found to retain a high adhesive force after standing for a long period of time before the application of the ultraviolet light, but were found to be greatly reduced in the adhesive force when the the ultraviolet light was applied thereto.
The pressure sensitive adhesive films of Reference Example Nos.1 and 2 which had no barrier layers between the base films and the adhesive layers were found to have a high adhesive force immediately after the preparation, and were found to be reduced in the adhesive force by the ultraviolet light irradiation. However, when the films were left standing for a long time after the preparation, the adhesive force of the films were found to reduce or change remarkably, but also the reduction in the adhesive force by the application of ultraviolet light is greatly fluctuated with time.
Further the pressure sensitive adhesive films of Reference Example Nos. 3 and 4 wherein the polyester polyurethane resins and polymethyl methacrylate were used as the barrier layer resins were also found to have a high adhesive force immediately after the preparation, and were found to be reduced in the adhesive force by the application thereto of the ultraviolet light. However, when the films were left standing for a long time after the preparation, degree of the reduction in the adhesive force of the films were found to be remarkably varied, and in some cases, the adhesive force was found to increase when irradiated by the ultraviolet light.
The pressure sensitive adhesive films of Reference Example No. 2 contains a polyvinyl chloride film which had no plasticizers therein as a base film and had no barrier layers between the base film and the adhesive layer. This film was also found to be reduced in the adhesive force with time before the application of the ultraviolet light.
Furthermore, as compared with Reference Example Nos. 5 and 6, the pressure sensitive adhesive films of the invention containing either polyisocyanate or silica powder show a greater reduction in the adhesive force by the application of the ultraviolet light. The pressure sensitive adhesive films containing both the polyisocyanate and silica powder were found to be reduced in the adhesive force to a further greater extent by the application of the ultraviolet light thereto.

Number	Date	Country
60-028030	Feb 1985	JPX
60-028031	Feb 1985	JPX
60-196540	Sep 1985	JPX
60-196541	Sep 1985	JPX
60-196542	Sep 1985	JPX
60-196543	Sep 1985	JPX
60-196544	Sep 1985	JPX
60-196545	Sep 1985	JPX
62-13035	Jan 1987	JPX

Number	Name	Date
3060023	Burg	Oct 1962
4312916	Kakumaru	Jan 1982
4398660	Pampalone	Aug 1983
4605592	Paquette	Aug 1986
4700208	Vanier	Oct 1987
4818621	Kuroda	Apr 1989

Number	Date	Country
110582	Jun 1984	EPX
121833	Oct 1978	JPX

Pressure sensitive adhesive film with barrier layer

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