WO2018235301A1

WO2018235301A1 - Transfer method using adhesive ink, transfer article, and transfer device

Info

Publication number: WO2018235301A1
Application number: PCT/JP2017/023321
Authority: WO
Inventors: 飛田　常司
Original assignee: 株式会社サンリュウ
Priority date: 2017-06-19
Filing date: 2017-06-19
Publication date: 2018-12-27

Abstract

Conventionally, hydraulic transfer has been used for transfer to a three-dimensional object; however, with this method, it has not been possible to control image deformation, achieve precise positioning, or ensure a good working environment. The extent to which hydraulic transfer can be applied to conductive circuits has also been limited. A transfer adhesive ink with which it is possible to obtain a silica hybrid cured film using a water transfer sheet has had limited applications as such a transfer adhesive ink cannot be transferred to a three-dimensional object, for example. The present invention solves the problems related to hydraulic transfer by forming an adhesive layer with the adhesive ink as an alternative to an activation treatment, and further pneumatic transfer is made possible by humidifying a PVA resin film. In addition, in a combination with a variety of transfer media, the present invention enables high-speed transfer or resist printing, circuit transfer with minimum dimensional change, and transfer to a three-dimensional object.

Description

Transfer method using adhesive ink, transfer material, and transfer device

The present invention relates to a method of transferring a transfer film to a three-dimensional object, an ink, a transferred material, and a transfer device.

A hydraulic transfer method is known as a method of providing a decoration on a (3D) transfer material having a three-dimensional shape, or as a method of transferring a conductive circuit pattern (see Patent Documents 1 and 2). In this hydraulic transfer method, the image layer itself is activated in the case of image transfer, but in the case of a circuit pattern in which the pattern is made of metal, an adhesive film layer is provided to transfer to the transfer material. Activation means that an activator composition comprising an organic solvent is spray-coated on an image layer formed of a thermoplastic resin to swell and tackify the image layer. Before or after the application of the activator composition or the formation of the adhesive film layer, the water-soluble resin film is floated on the water surface with the image layer or pattern layer up, and then the transfer material is placed on the water-soluble resin film. After pressing the water-soluble resin film into close contact with the transfer surface of the transfer material by water pressure, the water-soluble resin film is removed to obtain a target transfer product. Since the transfer material is transferred while pressing down toward the film floating on the water surface, the degree of image deformation can not be predicted and the image position can not be controlled, but it is used for transfer printing of wood grain or marble pattern. Since deformation is a problem in circuit pattern transfer, it is necessary to take measures to avoid the problem that the positions of the conductive patterns mutually change due to the expansion of the water-soluble resin film of the substrate. Measures such as Patent Document 3 in which a resin base layer for the purpose of suppressing deformation is transferred to a circuit pattern and transferred, and Patent Document 4 in which two kinds of solutions are used in a film substrate of two layers of hydrophilicity and lipophilicity are proposed. There is.
Patent Document 5 is also known as a method for transferring a pigment image to a curved surface. It is a proposal to solve the problem of image distortion and water pressure transfer which can not obtain the same image again. A toner image is formed on a transfer film made of polysaccharides, and then an adhesive and cold water are sprayed in this order to soften the transfer film, which is transferred onto the sheet by placing a silicone rubber film bag containing a liquid on a sheet, etc. It is supposed to press it. In addition, the example of a method of improving the breaking elongation of the film which consists of polysaccharides is patent document 16. FIG.
Although it is a dye image, as an example in which a polyolefin resin film is used for the purpose of image transfer under air pressure to a three-dimensional object, Patent Document 6 can be mentioned. A polypropylene resin (PP) film is used to place the transfer material and the transfer sheet under reduced pressure with respect to the outside, or press and contact to heat the material to sublimation transfer the image to a three-dimensional object. . The PP film is brought into close contact with a transfer material having a flat surface without heating and then heated, and the transfer sheet is heated while being in close contact with the transfer material having an uneven surface. In addition, polyvinyl alcohol (PVA) resin films have good releasability from thermosetting resins such as unsaturated polyester and epoxy, and acrylic resins, and are used for thermal transfer of toner images created by laser printers in image transfer ( Patent Document 7). It is a proposal regarding heat transfer printing on a flat surface such as a T-shirt by forming as a release layer on paper or film as a base material.
As a method of transferring the metal foil, using a metal foil for thermal transfer in which a release layer, a metal foil layer, and a hot melt adhesive layer are formed on a carrier film, prepare a press mold and heat and press from the carrier film side. The hot stamp method is widely spread. However, conditions such as the need for a pressing die and a heat pressing machine have been avoided, and a cold stamp method that does not require a pressing die has emerged. A UV transferable metal foil for cold transfer is placed on the UV curable adhesive layer formed on the printed sheet that corresponds to the material to be transferred, and UV radiation is applied from above to cure the adhesive layer, and then from the carrier film Patent Document 8 is an example of a method of peeling and transferring a metal foil layer only to an adhesive layer pattern portion, and Patent Document 8 is an example of an ultraviolet curable ink and a printing method.
Patent document 9 is a proposal regarding the method of obtaining a printing image and a reverse pattern using foil for thermal transfer. A pattern with a curable ink is directly printed on the surface of the hot melt adhesive layer of a foil for thermal transfer, the pattern is cured, and the cured product of the curable ink is hot stamped as a mask image to obtain a pattern opposite to the printed image. And
A transfer method is also used to form a printed circuit board. There are various methods for producing a pattern made of a conductive material, such as a screen printing method using a conductive paste on a resin film, an etching removal method for unnecessary portions, and an electrodeposition pattern transfer method formed on stainless steel. The produced pattern is transferred to a material to be transferred through the adhesive layer. Since the material to be transferred is not limited to the flat plate shape, a transfer method to a curved surface is also sought. A pattern is formed from a flat film to a cylinder by relatively rotating the film on which a predetermined pattern is formed by etching from a vapor deposition or sputtering metal layer and a cylinder on which the adhesive layer is formed on the entire periphery of the side. There is also a proposal like Patent Document 10 that can be transferred to the side of the body. By rotating the cylinder once along the film, transfer without wrinkles and misalignment is possible. It is said that it is preferable to use a tape-like insulating double-sided adhesive for forming an insulating adhesive layer on the side of the cylinder, because it is difficult to apply a liquid adhesive coating to a certain thickness. As an electrodeposition pattern transfer method said to be suitable for highly precise fine pattern formation, there are methods such as Patent Document 11 and the like. In this method, the electrodeposited material is transferred to the transfer material from the side of the base material made of stainless steel or the like by the adhesive force of the adhesive film layer formed on the transfer material. In this process, the peeling force by the adhesive film layer also acts on the electrodeposition mask layer formed on the substrate side, so that the photoresist layer which is a material of the electrodeposition mask layer is easily detached, and the electrodeposition metal pattern transfer is performed. It has been considered difficult to repeatedly use the base material. Patent document 11 is a proposal which employ | adopts and improves the electrodeposition mask layer which consists of silicone resin.
Patent Document 12 used for transferring an image formed on a water transfer sheet is known as an adhesive ink for ink jet comprising an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing. It is. After a toner image or the like is formed on the dextrin water-soluble layer formed on the base sheet, an adhesive ink is applied by an ink jet printer and pressed against the material to be transferred, and the image is released by applying moisture from the back. It is a method that can be transferred even without heating to peel off the base sheet.
Also known is an apparatus for transferring a pigment image, not a dye image, to a transfer material having a three-dimensional shape. For example, Patent Document 14 discloses that an ink layer is provided via a release layer formed on an elastomer base sheet, vacuum contact is made to the surface of a transfer material, and the ink layer is transferred by heating in a close contact state. Similarly, in Patent Document 15 in which the transfer film is brought into close contact with the surface of the transfer material by vacuum force and the periphery of the transfer material is heated in a close contact state, heating to the transfer film is good depending on the shape of the workpiece in the method of Patent Document 14 In order to remedy the drawbacks that do not occur. Heating of the periphery of the material to be transferred is performed with high temperature steam.

International Publication WO 98/46684 Unexamined-Japanese-Patent No. 2014-069503 JP, 2016-060089, A Patent No. 5472098 Japanese Utility Model Application Publication No. 5-012197 JP, 2011-240674, A Japanese Examined Patent Publication No. 09-087980 JP, 2010-280858, A JP, 2012-210715, A JP 2011-091304 A JP-A-11-068294 Patent No. 6074563 JP, 2014-193552, A JP 2007-168121 A JP, 2011-126263, A Japanese Patent Application Laid-Open No. 09-031246

The conventional water pressure transfer method described above has the disadvantage that it is not possible to position the image, to control the expansion and deformation of the image, and to reproduce the same transferred image result. In addition, there is also a disadvantage that the solvent is scattered by the activation spray application and the working environment is deteriorated. Furthermore, depending on the amount of application of the activation liquid, a part of the image layer may be dissolved too much to collapse, or conversely, if the dissolution is insufficient, a part of the transfer pattern may be dropped, or a protective layer may be formed As pointed out in Patent Document 2 which proposes an improvement method of providing the above, the organic solvent causes the image layer to swell and become tacky in the activation step in the hydraulic transfer method, so that the brightness of the image layer is impaired, etc. . Although patent document 13 describes an extension suppressing resin layer made of a polyolefin resin or the like as a method of controlling excessive elongation and deformation of a transfer film, the process becomes complicated and the application of an activator before transfer is The need is the same.
In Patent Document 5, since the adhesive is sprayed onto the pigment image, it is inevitable that the adhesive also adheres to portions other than the image of the transfer material. Later, some treatment of the exposed adhesive layer is required. In addition, it is a transfer method of pressing the swollen transfer film from the back surface to the material to be transferred with a silicone rubber film bag, and transfer to the side opposite to the thickness direction of the material to be transferred can not be expected. However, even if it tries to improve entrapment, pneumatic transfer is difficult. The tensile elongation at break of polysaccharide films is originally low at a few percent, and softening by moisture application is possible but not suitable for stretching purposes. The maximum elongation at break of the film obtained by the method of Patent Document 16 for improving the elongation at break is also 9%. Therefore, in order to make the film gelled by the addition of water follow the curved surface of a three-dimensional object, it is only possible to expand it while crushing it from a back surface with a soft material such as rubber as described in Patent Document 5. Since peeling and removal after transfer can not be performed, there is no alternative but to dissolve and wash the film with warm hot water.
As a method of forming a decoration having high designability on a 3D transfer material by pigment image transfer, there has been only hydraulic transfer other than Patent Document 5. For image transfer by air pressure to a 3D transfer material, a sublimation transfer method using a film made of PVA resin, polyolefin resin, non-stretched polyester resin or the like is known, but the image is a dye image, and heating is The transcription was
Methods for forming a transfer film on a substrate include dry coating methods including vacuum deposition and sputtering, wet coating methods using an aqueous solution or non-aqueous solution including plating, painting, etc., and glitter ink Printing methods including gravure coating of For hydraulic transfer of a transfer film having no thermoplastic resin, it is necessary to apply an activator containing a resin binder.
In conventional hydraulic transfer of conductive circuit patterns, the transfer membrane is patterned on the substrate prior to transfer. In order to suppress deformation of the circuit pattern, Patent Document 4 in which a hydrophilic and lipophilic two-layer film substrate is provided is not required to be dissolved twice in a hydrophilic solvent and in a lipophilic solvent. The adhesion to the material to be transferred requires heat treatment of the conductive paste after transfer. Although a method like the patent document 3 which formed the deformation suppression layer in the pattern lower side is also known, the transfer film which provided the foundation | substrate which consists of hardening resin takes the effort which obtains appropriate hardness by electron beam irradiation or heat processing. There is. The uppermost layer is provided with an adhesive image that requires activation treatment, and the point that management of the amount of coating solvent and environmental management by solvent scattering are required is the same as the conventional method.
In the cold stamp method, which does not require a pressing die, an ultraviolet curing device is used because an ultraviolet curing ink is used. In order to cure the ink, it is required that the material to be printed is transparent or that the transfer foil has ultraviolet transparency. If the UV curable ink is formed on the cold transfer foil side so that the print target is a three-dimensional object and can be transferred, UV irradiation becomes difficult. Irradiation may not be possible depending on the place. In addition, since a certain amount of heat is applied even when irradiated with ultraviolet light, when the material to be transferred is a vinyl chloride resin film package or the like, there is a risk of deformation due to low heat resistance and thin thickness. The same is true when cold stamping is performed with a thermosetting adhesive ink.
In the method of Patent Document 9 for obtaining a pattern reverse to the printed image, it is necessary to prepare a carrier film which has been subjected to adhesion adjustment processing such as easy adhesion processing on the surface. It is believed that commercially available thermal transfer foils can also be used, but this is questionable. Since the commercial product is subjected to peeling treatment to the carrier film, as shown in the present invention, the pattern part foil is also transferred and must be removed. In addition, if the pattern is to be formed of an ultraviolet curable ink or a thermosetting resin, the hardness after curing thereof is high, and it should be a problem that it has no flexibility. The pattern formed on the thermal transfer foil seems to risk breaking or falling off if it is curved after curing.
In the transfer of the printed circuit, it is not preferable to heat and transfer the circuit pattern formed on the resin film to the transfer material. This is because the thermal contraction of the resin film causes a dimensional error between the wires. In order to improve this, it is necessary to take measures such as preheating treatment of the film. If there is a thermoplastic component in the conductive paste binder, depending on heating temperature and transfer pressure, line thickening may occur. It is preferable that the adhesive film layer for which adhesion is required for both the circuit pattern and the transfer material in the transfer step be present only in the pattern portion. If a tape-like insulating double-sided adhesive or the like is attached in a range covering the entire surface of the material to be transferred, the adhesive film layer remains exposed in areas other than the pattern transfer area after transfer, and some treatment of the adhesive surface is required. In addition, if the material to be transferred is a transparent substrate, the remaining adhesive other than the pattern portion is problematic in terms of design. In order to form the adhesive film layer only on the pattern portion, it is suitable to use a digital printing method which enables precision printing and allows a personal computer to easily perform shape correction, positioning operation and the like according to the pattern. Among them, inkjet printing is preferable. However, no adhesive ink having initial adhesion and final adhesive strength sufficient to stably lift and bond the circuit pattern even without heating was the only ink selected in the present invention. In the method of forming the electrodeposition mask layer with a photoresist, when the electrodeposition layer such as copper plating is peeled off and attached with an adhesive formed on the entire surface of the substrate for transfer, part or all of the photoresist is covered. There was a problem of adhering to the adhesive material of the transfer substrate. In order to solve this, the electrodeposition mask had to be exfoliated in advance, or it took time and effort, and the adhesive had to be patterned. In the electrodeposition metal pattern transfer method according to the method of Patent Document 11, in order to obtain an electrodeposition mask layer made of silicone resin, it is necessary to preliminarily form a mask for electrodeposition mask layer formation using a photoresist, which is troublesome. ing.
It has been confirmed that an inkjet adhesive ink comprising an organic solvent containing an organic-inorganic hybrid composition can be used to transfer an image formed on a water transfer sheet. However, under conditions where water is applied from the back side to peel off the base sheet, it is not preferable for applications requiring high-speed cycles. In addition, since a water-soluble resin layer on which an image is formed is attached with a base sheet made of paper or film with low flexibility, the base sheet is peeled off after the image is brought into close contact with the image receiving material. Under the conditions of (1), transfer to the side of the rolling cylinder is possible, but transfer to the 3D transfer material is not possible. Even if the base sheet is peeled in advance for transfer to the 3D transfer material, the water-soluble film layer is formed as thin as several μm so that water can penetrate from the back surface and dissolve easily. , Not suitable for hydraulic transfer. A water-soluble film layer composed of dextrin, which is a natural polymer, is not suitable for pneumatic transfer.
In an apparatus for pneumatically transferring an image formed on a transfer sheet to a 3D transfer material, it is a condition to transfer while heating. The transferred material having insufficient heat resistance could not be transferred.
The present invention enables deformation suppression and positioning of a transfer film in transfer of a transfer film to a three-dimensional object, enables unheated transfer in air pressure transfer, and uses an inkjet adhesive ink other than a water transfer sheet. The object of the present invention is to improve the operability of transfer work, to speed up transfer, to automate, etc. by using in combination with various transfer media.

The first problem solving means of the present invention for achieving the above object comprises an organic / inorganic hybrid composition on the film side for transfer formed on a water-soluble resin film, from which a silica hybrid cured film can be obtained after drying and curing. Forming an adhesive film layer by printing using an inkjet printer using the obtained organic solvent as an adhesive ink, adhering the adhesive film layer side to a material to be transferred by a water pressure transfer method, and water-soluble resin film by water dissolution Forming a transfer film pattern on the material to be transferred via the adhesive film layer, the method comprising:
A second means for solving the problem is an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the transfer film side formed on a water-soluble resin film composed of a synthetic polymer. The water-soluble resin film after being printed and formed as an adhesive film by an inkjet printer using an adhesive ink, is placed in a space that has been humidified with water vapor to have a humidity of 60% or more, or the diameter after spraying is 100 μm or less Attaching water particles to the water-soluble resin film having the adhesive film layer formed by at least one method, and adhering the adhesive film layer to a material to be transferred by an air pressure transfer method Forming a transfer film pattern on the material to be transferred via the adhesive film layer, comprising the steps of: removing the water-soluble resin film by peeling or dissolving in water; A transfer method and butterflies.
The third problem solving means is an organic / inorganic hybrid in which a silica hybrid cured film is obtained after drying and curing on the transfer film side formed on a transfer film consisting of a polyolefin resin or a PVA resin filled with a plasticizer. An adhesive film layer is formed by printing using an ink jet printer using an organic solvent containing a composition as an adhesive ink, and then the adhesive film layer is applied to a material to be transferred by either air pressure or elastic pressure. Forming a transfer film pattern on the material to be transferred via the adhesive film layer, including the step of bringing into close contact, and the step of removing the transfer film by water dissolution or peeling. is there.
A fourth problem solving means is the transfer film of the present invention, wherein the transfer film is formed by at least one of dry coating, wet coating, and printing.
A fifth problem solving means is a transfer film in which the transfer film on the transfer film is patterned before transfer in the transfer method of the present invention.
A sixth means for solving the problem is an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the side opposite to the carrier film of the transfer foil or on the side of the transferred material. After the adhesive film layer side is printed and formed by an inkjet printer using the adhesive ink as an adhesive ink, the adhesive film layer side is brought into close contact with the material to be transferred by either non-heat pressing or low temperature heating pressing; And peeling the foil for transfer, and forming a foil pattern of the same shape as the adhesive film layer pattern on the material to be transferred through the adhesive film layer.
A seventh means for solving the problem uses an adhesive ink comprising an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the side opposite to the carrier film of the thermal transfer foil. And drying the adhesive film layer pattern after the adhesive film layer pattern is printed by an ink jet printer, and curing the adhesive film layer pattern until the adhesive property is lost; It is a transfer method characterized by including a step of transferring onto a material to be transferred and a step of removing only a portion of the transferred thermal transfer foil to which the adhesive film layer pattern is attached to the lower side.
The eighth problem solution means is a method of curing a silica hybrid after drying and curing on a water-soluble resin film or a patterned conductive layer having a thickness of 0.5 μm or more formed on a substrate for electrodeposition metal pattern transfer. An adhesive film layer is printed by an ink jet printer using an organic solvent containing an organic-inorganic hybrid composition from which a film is obtained as an adhesive ink, and the adhesive film layer has an insulating property on the adhesive film layer. Including the steps of non-heat-pressing or heat-press-contacting the transfer material, and removing the water-soluble resin film or the stainless steel plate while leaving the conductive layer on the transfer-receiving material. Forming a conductive layer on the material to be transferred via the adhesive film layer.
A ninth means for solving the problem according to the transfer method of the present invention, wherein the concentration of silica dispersed in the cured silica hybrid film is 5 wt% to 80 wt%, and the single particle diameter is in the range of 1 to 100 nm. An adhesive ink for inkjet printing.
The tenth problem solving means is an organic / inorganic material having a single particle diameter in the range of 1 to 100 nm and dispersed at a concentration of 5% by weight to 80% by weight and having affinity for both organic and inorganic substances. A transfer material is characterized in that a hybrid cured film is used as an adhesive layer and a conductive transfer film pattern having a thickness of 0.5 μm or more is held on the insulating surface of a material to be transferred.
The eleventh problem-solving means comprises the steps of subjecting the transfer film side formed on the PVA resin film to an activation treatment to obtain an adhesive film, and subjecting the PVA resin film to water vapor humidification to a humidity of 60% or more. And (b) swelling or softening the PVA resin film by placing the water particles of 100 μm or less in a fixed time for a fixed time or by spraying at least one method, and pneumatically transferring the adhesive film layer and the transfer material Forming a transfer film pattern on the material to be transferred via the adhesive film, including the steps of adhering by a method and removing the PVA resin film by water dissolution or peeling. It is a transfer method.
A twelfth solution is a transfer device for pneumatically transferring a transfer film formed on a water-soluble resin film onto a material to be transferred, in which the resin film on which the material to be transferred is placed is in close contact with the tray. Water particle spray having a close contact mechanism portion capable of depressurizing the inside space to the outside space, and a structure capable of spraying fine water particles having a diameter of 100 μm or less in the space enclosed by the cover of the outside space. A fine water particle spray before bringing the resin film into close contact with the material to be transferred, or a fine water particle spray before removing the resin film from the material to be transferred, at least one of It is a transfer device characterized in that it enables spraying.
A thirteenth solution means is a transfer device according to claim 13, characterized in that the water particle spray unit is constituted by an ultrasonic humidifier capable of spraying the fine water particles.
The function of the first problem solving means is the role of two layers of an adhesive film layer formed by activation treatment in water pressure transfer or adhesive application, and a pattern deformation suppression layer formed by electron beam irradiation or the like. , With one silica hybrid adhesive film layer. As a result, the hydraulic transfer work environment and the workability are improved, the transfer failure is reduced, and the extension and deformation of the transfer film can be controlled. The work environment and workability improvement can be achieved by eliminating the spray application work of the activator and eliminating the contamination of the work environment by the solvent splash.
The control of reduction in transfer defects and control of elongation deformation will be described by dividing the adhesion of the silica hybrid adhesive ink used in the present invention into two. The force required for transfer of the transfer film will be described as the initial adhesion, and the force required for the substrate for the intended use will be described as the final adhesion. The transfer membrane side formed on the water pressure transfer film is brought into close contact with the transfer target by water pressure. Since the hydraulic transfer film itself is dissolved in water, the transfer film transfers to the transferee side if a sticky film is present. In the conventional water pressure transfer, the thermoplastic resin image layer itself dissolved with the solvent by the activation treatment is used as the adhesive film layer. An adhesive film layer was applied to the transfer film which is not soluble in the solvent. The initial adhesive strength corresponds to the adhesive strength of the adhesive film layer.
The adhesive ink is made of an organic solvent and is weak. However, when the solvent evaporates from the film after printing to a certain extent, the adhesive ink develops adhesion. It is also easy to increase the tackiness by containing a tackifier or a plasticizer in the ink. The adhesion can be maintained for a long time by increasing the proportion of a slow-drying solvent such as high boiling point alcohol in the contained solvent. At the same time, it is possible to have stretch resistance in the non-dry state which could not be achieved with the thermoplastic resin adhesive film layer. A general adhesive film layer can not have stretch resistance unless it is dried and loses its tackiness. While the silica hybrid adhesive film layer exhibits tackiness, the curing reaction proceeds in the air and the hardness increases. It shows the properties of the film as a solid, not a free-deforming viscous agent. This is the reason why it can play a role as a deformation suppression layer of the transfer film.
The method of preventing the image layer (transfer film) luminance reduction shown in Patent Document 2 is the formation of a protective layer. The protective layer is applied with an active agent so that the protective layer itself is dissolved and tackified, while preventing excessive dissolution of the image layer. The silica hybrid adhesive film layer plays this role. That is, while the activator is a solvent for dissolving the coating agent, the adhesive ink contains only a solvent to an extent that the printability is improved, and the image layer is not excessively dissolved. When the adhesive film layer is transferred at a stage where the film shows properties as a solid, since the image layer is prevented from being broken and the smoothness is maintained, the reduction in luminance can be suppressed. Conversely, in applications where the image layer needs to be stretched, it may be transferred in an unreacted, low viscosity state. The final adhesion between the silica hybrid membrane and the substrate is reached by natural standing for several days and is not affected by the time allowed to stand before the transfer step.
Among the defects of hydraulic transfer, there are breakage of the image layer and adhesion failure due to the variation of the amount of applied solvent. Forming a coating with uniform thickness everywhere is a problem with difficult spray application techniques. On the other hand, the adhesive film layer formed by inkjet printing can be formed with uniform thickness. There is no transfer failure due to the variation of the solvent amount.
The transfer film referred to in the present invention is a film to be an image or circuit pattern formed by a method such as coating, printing or electrodeposition, and has a thickness of 10 nm to 500 μm. A vacuum deposited film of 50 nm, a silver nanopaste layer of 100 nm thick by inkjet printing, a conductive paste layer of 100 μm by screen printing, and the like are included, but these are in the easily transferable range. The transfer film may be not a single layer film but a multilayer film. The thickness of the water-soluble resin film is preferably about 10 μm to 100 μm. The adhesive film layer is preferably formed to a thickness of about 100 nm to 5 μm.
The action of the second problem solving means adopts a water-soluble resin film composed of a synthetic polymer as a medium for transfer, so non-heated transfer to a 3D transfer material is possible with air pressure, as well as water pressure transfer. become. To solve the problem of hydraulic transfer, in addition to the action by the first problem solution means, the transfer film pattern can be positioned on the material to be transferred, and the same transfer result can be easily repeated. Bring. The elimination of the need to immerse both the water-soluble resin film and the material to be transferred in water has these effects.
Although the water-soluble resin film floating on the water surface can not be controlled in position, the position can be fixed by using an air pressure transfer method in which the film is placed on a fixed position of a vacuum tray containing the transfer material. Next, when the pressure in the tray is reduced, the transfer position of the transfer film pattern on the transfer material becomes constant.
Deformation was also unpredictable by hydraulic transfer. Even if the expansion and deformation of the transfer film can be controlled to a certain extent by the curing level of the adhesive film layer, there is a limit in hydraulic transfer. This is because swelling and softening progress continuously and rapidly in the step of adhering the film and the transfer material in water. In the case of the pneumatic pressure transfer according to the means for solving the problem, the swelling and softening of the water-soluble resin film does not proceed in the adhesion step. Swelling and softening are performed by placing the water-soluble resin film in a space under high humidity for a certain period of time, or depositing fine water particles to be sprayed from an ultrasonic humidifier, etc. Because Even if the fine water particle spray is continued during the bonding process, the change in the swelling and softening level is much slower than in water. This is the basis for making the degree of deformation of the transfer film pattern on the transfer material constant. In addition to the degree of deformation becoming constant, there are cases where it is desirable to suppress deformation locally. This is made possible by covering the local area with a mask to limit the adhesion of moisture, rather than applying a deformation suppressing layer. The film locality with little moisture adhesion does not easily stretch even under air pressure, and the transfer film deformation is suppressed.
The air pressure in the present invention for bringing the film into close contact with the material to be transferred means that the space between the material to be transferred and the transfer film is a negative pressure or a high pressure is applied to the outside to reduce the pressure relative to the outside. It means putting it down. Both may be moved relative to each other in the distance direction in the decompression space. If the pressing force from the back of the transfer film is air pressure and there is no object in contact, the water-soluble resin film made of a synthetic polymer that stops swelling and softening at a certain level does not open in the adhesion step under reduced pressure. It is also possible to peel off after adhesion. It can be said that the above-described improvement of the workability can be further improved if there is no work of washing away the residual swollen water-soluble resin that clings to the transferred material after close contact in water pressure transfer. However, when the size of the water particle to be sprayed exceeds 500 μm diameter, the water particles are connected to each other on the adhering surface and easily aggregate before uniformly penetrating on the PVA resin surface. Since the transfer film of the aggregation portion is excessively softened, holes are instantaneously opened when the pressure is reduced. The adhesion between the transfer film and the material to be transferred is incomplete. The size of the water particles is preferably 100 μm or less, more preferably 10 μm or less. Although it takes more time than fine water particle deposition, steam humidification is more preferable to achieve uniform softening.
It should be noted here that the water-soluble resin film made of a synthetic polymer swollen with water to a certain extent also has the effect of improving the releasability of the transfer film. Even in the early stage of ink curing, the film for transfer is likely to be transferred to the material to be transferred from the swollen water-soluble resin film. The water content that makes it easier for the transfer film to peel off is higher than the water content that is required to stretch flexibly without breaking under air pressure. Therefore, it is preferable to stop the water-soluble resin film from the material to be transferred again before stopping the process of swelling and softening the film by adding water, before the step of adhering the film and the material to be transferred. The film in a state of being wound around the material to be transferred before peeling has a surface that faces in any direction along the shape of the material to be transferred. In general spray application with directivity, it is difficult to uniformly apply the entire surface. It is relatively easy to deposit water particles on all of these surfaces with a spray of fine water particles of 100 μm or less in diameter, which easily float in the air.
As an action when compared with the conventional pneumatic transfer by the second problem solution means, non-heat transfer becomes possible, and it is not necessary to form a release coat layer or the like on the transfer film. Transfer of the transfer film to a low heat-resistant transfer material is possible.
It was previously shown that the method of Patent Document 5 using a polysaccharide film is not suitable for pneumatic transfer because of low tensile elongation at break. The water-soluble resin film made of a synthetic polymer has a large tensile elongation at break, and for example, the tensile elongation at break of a PVA resin film is originally 150 to 200% or more in many cases, and is suitable for pneumatic transfer onto a three-dimensional object. If it is softened by the addition of water, a larger elongation can be obtained.
The thickness of the water-soluble resin film made of a synthetic polymer is preferably about 10 μm to 100 μm. Examples of the water-soluble resin made of a synthetic polymer include PVA resin, water-soluble polyurethane resin, polyethylene glycol resin and the like. You may mix and use with other water soluble polymers. Depending on the degree of polymerization and the degree of saponification, or the plasticizer addition ratio, flexibility can be provided without the addition of water, but the moisture resistance during handling is inferior and film deformation may occur during the printing operation. In the case of a PVA resin, one having a polymerization degree of 1000 to 4000 and a saponification degree of 70 to 99 mol% is preferable. The adhesive film layer is preferably formed to a thickness of about 100 nm to 5 μm.
The action of the third problem solving means is as follows. The second problem solution means is dry transfer, but it is a method that requires transfer of water to the transfer film. The third solution is a completely dry method. Since it is not necessary to control the amount of water permeation into the transfer film, positioning of the transfer film pattern on the material to be transferred and repetition of the same transfer film pattern result can be performed as well as effect of facilitating work control. . Many of the conventional hydraulic transfer challenges are eliminated.
A film made of either a polyolefin resin or a PVA resin filled with a plasticizer has a certain degree of flexibility even without heating, and can be used as a transfer film to a 3D transfer material. Among the polyolefin resins, the non-stretching type is excellent in flexibility, and non-stretching type polypropylene (CPP) and non-stretching type polyethylene (LDPE) are preferable. All of these films have the property of being difficult to adhere without release coating, which is advantageous for transfer films. As the dry curing of the adhesive ink proceeds, the adhesive strength is sufficient to peel the image from the transfer film. If a release coat layer is provided on the film surface, peeling is further facilitated, and the transfer cycle time can be shortened.
The adhesion between the transfer film and the material to be transferred can be performed by either pneumatic pressure transfer or elastic body pressure transfer. The elastic body pressure in the present invention is a pressure applied by relatively moving a flexible elastic body such as rubber from the back side of the transfer film so as to press the material to be transferred. The transfer film is contact-pressed between the elastic body and the material to be transferred, but the transfer film without swelling and softening does not break and peeling off after adhesion between the film and the material to be transferred is easy. If curing of the adhesive is insufficient and the image is peeled off with the film attached when releasing the reduced pressure, heat curing is promoted or the periphery is cut and cured so that the film remains on the material to be transferred Take time.
By temporarily bonding the support base through the laser printer, it is possible to form a toner image on these films. In the case of using an ink jet printer, a resin ink may be used so that the image does not blur. Even without the ink receiving layer, an image can be formed by printing while warming. The resin ink mentioned here refers to an ink containing a resin component in a solvent, and a UV ink cured by UV irradiation from a latex ink used for thermosetting and a water based resin ink used for T-shirt printing and the like. Including up to. The thickness of each of the polyolefin film and the PVA resin film is preferably about 10 μm to 100 μm. The adhesive film layer is preferably formed to a thickness of about 100 nm to 5 μm. The plasticizer is preferably a polyhydric alcohol plasticizer such as glycerin. The filling is preferably 10 parts by weight or less, based on 100 parts by weight of the PVA resin.
The operation of the fourth problem solving means is as follows. In the conventional water pressure transfer method, the tackiness can not be obtained unless it is a transfer film made of a thermoplastic resin which is soluble in the activated processing solvent, but in the present invention, it is a method of applying an adhesive film layer to obtain tackiness. Various materials formed by at least one of a coating method or a wet coating method or a printing method can be used as a transfer film. By forming an adhesive film layer pattern on a part of the transfer film, the transfer film of only the pattern portion can be transferred to the printing material. In order to facilitate transfer, a release layer may be provided between the transfer film and the transfer film. The transfer film may be multi-layered not with a single layer but with a print layer, a vapor deposited foil layer, a print layer, and the like.
The operation of the fifth problem solving means is as follows. The metal deposition layer pattern formed on the water transfer sheet by removing unnecessary portions by the etching process is an example of the transfer film patterned. If the adhesive film layer is formed on the side of the patterned transfer film, the transfer film of only the pattern portion can be transferred to the printing material. It is needless to say that accurate transfer can be achieved by transferring a film that has already been patterned, rather than by peeling off a part of the transfer film by the adhesive force of the adhesive film layer to obtain a pattern. The patterned transfer film includes a thermal transfer foil thermally transferred onto a transfer film, and a printed image.
The operation of the sixth problem solving means is as follows. Cold foil transfer using conventional UV curable inks can be replaced with silica hybrid adhesive inks. Since transfer of a foil is possible without applying heating or high pressure, transfer can be performed by applying pressure to a silicone rubber roller without using a heated pressing die. Not only commercially available cold transfer foils, but also commercially available heat transfer foils can be transferred by this method. Not only metal foil but also pigment foil or the like may be used as long as the foil layer is mounted on the release layer of the carrier film.
Since the adhesive ink used in the present invention is not UV curable, the UV transparency of the transfer layer need not be considered. Therefore, an opaque image layer may be interposed between the adhesive film pattern and the foil layer. It is not necessary for the material to be transferred to be transparent. In addition, an ultraviolet irradiation device for curing the adhesive is not necessary. If inkjet printing of a heat-curable adhesive is possible, transfer can be performed in the same process as in the present invention, but heating must be performed during transfer. A heat treatment device is required. Furthermore, the material of the material to be transferred is limited to the range of products that can withstand the thermal conditions.
As compared with the case where the adhesive ink for inkjet is used in combination with the water transfer sheet, the step of applying water is eliminated, the transfer operation is simplified, and the speed of transfer can be increased. Although the foil of the adhesive film layer pattern can be pressed and transferred onto the material to be transferred without heating, it may be heated and pressed at a low temperature for the purpose of promoting curing of the adhesive ink. Applicable heating temperature conditions are a range in which the curing of the ink proceeds too much and the sufficient adhesiveness for transfer is not lost, a range in which the transferred material is not deformed, and a range in which transfer of the thermal transfer foil does not occur.
In addition, although the transfer foil which can be used consists of at least three layers of a carrier film, a peeling layer, and a foil layer, the transfer foil which formed the color layer, the contact bonding layer, the protective image etc. in the interlayer or surface layer may be sufficient. The release layer can be formed by coating a silicone-based or wax-based resin.
The operation of the seventh problem solving means is as follows. Commercial heat transfer foils can be used to obtain printed patterns and reverse images (white negative images). The adhesive ink used in the present invention is a silica hybrid film that exhibits flexibility following the substrate when the cured film itself is formed on the flexible substrate. As compared with the case of using an ultraviolet curing resin or a thermosetting resin, it is soft even after curing, and it does not come off or break even if the foil is curved before use. Further, on the surface of the silica hybrid film, the stain resistance of the inorganic polymer is exhibited, and a coating film such as an overcoat agent is also difficult to adhere to. It has advantageous properties as a hot stamp heat adhesion resist.
The thermal transfer foil is transferred to all the portions on the printed material side that are heated and pressed, but the foil portion to which the adhesive printing pattern is attached on the lower side is not thermally welded to the printed material side. This unnecessary part of the foil can be easily removed by means of an adhesive tape or by means of a water jet or the like which blows pressurized water. Not only metal foils but also various foils such as pigment foils can be used as the thermal transfer foil. Curing of the adhesive film layer pattern may be left as it is for a certain period of time, but if heat treatment is performed at a temperature that does not affect the function of the thermal transfer foil, the time can be shortened.
The operation of the eighth problem solving means is as follows. By using a water-soluble resin film instead of a resin film for circuit transfer conventionally used to form a conductive circuit pattern and adhering the hybrid ink of the present invention which exhibits adhesion even without heating, Unheated transfer to the transfer material is possible. Therefore, the occurrence of dimensional error between the wires due to the thermal contraction of the transfer resin film is avoided. Even if a thermoplastic paste is used, the problem of thickening of fine pattern lines due to high heat does not occur.
It is preferable that the water-soluble resin film be temporarily adhered to a substrate such as a polyester (PET) film, because the water-soluble resin film alone may cause swelling due to moisture. If it is brought into close contact with the material to be transferred in a state of being temporarily bonded to the substrate film, no dimensional error occurs. However, prior peeling is also acceptable if it is brought into close contact with the material to be transferred immediately after peeling of the substrate film.
According to Patent Document 10, it is difficult to apply a liquid adhesive to a certain thickness, and tape-like insulating double-sided adhesive material bonding is preferred. In the case of ink jet printing, not only constant thickness coating, but also selection of thickness according to the surface roughness of the transferred material is easy. In addition, since the adhesive film layer is formed only on the circuit pattern portion, the remaining treatment of the adhesive film layer is unnecessary except for the transfer portion. Even if the adhesive film layer is exposed, the adhesive film layer used in the present invention cures and disappears, so there is no problem.
In electrodeposition metal pattern transfer using a stainless steel plate as a transfer substrate, when the circuit pattern is peeled off from the substrate, the photoresist layer is transferred from the recess on the side surface of the photoresist layer remaining on the substrate as an electrodeposition mask onto the transfer material Since the friction with the side of the electrodeposition substance occurs, the transfer difficulty is higher than the normal transfer using a water-soluble resin film. However, if it is necessary to withdraw the electrodeposition substance more than the initial adhesion of the hybrid ink of the present invention, it is sufficient to leave the circuit pattern for a fixed time or to accelerate the curing reaction at a low temperature of 60 to 80 ° C. Power is obtained. A condition that may accelerate the curing reaction is that the adhesive layer pattern does not cover the electrodeposition mask.
In the case of a material to be transferred in which the adhesive film layer is formed on the entire surface, the electrodeposition mask layer is detached from the base material. However, since the hybrid ink of the present invention is capable of inkjet printing, this operation corresponding to the patterning of the adhesive which is required in the conventional method can be easily performed. If the adhesive film layer does not cover the electrodeposition mask layer, there is no problem that the electrodeposition mask layer is peeled off from the substrate by the adhesive force of the adhesive film layer, so that the durability of the electrodeposition substrate for transfer is improved.
The substrate for electrodeposition metal pattern transfer referred to in this solution means a metal plate such as stainless steel, nickel, chromium, titanium, tin, an alloy plate of the metals, and the like. In the stainless steel sheet, it is preferable that the electrodeposition metal is easily peeled off if the chromium content is large. Adhesive ink printing on these rigid transfer substrates may be performed with a flat bed type ink jet printer.
If the circuit pattern thickness is extremely thin, wrinkles are likely to occur in the pattern metal layer during transfer, or fine cracks are likely to occur, and there is a problem that the conductivity is reduced due to entanglement with the insulating adhesive film layer transferred together. Occur. In order to transfer while maintaining the conductivity, the thickness of the circuit pattern before transfer is preferably 0.5 μm or more.
The operation of the ninth problem solving means is as follows. In the transfer method of the present invention, by using the organic / inorganic hybrid adhesive ink, it is possible to shorten the transfer cycle time when combined with a water transfer sheet that applies moisture from the back surface to peel off the base paper, 3D transfer material Various effects can be obtained, such as transfer to the surface, control of the degree of image deformation, reverse pattern transfer, and elimination of an ultraviolet irradiation device by non-heating foil transfer. Further, in the transfer of the conductive circuit, the adhesive ink itself is insulating, and there is no danger of shorting between the wires even if there is an ink portion which is out in the transfer of the fine circuit. It is necessary to have high adhesion to both sides of the conductive transfer film made of metal and thermoplastic resin that form the circuit and the transferred material made of a wide range of insulating materials such as ceramics, glass, polyimide resin and polyester resin. However, organic-inorganic hybrid adhesive inks are inks that meet this requirement. Although flexibility is also required for flexible substrates and the like, the silica hybrid cured film is optimum also for this requirement.
According to the function of the tenth problem solving means, it is possible to provide a transfer material in which a flexible conductive pattern is formed firmly adhered on the insulating surface of the substrate. The conductive pattern thickness of 0.5 μm or more has been described in the operation of the eighth problem solving means, and thus the description is omitted here.
The operation of the eleventh problem solving means is the same as that of the second problem solving means, and thus the description thereof is omitted here. There is a difference in whether the method of forming the adhesive film is inkjet printing or activation processing. Either of the activation treatment and the swelling and softening step of applying moisture to the PVA resin film may be performed before or after, or may be performed simultaneously or may be repeated.
The local deformation suppression method described in the second problem solution means is also effective in the eleventh problem solution means. Instead of applying a deformation suppression layer, in the step of applying moisture to swell and soften, deformation can be suppressed by covering a mask on the local portion of the PVA resin film to limit the adhesion of moisture. It is difficult for the film locality with little water adhesion to expand under air pressure, and the transfer film deformation is suppressed. The thickness of the PVA resin film is preferably about 10 μm to 100 μm.
According to the function of the twelfth problem solving means, it is possible to provide a transfer device capable of air-pressure transfer of a transfer film formed on a water-soluble resin film by coating, printing or the like onto a 3D transfer material without heating. That is, the step of sending fine water particles to the back side of the resin film so as to extend the resin film following the three-dimensional shape of the transferred material and swelling / softening it, and the variation due to the location of the water amount distribution attached on the resin film is averaged. To allow the resin film to adhere closely to the material to be transferred by air pressure, and to make the resin film easy to peel off the material to be transferred from the material to be transferred on the back side of the resin film It is possible to automatically control a series of steps of the step of sending again. Depending on the shape and material of the material to be transferred, fine water particle spraying is not necessarily performed for both the purpose of film swelling and softening before transfer and for the purpose of film peeling from the material to be transferred.
Although unheated transfer to a 3D transfer material such as a coating film or a pigment image can be performed only by a hydraulic transfer device, the same purpose can be achieved by unheated pneumatic transfer using the transfer device of the present invention. It also becomes easy to suppress the transfer film deformation and to position the transfer material.
The adhesion mechanism portion can be manufactured by using a known method such as connecting an inner space formed by bringing the resin film and the vacuum tray into close contact to a vacuum pump and applying a negative pressure. The cover that encloses the space is temporarily shifted from the top of the vacuum tray so that fine water particles do not fly around unnecessarily, and the pressure tray is in close contact from the top of the vacuum tray, and not only the negative pressure on the lower side but also the compressed air on the upper side. Feeding high pressure may be applied. A fine water particle spray unit incorporates a commercially available ultrasonic humidifier that generates and sends fine water particles of about 1 to 10 μm into an apparatus, and is connected to the enclosed back side space above the resin film which is a blow destination. It is good enough to be able to send fine water particles. The time and timing control of each process is easily possible with electrical control.
The action of the thirteenth solution means can easily procure a source of fine water particles having a diameter of 100 μm or less and a blower. The diameter of the fine water particles delivered from a number of commercially available ultrasonic humidifiers for home use is about 1 to 5 μm.

As described above, according to the present invention, in transfer of a transfer film to a three-dimensional object, deformation suppression and positioning of the transfer film are enabled, and in air pressure transfer, non-heat transfer is enabled, and an inkjet adhesive ink is used. By using it in combination with various transfer media other than water transfer sheet, it becomes possible to improve the workability of transfer work, to speed up transfer, to automate, etc., and to provide a transferred product and a transfer device using the ink. It can.

FIG. 1 is a cross-sectional view in which an adhesive film layer is placed on a transfer film pattern on a transfer sheet showing an embodiment of the present invention. (A) is a cross-sectional view in which the adhesive film layer is mounted in the same shape as the transfer film pattern, (B) is a cross-sectional view in which the adhesive film layer is mounted so as to cover the transfer film pattern. FIG. 2 is a cross-sectional view showing the steps of printing an adhesive film pattern on a thermal transfer foil to form a thermally adhesive resist removable even after heat and pressure, and obtaining an image reverse to the printed pattern. (A) is a cross-sectional view in which the thermal transfer foil on which the lower transfer material and the upper adhesive film layer are formed is opposed, (B) is a cross-sectional view showing after thermal transfer, (C) is not yet It is sectional drawing which is peeling the adhesion part. FIG. 3 is a schematic view showing a state in which a transfer film sandwiched by a clamp frame is covered on a vacuum tray on which a material to be transferred is disposed. FIG. 4 is a schematic view in which a vacuum tray on which a transferred material covered with a transfer film sandwiched by clamp frames is disposed and an upper cover for enclosing sprayed fine water particles are opposed to each other.

Hereinafter, an example of a transfer method using, as an adhesive ink, an organic solvent containing an organic-inorganic hybrid composition capable of obtaining a cured silica hybrid film according to the present invention will be described with reference to the drawings.
As shown in FIG. 1, the transfer film pattern 3 is formed on the side of the transfer film 2 of the transfer sheet, and the adhesive film layer 4 is printed on the transfer film by an inkjet printer. The adhesive film layer 4 may be formed only on the transfer film pattern portion (A) or may be formed to cover the transfer film pattern portion (B). In hydraulic transfer, the latter is more effective in suppressing pattern deformation. Since the tackiness disappears after drying, post-treatment of the exposed portion protruding from the transfer film pattern to the periphery is unnecessary. The base paper 1 provided on the lower side of the transfer sheet is attached in order to improve the handling such as the printing operation. It is removed before or during the transfer step.
As shown in FIG. 2A, in the commercially available foil for thermal transfer, a peeling layer 9 is formed on a carrier film 10. The three layers consisting of the thermosensitive adhesive layer 6, the foil layer 7 and the surface protective film layer 8 thereon are transferred onto the material to be transferred 5 (B). Although there is no adhesive force at the adhesive film layer 4 portion that has already been cured, the foil of three layers around is transferred, so as shown in FIG. Metastasize. Since it is desirable to whiten the adhered portion of the adhesive film layer 4, next, the adhesive tape 11 is pressed and then peeled off. Since it does not adhere to the material to be transferred 5, the four layers consisting of the three layers and the adhesive film layer 4 are easily peeled off.
As shown in FIG. 3, in the case of pneumatic transfer, the material to be transferred 5 is disposed in a vacuum tray 12. The transfer film 2 is sandwiched between the two clamp frames 13 in the form of a sandwich, and the transfer film 2 is placed on the fixed position of the tray 12. In the next transfer process, the tray inner space 15 on the lower side of the transfer film is depressurized, and the drooping transfer film 2 adheres to the transfer material 5. Depressurization is performed by a vacuum pump VP.
As shown in FIG. 4, the moisture application to the transfer film 2 in the air pressure transfer is performed by the outer space 16 surrounded by the cover formed under the upper cover 14 moved to the upper side of the vacuum tray 12 covered with the film. Spray fine water particles. Fine water particles are fed from the ultrasonic humidifier UF through a pipe connected to the upper central hole provided in the upper cover 14. The upper central hole is preferably provided with a filter 17 for diffusing the inflowing fine water particles. In FIG. 4, there is a gap between the tray and the upper cover so as to eject fine water particles, but if the discharge hole is provided in the upper cover, the upper cover may be in close contact. The upper cover 14 is movable by an up and down movement or a swing mechanism or the like so as not to be an obstacle when setting the material to be transferred 5 in the vacuum tray 12.
The differences between the water pressure transfer sheet and the water transfer sheet in the examples will be described. Both are composed of two layers of a water-soluble resin layer and a base paper, and the handling property for printing and the like is good. The base paper is removed at the time of transfer. The water-soluble film separated from the water pressure transfer sheet is as thick as several tens of microns and swells on the surface of the water and does not dissolve immediately. On the other hand, the water-soluble film of the water transfer sheet separated from the base paper is as thin as several microns and readily dissolves in water. In order to prevent the water decomposition of the image formed on the water transfer sheet, it is necessary to previously form a resin layer by spray coating or the like so as to cover the vicinity of the image. When a water transfer sheet is used for transfer to a flat surface, there is a usage to press against the material to be transferred with the base paper attached and apply water from the back to slide off the base paper. Thinner layers are better. Examples of the water-soluble resin referred to in the present invention include PVA resin, water-soluble polyurethane resin, dextrin, gelatin, glue, casein and the like among synthetic polymers and natural polymers. These resins may be used alone or in combination of two or more. Although a sheet for water transfer can be freely selected, for pneumatic transfer, a synthetic polymer resin which can simultaneously obtain tear strength and flexibility is preferable. In particular, PVA resin is preferred.

EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
Example 1 (water pressure transfer)
A temporary adhesive base paper is attached to a 30 μm water-soluble Poval film (trademark, Kuraray Co., Ltd.) made of PVA resin and a toner image is formed by a laser printer to form a toner image, which is an organic / inorganic hybrid adhesive ink. An adhesive film layer was formed on the toner image with a PX-S160 T-type inkjet printer (trademark, Seiko Epson Corporation). Since the single-color monochrome printer, the adhesive film layer is 100% solid ink printing. The ink drying rate is set to maintain the adhesion of the solid printing layer for about 24 hours. An ABS resin-made round pipe cut product was selected as a material to be transferred for hydraulic transfer. In order to compare image deformation levels, the set ink leaving time before transfer is three steps of 5 minutes, 1 hour, and 2 hours. The circular pipe side was held in the horizontal direction, and the film floated in the water tank was sunk slowly and straightly, but after 5 minutes, an unmeasurable image elongation was observed on the side of the circular pipe. After 2 hours of drying and curing time, there was almost no image elongation as when the cylindrical side was rolled. The deformation was an intermediate level although the 1 hour drying and curing time was taken. The adhesion strength levels of the transferred images were also compared. The complete curing time of the simple transfer ink under natural leaving conditions depends on the leaving place environment, but it is about one month, so the round pipe adhesive film layer curing conditions after transfer are naturally leaving for 1 day, 1 week, 4 weeks, There were four conditions of forced drying at 80 ° C. for 20 minutes. Both the peeling and scratching tests on the first day were not sufficient, but otherwise there was no drop-off due to grid peeling, and there was no problem with the nail scratching test.
Example 2 (humidified air pressure transfer)
A vacuum transfer device was prepared, and image transfer to a 3D transfer material was attempted using a 30 μm water-soluble Poval film for curved surface transfer. When a 160 mm × 260 mm × depth 30 mm tray was covered and adsorbed, the film was broken and could not be absorbed to the bottom. However, when it was left for 3 minutes in a space sprayed with 1 to 5 μm of fine water particles using an ultrasonic humidifier AHD-013 SHIZUKU Plus (trademark, Apix International Co., Ltd.), it was sucked with the tray, and the bottom was completely reached. I did not tear it closely. Example 1 A similar toner image and adhesive film layer were formed on a Poval film, and a polycarbonate resin portable cover was placed at the center of the tray and transferred, and the image was clearly transferred from the top face of the portable cover to the curved side. . The film may be dissolved in water, but the film could be peeled off leaving the image on the transfer material side without being broken even if the film is peeled off immediately after the end of the vacuum time. On the other hand, Poval film sprayed and sprayed with water by a commercially available spray gun was put on a tray and holes were opened immediately after the start of adsorption and it was not absorbed. Also, if the depth of the tray is reduced to 10 mm and a polycarbonate resin flat plate is placed at the center and a poval film that has been left in the fine water particle spray space for only 2 minutes is adsorbed, the film can be peeled off. About half of the film remained on the film side. When the adhesion of the adhesive layer was raised by leaving it for 10 minutes instead of immediately after the end of the vacuum time, about 80% of the image was transferred. Immediately after the end of the vacuum time, when an additional spray was applied from the portable cover to the Poval film before peeling and removal for 2 minutes with the ultrasonic humidifier, the image could be peeled off leaving the image on the transfer material side.
Example 3 (dry pressure transfer)
Select 60 μm thick plain film CTP1147 as unstretched type CPP resin film, and select 60 μm thick Lick film L6100 (trademark, Toyobo Co., Ltd.) as unstretched type LLDPE resin film, and inkjet with Latex 360 printer (trademark, HP company) A printed image was formed. The loaded latex ink can be printed directly on these olefin films without an ink receiving layer by printing while heating with a kind of aqueous resin ink. Next, an adhesive film layer was formed on the latex ink image by an inkjet printer model VJ-628 (trademark, Mutoh Kogyo Co., Ltd.). The tray bottom of Example 1 was lowered to attempt transfer by placing the cell phone cover in the center of the tray as a 160 mm × 260 mm × 40 mm deep volume. The film was stretched under the side by vacuum force and rolled up, and a good transfer was made. When both films of the non-stretching type CPP resin film and the non-stretching type LLDPE resin film are stretched by a certain degree or more, the contraction force is not strong even if the vacuum is released. The film did not come off from the cell phone cover as it returned to its original size. After leaving the film as it was and peeling off the film the next day, the image was clearly transferred.
Example 4 (thin film transfer and conductivity)
An aluminum layer is formed with a thickness of 10 nm on the entire surface of a water transfer sheet B (trademark, Sanryu Co., Ltd.) having a dextrin water-soluble layer on the surface by a dry coating method, and a PX-S160T type is formed thereon A circular adhesive film layer was printed and formed by an inkjet printer (trademark, Seiko Epson Corporation). This was pressed against an epoxy resin plate to carry out water transfer in which water was applied from the back side. The aluminum layer was transferred onto the epoxy resin plate in the quadrangular shape of the water transfer sheet B that was cut out, but the outer side is the adhesion where the dissolved dextrin acts as a water-soluble paste, so the circular shape is washed with a damp sponge It could be removed easily except the part. A round foil could be formed on the epoxy resin plate. That is, it was confirmed that the adhesive film layer was printed on a part of the coating film formed in a wide area with the adhesive ink, and the coating film could be transferred only to the pattern portion.
When the conductivity was confirmed, the 50 nm-thick vacuum-deposited aluminum layer on the water transfer sheet B before transfer was conductive, but the circular aluminum layer after transfer had lost conductivity.
Next, on a PVA resin surface of a hydraulic transfer sheet SO sheet (trademark, Icero Co., Ltd.) in which a PET film is temporarily adhered to a PVA resin film, a copper layer is formed to a thickness of 50 nm by vacuum evaporation in dry coating. Copper plating was applied by electroplating to form a copper layer having a thickness of about 5 μm. Thereafter, a resist layer was further formed on the copper layer, exposed and developed to form a resist mask for a circuit pattern, and then etching was performed to obtain a circuit pattern composed of the copper layer after peeling off the resist mask. . An adhesive film layer of the same shape and size was printed and formed only on the circuit pattern portion with a PX-S160T ink jet printer (trademark, Seiko Epson Corporation). This was pressed against an epoxy resin plate and then the PET film on the back side was peeled off. Furthermore, 1 to 5 μm fine water particles ejected from an ultrasonic humidifier AHD-013 SHIZUKU Plus (trademark, Apix International Inc.) were sprayed on the back surface of the exposed PVA resin film, and then the PVA resin film was peeled off. When the conductivity of the circuit formed on the epoxy resin board was confirmed, the conductivity could be confirmed.
Example 5 (non-heat transfer of commercially available transfer foil)
Commercially available cold transfer foil AL KPW MATT (trademark, Kurtz Japan Co., Ltd.), thermal transfer hologram foil, HK038U2 (trademark, Katani Sangyo Co., Ltd.) on the foil side opposite to the carrier film, inkjet printer type VJ-628 (trademark The adhesive film layer pattern was printed and formed by Muto Kogyo Co., Ltd.). Select PET film as material to be transferred, take drying time of adhesive film layer for about 1 minute and press it on it, and simply peel off the carrier film to make these foil patterns of the same shape as the adhesive film layer pattern on the PET film It could be formed. Although the ink for simple transfer, which is an organic / inorganic hybrid adhesive ink (trademark, Sanryu Co., Ltd.), requires a drying time of about one minute to obtain sufficient adhesion for cold foil transfer, but at the time of ink production If the amount of solvent is adjusted in the direction of quick drying such as reducing the ratio of the amount of high boiling alcohol to the middle boiling alcohol, transfer without drying time is also possible.
Example 6 (heat transfer resist)
A commercially available thermal transfer foil, on the foil side opposite to the carrier film of Fine Foil VC-PK2 (trademark, Katani Sangyo Co., Ltd.), using a simple transfer ink (trademark, Sanryu Co., Ltd.) which is an organic / inorganic hybrid adhesive ink The adhesive film layer pattern was printed and formed by an ink jet printer. The printed thermal transfer foil was placed in a 140 ° C. drying oven for 30 minutes to cure the pattern and lose adhesion. When the printed thermal transfer foil taken out of the furnace was heated and pressed at 180 ° C. for 1 minute against a PET film as a material to be transferred, the thermal transfer foil was transferred over the entire area pressed against the PET film. However, the foil of the pattern portion is connected only to the surrounding foil and transferred from the carrier film to the material to be transferred, but not bonded. When an area covering the pattern portion was pressed against a commercially available adhesive tape and slowly rolled, only the portion where the pattern adhered to the lower layer was removed together with the adhesive film layer. It was confirmed that the adhesive film layer pattern was effective as a thermal transfer resist. In addition, before thermal transfer, the pattern after curing was not broken or dropped following the foil surface even when it was bent in the direction opposite to the winding of the thermal transfer foil.
Example 7 (humidified air pressure transfer after activation treatment)
Inkjet printed images were formed on a 30 μm water soluble Poval film with a Latex 360 printer. Next, a pressure-sensitive adhesive layer was formed on the image layer side by spray coating of an activator composition comprising a resin such as a short oil alkyd, a solvent containing butyl cellosolve and a ketone ester, and a dibutyl phthalate plasticizer. Next, after leaving the printed image formed poval film in a space sprayed with 1 to 5 μm of fine water particles for 3 minutes using an ultrasonic humidifier AHD-013 SHIZUKU Plus (trademark, Apix International Co., Ltd.), A tray with a polycarbonate resin portable cover placed at the center, 160 mm × 260 mm × depth 30 mm, was drawn and sucked. Poval film was adhered from the top of the cell phone cover to the curved side. After that, not only Poval film could be removed by water dissolution while leaving the image on the portable cover, it was heated at 130 ° C for 5 minutes to dry and cure the adhesive layer, and then it was again in the space sprayed with fine water particles. It was also allowed to stand for 3 minutes to allow film peeling.

The various transfer methods of the present invention can transfer images and circuit patterns onto a three-dimensional object with high accuracy and efficiency. It can be used to manufacture automobile interior materials, building materials, furniture, electric circuit boards, souvenirs, etc.

DESCRIPTION OF SYMBOLS 1 ... base paper, 2 ... transfer film, 3 ... transfer film pattern, 4 ... adhesive film layer, 5 ... material to be transferred, 6 ... heat-sensitive adhesive layer, 7 ... foil layer, 8 ... surface protective film layer, 9 ... peeling Layers 10 Carrier film 11 Adhesive tape 12 Vacuum tray 13 Clamp frame 14 Top cover 15 Inner space 16 Outer space surrounded by a cover 17 Filter VP Vacuum pump , UF ... ultrasonic humidifier

Claims

An adhesive film layer is formed by an ink jet printer using an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the transfer film side formed on a water-soluble resin film. The adhesive film comprising the steps of adhering the adhesive film layer side to the transfer material by water pressure transfer method after printing and forming the water-soluble resin film and removing the water-soluble resin film. Forming a transfer film pattern through a layer.
Ink jet printer using an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the transfer film side formed on a water-soluble resin film composed of a synthetic polymer as an adhesive ink The water-soluble resin film, after printing and forming the adhesive film layer, is placed in a space humidified with steam to a humidity of 60% or more for a certain period of time, or water particles having a diameter of 100 μm or less are attached Applying water to the water-soluble resin film having the adhesive film layer formed by one method, adhering the adhesive film layer and the material to be transferred by an air pressure transfer method, peeling, or dissolving in water Removing the water-soluble resin film by the step of forming a transfer film pattern on the transfer material via the adhesive film layer.
An organic solvent containing an organic-inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing is formed on the transfer film side formed on a transfer film comprising a polyolefin resin or a PVA resin filled with a plasticizer. After printing and forming an adhesive film layer using an inkjet printer using an adhesive ink, the step of adhering the adhesive film layer to a material to be transferred by air pressure or elastic pressure, and peeling off And removing the transfer film, forming a transfer film pattern on the transfer material via the adhesive film layer.
The transfer method according to any one of claims 1 to 3, wherein the transfer film is a transfer film formed by at least one of dry coating, wet coating, and printing.
5. The transfer method according to claim 1, wherein the transfer film on the transfer film is a transfer film patterned before transfer.
An organic / inorganic hybrid that provides a cured silica hybrid film after drying and curing on the foil side opposite to the carrier film of the transfer foil consisting of at least a carrier film, a release layer, and a foil layer, or on the transfer material side. The adhesive film layer side is printed on the adhesive film layer side after printing and forming an adhesive film layer pattern using an ink jet printer using an organic solvent containing the composition as an adhesive ink, and either the non-heat pressure or the low temperature heat pressure on the transfer material Forming a foil pattern having the same shape as that of the adhesive film layer pattern on the material to be transferred via the adhesive film layer including the step of bringing into close contact with the substrate and the step of peeling and removing the transfer foil. And the transfer method.
Adhesive film layer pattern by an ink jet printer using an adhesive ink comprising an organic solvent containing an organic / inorganic hybrid composition capable of obtaining a cured silica hybrid film after drying and curing on the foil side opposite to the carrier film of a thermal transfer foil Drying and curing the adhesive film layer pattern until it loses adhesiveness, and heat-pressing the foil side against the material to be transferred to transfer the thermal transfer foil onto the material to be transferred And a step of removing only a portion of the transferred thermal transfer foil to which the adhesive film pattern is attached to the lower side.
Organic / inorganic hybrid that provides a cured silica hybrid film after drying and curing on a water-soluble resin film or a patterned conductive layer with a thickness of 0.5 μm or more formed on a substrate for electrodeposition metal pattern transfer After printing and forming an adhesive film layer pattern by an inkjet printer using an organic solvent containing a composition as an adhesive ink, the adhesive film layer is not heated against the transferred material having an insulating property at the transfer location, or The adhesion on the material to be transferred, including the steps of heat pressure bonding, and leaving the conductive layer on the material to be transferred and peeling or dissolving the water-soluble resin film or the stainless steel plate by water dissolution. Forming a conductive layer through the membrane layer.
The transfer method according to any one of claims 1 to 8, wherein the concentration of silica dispersed in the cured silica hybrid film is 5 wt% to 80 wt% and the single particle diameter is in the range of 1 to 100 nm. Adhesive ink for inkjet printing.
Silica having a single particle diameter in the range of 1 to 100 nm is dispersed at a concentration of 5% by weight to 80% by weight, and an organic / inorganic hybrid cured film having an affinity for both organic and inorganic substances is used as an adhesive layer A transferred material characterized in that a conductive transfer film pattern having a thickness of 0.5 μm or more is held on the insulating surface of a material to be transferred.
The step of applying an activation treatment to the transfer film side formed on the PVA resin film to obtain an adhesive film, or placing the PVA resin film in a space which has been humidified by steam so as to have a humidity of 60% or more for a predetermined time Alternatively, a step of adhering or spraying the sprayed water particles of 100 μm or less or swelling and softening the PVA resin film by at least one method, a step of adhering the adhesive film layer and the transfer material by an air pressure transfer method, and water dissolution And the step of removing the PVA resin film by peeling, forming a transfer film pattern on the transfer material via the adhesive film.
A transfer device for pneumatically transferring a transfer film formed on a water-soluble resin film onto a material to be transferred, wherein an inner space formed by bringing the resin film on which the transfer material is placed into close contact with the tray is an outer space. And a water particle sprayer having a structure capable of spraying fine water particles having a diameter of 100 μm or less in a space surrounded by a cover of the outer space, and the resin film It is characterized in that it is possible to spray at least one of the fine water particle spray before adhering to the transfer material, or the fine water particle spray before removing the resin film from the transfer material. And a transfer device.
The transfer device according to claim 13, wherein the water particle spray unit is configured by an ultrasonic humidifier capable of spraying the fine water particles.