WO2000002970A1

WO2000002970A1 - Adhesive, method of bonding, and high-hardness product having layer of the adhesive

Info

Publication number: WO2000002970A1
Application number: PCT/JP1999/003743
Authority: WO
Inventors: Akiyoshi Tanimoto
Original assignee: Hyogo Trading Co., Ltd.
Priority date: 1998-07-13
Filing date: 1999-07-12
Publication date: 2000-01-20
Also published as: AU8129998A; AU4650999A; WO2000002739A1

Abstract

An adhesive usable for mass-producing interior building materials, exterior building materials, furniture materials, etc. by the transfer method. The adhesive comprises an E•B-curable glue, a low-viscosity radical-polymerizable monomer or oligomer which gives a resin and is incorporated for reducing the viscosity, and a photopolymerization agent contained in such an amount as not to enable the UV curing of the monomer or oligomer to proceed completely. After the adhesive is semicured by UV irradiation, bonding of a stamped film is conducted with a hot stamper. Thus, smoothness after transfer, paper laminating, or film laminating can be improved. Subsequent E•B irradiation can complete curing and bonding. The rate of transfer and laminating depends on the rate of E•B curing. Hence, transfer and bonding can be conducted at a rate as high as 30 m/min or higher. Thus, a transfer-coated material or transfer-coated mirror-surface material can be provided which is excellent in all of appearance, stain resistance, chemical resistance, heat resistance, fire resistance, marring resistance, and mirror properties, which all are required of, e.g., interior building materials.

Description

Specification

Adhesive, bonding method, and high-hardness product having the adhesive layer

The present invention relates to a transfer coating material that can be used for, for example, building interior materials, exterior materials, and furniture materials, and an adhesive material and a bonding method capable of manufacturing a transfer mirror surface coating material at a high speed. It is characterized by using a new adhesive that mixes monomers and oligomers of radically polymerized resins with low viscosity to lower the viscosity, and furthermore uses a photopolymerizing agent mixed into the resin so that UV curing does not proceed 100%. As a result, for example, a transfer coating material or transfer excellent in design, stain resistance, chemical resistance, heat resistance, flame resistance, abrasion resistance, and specularity required for building interior materials The present invention relates to an adhesive and a bonding method capable of providing a mirror surface coating material by high-speed bonding, and a high-hardness product having the adhesive layer.

Background art

As a typical representative interior material for construction, a veneer that makes use of beautiful wood grain, such as natural wood, a sliced veneer, a thorn veneer, and a half-round veneer, is used to attach this veneer to the surface of plywood. There is a board overlay plywood.

However, because it is difficult to obtain a veneer with beautiful wood grain and it is expensive, direct printing is performed by filling and filling the surface of inexpensive material, and then transferring the wood grain or the required pattern by elaborate printing. Plywood is produced and used.

In addition, as a resin overlay plywood in which a synthetic resin film, impregnated paper, and a resin laminate are pressed against the surface of the plywood, a resin film overlay plywood, which is covered with a resin film on which a pattern or the like is printed as necessary, and a plastic laminate. Simultaneous overlaying, resin sheet overlay plywood using colored or patterned paper, There is a resin plate overlay plywood in which a resin plate prepared by previously impregnating resin into paper or cloth, such as a lamin resin decorative plate, is attached to the plywood.

In recent years, the base material for overlaying the above-mentioned synthetic resin films, impregnated paper, resin laminates, etc. is not limited to the above-mentioned plywood, but also paper boards, fiber boards, vegetable boards, wood chips, etc. Various materials such as cement boards, rubber materials, inorganic materials, metals, and laminates thereof have been adopted.

The conventional thermal transfer film has a pattern adhesion color layer provided on a base film via a release layer, and further has an adhesive layer laminated thereon.The adhesive layer of the thermal transfer film is brought into contact with the surface of the transfer partner material and heated. It has the function of fixing the pattern-attached color layer to the surface of the material to be transferred by applying pressure through the adhesive layer.

The above-mentioned release layer, pattern-attached color layer, and adhesive layer can be easily printed on the substrate film by various printing methods, especially gravure printing. Therefore, PET and PVC films, which are thin films, have excellent heat resistance and thermal conductivity, and are flexible enough to conform to the shape of the adherend, have been used.

In particular, from the viewpoint of durability, heat insulation, and productivity, inorganic plates such as cement boards, lightweight concrete, and ceramics have come to be used for exterior wall materials today. At first, the surface design ability utilizing the properties of the material was used, but the design property was gradually gaining importance as in the above-mentioned resin overlay plywood.

On the other hand, inorganic plates have come to be used as the base material for today's building interior materials, and the design properties required as essential functions can be realized by the various overlay methods described above. At the same time, many functions have been required to be added to physical properties because they are not natural materials.

In other words, the characteristics required for today's building interior materials are:

(1) Pollution resistance Not to be affected by various pollutants in the home, (2) Chemical resistance Not affected by various chemical substances,

(3) Heat resistance Not to be destroyed by high temperature (eg 140 ° C),

(4) Flame resistance Although it is a short time, it does not burn by flame,

(5) Scratch resistance It is required that the material has an appropriate hardness and that scratches and roots are not easily formed.

Another characteristic that is required depending on the application is specularity.

(a) The surface should be as smooth as possible without distortion,

(b) high gloss,

(c) that the above two points can be retained for many years;

Are required.

In short, today's architectural interior materials have been required to have excellent physical properties and high specularity at the same time as being applied with transfer coating to impart design properties using inorganic plates as base materials. No material that satisfies all requirements has been proposed.

Therefore, it is necessary to analyze the conventional transfer films and processing methods for inorganic plates, and consider their advantages and disadvantages together with the future of production technology. The inventor's consideration is shown below.

First, regardless of the type of transfer film, there are always problems such as poor adhesion and peeling over time.

PVC films are inexpensive and have good design, but have poor heat resistance and have the problem of generating dioxins, especially when burned. There is a film coated with fluorine to impart stain resistance and chemical resistance to this PVC film, and it is extremely expensive due to the fluorine treatment, but the above problem has not been solved.

Among the melamine resins, low-pressure melamine has excellent scratch resistance, but cannot be mirror-finished and has poor design properties. High-pressure melamine is excellent in various physical properties such as design properties, scratch resistance, chemical resistance, etc., but is expensive because it requires labor for production. Dup film is excellent in various physical properties such as scratch resistance and chemical resistance, but cannot be mirror-finished and has poor design properties.

In addition, there have been proposed various types of synthetic resins alone or films in which various films are laminated in accordance with required physical properties, and have the advantage of being excellent in productivity because they only need to be bonded to a base material. Is not easy to change, and there are problems such as peeling due to poor bonding.

On the other hand, with regard to the coating treatment, typical urethane coatings have the advantages of being easy to handle, inexpensive, and have low capital investment. Their design is poor, and the aforementioned physical properties are inferior.

UV coating can be expected to have higher physical properties than urethane, has the advantage of high productivity and low capital investment, but is difficult to apply to applications that require high hardness because the required film thickness cannot be obtained.

Inorganic coatings and fluorine coatings have the potential to produce the required high-performance products, but have the problem of poor mass productivity and the inability to provide interior materials at low cost.

If the current mainstream transfer (Hot Stamp) technology is introduced, the following problems will be added. In the transfer layer, a pattern-attached color layer and a coating film are laminated on the substrate surface via an adhesive layer (Hot me). However, in particular, the physical properties of heat resistance and flame resistance deteriorate significantly due to the adhesive layer.For example, when the temperature becomes high, there is a problem that the adhesive layer softens or burns and the coating film is destroyed. is there.

The transfer includes paper pasting and resin film pasting. For example, as shown in FIG. 1A, a stamp film 5 having a three-layer structure of an ink pattern printing layer 3 and an adhesive layer 4 by providing a release treatment layer 2a on a PET film 2 that is usually used frequently is shown in FIG. 1B. As shown in the drawing, the substrate 1 is pressed against the surface of the substrate 1 with a heated press roll. Thereafter, as shown in FIG. 1C, since the PET film 2 is peeled off, an ink pattern printing layer 3 is formed on the surface of the substrate 1 via the adhesive layer 4. Since this transfer is performed only with heat and pressure energy, it is difficult to perform high-speed transfer of 10 to 15 m or more per minute. The use of an adhesive made it impossible to increase the speed to 30m or more.

For the purpose of improving the transfer speed, an adhesive (Ε · 線 glue) made of an electron beam curing resin using electron beam curing (硬化 · Β curing) has recently been developed. The process is as follows. As shown in Fig. 2 (1), a glue 7 is applied to the surface of the substrate 1 with a roll coater 6 and, as shown in Fig. 2 (1), a stamp film 8 is provided with an ink pattern printing layer on a release-treated PET film. The laminator or hot stamper press roll 9 is applied to the 7 layers of Ε · 先 glue, and then irradiated with an electron beam as shown in Fig. 2C to cure Β. To complete the bonding, and then peel off the PET film.

Since the transfer method using E-B glue uses electron beam curing of the adhesive, the processing speed can be increased. However, because the viscosity of the Ε · 高 glue is increased to improve the adhesiveness, it is difficult to apply it uniformly and accurately to the surface of the substrate, and the surface after transfer such as transfer or paper pasting, film pasting, etc. Poor quality and problems. Disclosure of the invention

An object of the present invention is to provide a transfer coating material or a transfer mirror surface coating material that can be used for building interior materials, exterior materials, furniture materials, and the like that are mass-produced using the transfer method. The present invention is excellent in all of the design properties, stain resistance, chemical resistance, heat resistance, flame resistance, abrasion resistance, and specularity required for building interior materials, and all properties are satisfied. It aims to provide a transfer coating material or a transfer mirror surface coating material to be added.

In addition, the present invention provides a transfer coating material or a transfer mirror coating material which satisfies all the characteristics of design, stain resistance, chemical resistance, heat resistance, flame resistance, abrasion resistance, and mirror finish. The purpose is to provide a transfer coating or transfer mirror coating method that can be mass-produced by high-speed transfer. Another object of the present invention is to provide an adhesive material and an adhesive method capable of performing high-speed bonding, such as high-speed transfer and film bonding, with a high degree of adhesion.

The inventor of the present invention is to uniformly and accurately apply an adhesive to a substrate surface in a transfer method using a Β · にする glue, and to improve surface properties after transfer, such as transfer or paper pasting or film pasting. Various studies were carried out for the purpose. As a result, low-viscosity monomers and oligomers of radically polymerized resins are mixed into the glue to lower the viscosity, and a new photopolymerizing agent is mixed into the resin to prevent UV curing from proceeding 100%. By using an adhesive (EB / UV glue), it was found that this adhesive was easy to apply due to its low viscosity, and that a smooth flat surface could be easily obtained by using a reverse opening.

In addition, the inventor has conducted intensive studies on the E and B / UV glues. As a result, after application, semi-curing by UV irradiation was performed to cure a layer having a certain thickness or more from the surface, and at the same time, added to reduce the viscosity. It was found that it is possible to restore the original tackiness by curing the resin. That is, the adhesiveness can be improved by UV semi-curing after the application of the adhesive, and the workability is improved, as well as the smoothness during the previous application. More specifically, by applying a stamp film by a hot stamping machine after semi-curing by UV irradiation, the smoothness after transfer or pasting on paper and after film pasting is improved. It was found that transfer and bonding speeds up to a maximum of 80 m / min were theoretically possible, since the transfer and bonding speeds were similar to the curing speeds.

Further, the inventor studied the resin layer provided on the base material surface by bonding a stamp film using the E'B / UV glue, performing a semi-curing and a semi-curing on the UV, and performing a UV curing. As a result, the use of UV glue has a significant effect on improving the peel strength, heat resistance, and flame resistance of stamp films and papers, and finally, from the top coat on the surface to the UV-cured parts, all at once As a result, it was found that it was possible to completely polymerize completely by Ε · Β irradiation. In addition, the polymer resin is chemically integrated between the layers by Ε · Β irradiation, and has extremely high peeling strength. Furthermore, radical polymerization by Ε-Β results in extremely strong intermolecular bonding force. (4) It has been found that flame resistance is remarkably improved because it is resistant to shrinkage due to heat and because there is no oxygen that causes combustion in the cured resin. By the transfer method using the E'B / UV glue of the present invention, a resin layer that satisfies all the properties of design, stain resistance, chemical resistance, heat resistance, flame resistance, scratch resistance, and specularity is obtained. It was found that it was possible.

In short, the new adhesive, EB / UV glue, according to the present invention is capable of applying a low viscosity once and applying it uniformly and at high speed with smoothness. After hardening, the original viscosity is restored to increase the adhesive strength, and the flatness and homogeneity of the tip make it possible to greatly improve the bonding workability, and it is possible to completely solidify by subsequent EB irradiation. The present inventors have found that it is possible to increase the bonding speed of transfer and pasting to the curing speed, and completed the present invention. BRIEF DESCRIPTION OF THE FIGURES

FIGS. 1A, 1B, and 1C are explanatory views of a substrate and a stamp film showing steps of a transfer (hot stamp) method.

FIGS. 2A, 2B, and 2C are explanatory views of a substrate and a stamp film showing the steps of a transfer method using E-B.

3A, 3B, 3C, and 3D are explanatory views of a substrate and a stamp film showing the steps of a transfer method using an E.B / UV glue according to the present invention.

FIG. 4A is an explanatory view of a substrate showing an E'B / UV glue coating process according to the present invention. FIGS. 4B, 4C, 4D, and 4E are diagrams of a transfer method using EB / UV dull according to the present invention. FIG. 3 is an explanatory cross-sectional view showing a stacked state. BEST MODE FOR CARRYING OUT THE INVENTION

The steps of the transfer method using the adhesive according to the present invention will be described. First, an EB glue as an adhesive, a monomer or oligomer of a low-viscosity radically polymerized resin, and a light such that UV curing does not proceed 100%. Prepare an EB / UV glue that is mixed with a polymerization agent to reduce the viscosity to a predetermined level. As shown in FIG. 3A, when the above E'B / UV glue 10 is applied to the surface of the base material 1 with a roll coater 6, the application is easy due to the low viscosity, and the smoothness is easily achieved by using a reverse roll. A plane is obtained.

Next, as shown in Fig. 3Β, semi-curing by UV irradiation is performed after application, and a layer with a certain thickness or more is cured from the surface of the substrate 1, and at the same time, the resin added for lowering the viscosity is also cured. Create 10a. This makes it possible to return to the original tackiness, while improving the smoothness during the previous application and improving the adhesiveness by semi-curing the UV after applying the adhesive.

As shown in FIG. 3C, a stamp film 11 having a release pattern of a PET film provided with an ink pattern printing layer on an uncured layer 10b on the upper layer of the EB / UV glue 10 was pressed by a laminator hot stamping machine. Laminate with roll 9, then peel off PET film. Next, as shown in Fig.3D, the EB / UV glue 10 is cured by irradiating an electron beam to complete the bonding, and the separately applied surface from the top coat to the UV cured part is collectively processed. A series of steps are completed by completely integrating polymerization by irradiation.

Transfer according to the present invention The process of forming the coating film is described in detail. As shown in FIGS. 4 and 4, the EB / UV glue 10 is transferred to the surface of the base material 1 by a mouth coater 6 using a transfer layer and paper. An amount corresponding to the thickness of the adhesive is applied, and then semi-cured by UV irradiation to form a cured layer 10a and an uncured layer 10b.

As shown in Fig.4C, transfer by hot press, ie heated press roll

: Pattern to be laminated and peeled off PET film 13 The uncured layer is impregnated into the attachment layer 12 or the paper application layer to form the impregnated pattern attachment layer 12.

Next, as shown in FIGS. 4D and 4E, a clear layer 14 made of a curable resin as a top coat is applied on the impregnated patterning layer 12, and then the UV light is applied to the clear layer 14 by UV irradiation. The whole of the hardened layer up to the hardened layer 10a is completely integrated and polymerized by Ε · Β. In other words, each layer becomes a polymerized resin that is chemically integrated, and due to the radical polymerization by Ε · Β, the bonding force between the molecules becomes extremely strong, and the shrinkage due to heat becomes strong. Flame resistance is improved because there is no mixing of oxygen, which is a factor.

Mirror coating with the cross-sectional structure shown in Fig. 4 ΕThe coating is from the clear layer 14 composed of the curable resin on the surface to the cured layer 10a of the EB / UV glue at the lowermost layer. Different powers such as という and 、, UV Both resins are integrated by the same resin such as monomer and oligomer of radical polymerized resin such as acrylic resin and unsaturated polyester resin, and distortion occurs between each layer Since the adhesion does not decrease and the adhesion does not decrease, it can withstand the stress given by heat or the like under similar conditions.

In particular, the top Β · Β resin clear coating film is an acrylic resin that is polymerized by the highest energy content of a monomer of an extremely high-performance resin called an acrylic resin and a basic molecule called an oligomer. Due to the formation of the film, it becomes a very strong coating film.

The conventional urethane coating film is a polymer and has gaps between molecules.The UV coating film has weak bonding between molecules, so all contaminants easily penetrate, and destruction by external energy can occur. Easy to get up.

On the other hand, the acryl / EB / UV glue coating film according to the present invention has a low molecular weight, a small intermolecular gap, a strong intermolecular bond, makes it difficult for contaminants to penetrate, and is not easily damaged by external energy. Unlikely to happen. A similar example is diamond. Diamond is basically a bond of carbon and, as is well known in elemental terms, a very weak force. In this generation, it is produced at very high temperatures and pressures, far exceeding normal energy levels. I have. This has very high physical properties. Similarly, acrylic monomers and oligomers are also polymerized by electron beam energy, which is not usually considered, so that a naturally formed coating film is less likely to be destroyed by normal state energy. .

Unlike the conventional transfer layer, the impregnated patterning layer 12 uses a material that is very easy to permeate the resin molecules.When a clear resin is applied, acrylic monomers and oligomers can easily pass through. And are united.

The cured layer 10a of EB / UV glue strengthens the bonding strength of the base material by infiltrating low-molecular NCO, low-molecular acrylic monomers and oligomers, and changes the temperature and moisture of the base for many years. The movement of the material can be prevented. In other words, one of the important points in mirror-painting is to suppress the occurrence of distortion in the mirror-finished plane due to changes in the situation over time.

In the present invention, it is particularly important to use a paint having a solid content of 100% in all steps to form a moderately thick film, easily obtain the smoothness of the coating film, and obtain a paint free coating. That is, solvent conversion has been achieved.

Hereinafter, the adhesiveness, heat resistance, chemical resistance, stain resistance, bacteriostatic property, and weather resistance obtained by the transfer coating or transfer mirror coating method according to the present invention will be described. Inorganic materials, such as gaical plates, have a small organic content required for binding inorganic particles to secure the physical properties required for the certification of noncombustible materials. Up to now, it has been important to use a high-density, high-density material to improve the adhesion, but it is inevitably heavy and disadvantageous. Therefore, in the present invention, as a method of improving the adhesion strength of the inorganic material having a low specific gravity, about 10% of an isocyanate is blended with a permeable low-viscosity UV sealer to cure the inside of the inorganic material. The method can be adopted. Therefore, on the production line

UV curing does not hinder polishing, etc., and can be used to stop alkali in the carousel by reacting with the OH group of the isocyanate, and the effect of strengthening the bonding of inorganic particles by the OH group reaction of the isocyanate can be expected. .

Heat-resistant

Conventionally, when a seal layer provided on the surface layer of the base material, and furthermore, a colored or patterned layer, and a heat-resistant coating film as the outermost layer, a resin having no heat resistance is used for the seal layer and the patterned layer. Then, there is a problem that the weak portion softens and cannot support the heat-resistant coating film, resulting in deterioration.

Therefore, in the present invention, the heat-resistant coating film (top coat), the coloring and patterning layer, and the sealer layer are formed into one acrylic resin layer, that is, an inorganic pigment is used for the transfer layer used for the patterning layer. The resin must have a molecular weight greater than the molecular weight of the topcoat, so that the heat-resistant topcoat paint can easily infiltrate, and the resin has a high polymerization density so that it does not contain oxygen necessary for combustion. Make the coatings flexible to withstand high temperatures (around 14CTC). As a result, heat resistance of about 450 ° C is obtained.

Chemical resistance, stain resistance, bacteriostatic

The use of high polymerization density, which is inherent in cured resins, will inevitably provide chemical resistance, stain resistance, and bacteriostatic properties. When the pigment is mixed with some pigments such as enamel, it is necessary to use an inorganic pigment system.

Weatherability

In order to improve the weather resistance, it is necessary to mix an ultraviolet absorber to prevent the pigment and resin from changing color due to ultraviolet rays. We also selected inorganic pigments To ensure strong adhesion between paint layers to withstand unique movements in each layer, for example, differences in expansion and contraction due to moisture absorption, and differences in expansion and contraction due to heat. It is necessary to prevent intrusion and prevent adhesion of contaminants that chemically attack the coating film. The transfer coating according to the present invention has extremely high weather resistance because the heat-resistant coating film (top coat), the coloring or patterning layer, and the sealer layer can be formed into one acrylic resin layer.

Creativity

In the present invention, the following method is desirable in order to enhance the design of the coloring and patterning layer.

(1) The transfer resin layer is laminated on a sheet or roll-shaped base film for thermal transfer, and the transfer resin layer is transferred and adhered to the transfer substrate while applying heat to the transfer resin layer by pressing or rolling. In a transfer method, the transfer resin layer provided on the base film via a release layer is preheated by using 23 g / m2 to 50 g / m2 paper or aluminum foil or a composite paper of paper and aluminum foil for the base film. And then heat transfer onto the substrate.

(2) In a membrane press transfer method in which a transfer resin layer is laminated on a sheet-like base film for thermal transfer and heat is applied to the transfer resin layer while applying heat to the transfer resin layer by a NORMAL type heat press, Using a biaxially stretched foamed PP film for the base film, a transfer resin layer is directly laminated on the base film and thermally transferred.

(3) In the transfer method described above or the conventional transfer method, in which at least one resin layer is transferred onto a transfer-receiving substrate by coloring and / or patterning, the transfer method is applied to the transferred resin layer. Apply low molecular weight paint or resin with a smaller molecular diameter than the pigment, paint, resin, etc., on the transfer resin layer. (4) In the above transfer method for applying a top coat, the substrate to be transferred is an inorganic plate, and the substrate to be transferred is subjected to an alkali neutralization treatment or a pretreatment for providing a surface solidification resin layer.

When performing thermal transfer to fine irregularities by the hot-press roll transfer method, if paper is used for the substrate film, the total thickness of the paper and composite substrate film cover will be reduced to fine irregularities during the hot-press roll transfer. Make it thick enough not to break. In the conventional method of applying heat from the substrate film on the side opposite to the transfer layer, for example, a method is adopted in which a concave portion larger than a fine concave portion on the surface, such as a scratch on the substrate to be transferred or a groove generated in manufacturing the substrate, is used. However, since the yield point for pulling the paper is low, there is a problem that the substrate film always breaks at the concave portion and remains on the transfer surface without releasing when releasing.

To solve the problem, the paper may be made thicker. However, in this case, the heat conductivity of the paper is so low that the conventional method of heating from the base film side does not provide sufficient heat to the transfer layer for adhesion. Moreover, if the paper is thick, it will not fit well into fine irregularities. However, according to the present invention, the transfer layer is mainly formed by providing a release layer on both sides of a paper (23 g / m ² to 50 g / m ² ) which is not too thick and a colored pattern adhesive layer and a transfer layer. This is pre-heated from the layer side to about 50 ° C, and the substrate to be transferred is also pre-heated to about 50 ° C, and then the transfer film and the substrate are combined and transferred by a hot-press roller.

Therefore, in the present invention, a paper having a predetermined rigidity is used, the stretch is small at the time of roll winding, etc., and it is easily adapted to fine irregularities on the substrate to be transferred, and extra heat is applied to the release layer at the time of heating. Since it is not applied too much, release from the base film is better than before, and it has the effect of improving the bonding reliability of thermal bonding. In addition, the activation of the transfer layer can be promoted by the preheating, and the transfer and bonding efficiency have been improved, so that it is not necessary to apply unnecessary tension to the paper, and it is possible to prevent the paper from being broken at the above-mentioned concave portion. You.

In addition, the composite substrate film made of paper and resin according to the present invention has the following advantages over the conventional substrate films made of PET film and PVC film. You In other words, conventional PET film and PVC film substrates cannot be preheated to about 50 ° C because heating the film to about 50 ° C stretches the film itself. This eliminates unnecessary stretching of the base film, enables printing with dimensional accuracy when the transfer layer is printed, and can further increase the transfer speed.

In the present invention, the composite base film made of paper and resin can be a composite base film of aluminum foil and resin film, or a composite base film of aluminum foil and paper and resin film. By using aluminum foil for the composite substrate film, there is an advantage that heating from the substrate film side can be performed with high thermal efficiency. As the aluminum foil, various known thicknesses can be used, but a laminate of a polyethylene sheet or a polypropylene sheet is preferable to improve the releasability of the transfer layer.

In this invention, the paper 23g / m2~50g / m ² of Ru with a sheet or roll of thermal transfer base one Sufuirumu, such as kraft paper are available, 30 g / m ² or more preferably paper. For the release layer provided on one or both sides to promote the release property of the transfer resin layer and prevent migration, polyethylene, polypropylene and the like can be used, and a laminate of these sheets is preferable.

Conventionally, in the membrane press transfer method, a PVC film has been used as a base film. The reason for this is that PVC film can be relatively easily stretched in response to an increase in heat, and is well suited for transferring to a three-dimensional shape. However, there was a problem that the temperature control had to be controlled and maintained in an extremely narrow range of 170 ° C to 175 ° C in order to conform to the three-dimensional shape.

The present invention is characterized in that a biaxially stretched foamed PP film is used as a sheet-shaped base film for thermal transfer, and the biaxially stretched foamed PP film has a good heat resistance and a film at the time of pressing. Good elongation and contains a large number of air layers, so it has excellent follow-up ability to elongation force, and exceeds the softening point of resin from one direction Even if heat is applied, the air layer functions as a buffer for heat conduction, so the rigidity of the entire base film is secured, and the resin layer can be reliably transferred onto the uneven surface of the plate material with good adhesion Has an effect.

In other words, when the biaxially stretched foamed PP film is stretched with the same force under the same temperature conditions as compared with a solid PP film, the elongation Δ なり ^ is larger than the L _{2 of the} PP film. It has the property of being better than a solid PP film and more easily adapting to a three-dimensional shape. Also, in order to adapt to the three-dimensional shape,

Transfer was possible by controlling the temperature from 150 ° C to 175 ° C.

In the present invention, the transfer resin layer may have any one of known one to many layers. For example, when an inorganic plate is used as the substrate to be transferred, it is subjected to an alkali neutralization treatment or a pretreatment for providing a surface-solidification resin layer, followed by a colored undercoat, and then a transfer and lamination of a transparent resin layer on which a color pattern is printed. Or, by transferring and laminating a transparent resin layer printed with coloring and color pattern, by combining the uneven surface of the substrate, the pattern and the transparent colored pattern of the transfer sheet, while taking advantage of the pattern and the color developing action of the substrate, Various design patterns can be applied.

By using a structure in which a colored undercoat transparent resin layer, a transparent resin layer with a colored pattern, and a colored overcoat transparent resin layer are sequentially laminated on the transfer resin layer, a small number of patterns can be obtained while making use of the design pattern of the uneven surface of the base material. Many resin patterns can be produced with good reproducibility by combining these resin films. In addition, a two-layer film in which a colored undercoating transparent resin layer and a transparent resin layer with a colored pattern are a transfer film and are preliminarily laminated, or each of the transparent resin layers is a transfer film in which the transfer film is laminated in advance 3 By using a layer film, mass productivity is improved. In the present invention, the target substrate is not only a natural wood board but also a veneer overlay plywood in which a veneer such as a sliced veneer, a son veneer, a half round veneer, a rotary veneer, etc. is adhered to the surface of the plywood. Not only plywood but also veneer, paper board, fiber board made of resin made of plant fiber and wood chips, and particles Various materials such as boards, MDF, wood cement boards, rubber materials, inorganic materials such as various ceramics, metals, and laminates thereof can be used.

In the present invention, a transparent resin material such as a transparent film, a transparent adhesive, a colored transparent paint can be appropriately selected for the resin layer to be laminated, and an acrylic resin film, a vinyl chloride resin film, polypropylene Resin coatings made of acrylic polymer, vinyl polymer, cell mouth derivative, epoxy resin, etc. on base resin film and release-treated base film. Transparent films suitable for lamination are acrylic Or a transparent film of vinyl chloride is desirable.

Examples of the transparent adhesive include a solvent-type polyurethane adhesive, a moisture-curable polyurethane adhesive, an acrylic adhesive, and a vinyl acetate adhesive. Colored transparent coatings include polyurethane coatings, UV-curable epoxy coatings, polyester coatings, acrylic coatings, and aminoalkyd coatings. As a film-forming resin that can be dissolved in a coating solvent, a resin film having a thickness of about 2 to 3 μπι formed of an acrylic polymer, a vinyl polymer, a polyethylene wax, an epoxy resin, a cellulose derivative, or the like is preferable.

Depending on the method of bonding the resin film to the substrate, the adhesive side of the transparent resin film to be colored undercoat is arbitrarily determined as to whether an adhesive is to be applied to the film or to the substrate in advance. When the colored patterned transparent resin film and the colored overcoating transparent resin film are laminated, the basic configuration is the same except for the order of lamination. In this case, examples of the applied colored undercoat or overcoated transparent resin film include a vinyl chloride resin and an acrylic resin film, and the colored undercoat include a vinyl acetate film. In addition, the three-layer laminate structure is basically performed by the same lamination method as the two-layer structure. In the present invention, a low-molecular-weight paint or resin, such as a pigment, a paint, and a resin used for the transferred resin layer, is applied on the transfer resin layer so that the coloring and patterning resin layer is applied to the base material. The patterning is further strengthened. Specific examples of this include a colored undercoating transparent resin layer, a colored patterning transparent resin layer, and a colored topcoating transparent resin layer. The transparent resin layer uses a paint such as urethane paint, UV-curable polyester, UV-curable epoxy, or UV-curable acrylic, and the transparent resin layer with a colored pattern is laminated with a thermal transfer sheet made of the above acryl polymer etc. This can firmly fix the color tone and pattern on the base material.

Therefore, the method according to the present invention provides a transfer coating material or a transfer mirror coating material which satisfies all the properties of design, stain resistance, chemical resistance, heat resistance, flame resistance, abrasion resistance and specularity. It can be manufactured easily and with high productivity by mass production.

Process control

Hereinafter, the process control in the case where the coating according to the present invention is applied to the car board will be described.

1) To control the thickness of the car board (grinding), perform a back sanding process.

2) A surface sanding process is performed to ensure the smoothness of the surface of the sheet (grinding → polishing).

3) Apply a UV seal on the back side to prevent warping of the car board.

4) Apply a UV drying process to completely cure the UV sealer.

5) NCO is sufficiently penetrated into the substrate of the car board to strengthen the adhesion between the base particles, while the NCO reacts with the OH groups in the car board to neutralize the alkali, Apply NCO + 10% white base process.

6) Apply an NCO scraping step to completely scrape any NCO remaining on the surface to apply the UV filler. 7) Apply a UV filler process to completely seal the car board and reduce the load on the sealer sander.

8) Apply a UV drying process to completely cure the UV filter.

9) In order to smooth the surface roughness of the surface where the car board is filled with the UV filter, a seal polishing process is performed.

10) UV white glue is used to ensure that the transfer film of the next process can be applied at high speed and easily, and that the acrylic monomer and oligomer, the main resin of Glue, infiltrate into the transfer film. I do.

Glue is applied to the base material surface so that the transfer film of the next process can be applied at high speed and easily, and a white coat is applied to the base material surface so that the transfer film of the next process can be applied at high speed and easily. This is because tackiness is imparted, the applied glue uniformly impregnates the transfer film, and the main resin of the glue is reliably mixed into the transfer film.

To achieve these, it is required that the adhesive be applied uniformly and easily, that the applied adhesive surface have sufficient tackiness, and that a certain amount of resin be impregnated into the transfer film. Is done. Example

Example 1

Ε · Β The following steps were performed as a mirror-surface transfer coating using transfer and transfer. Process 1 Polishing the back side of the car board, dimensional tolerance within ± 0.05mm

Process 2 Surface polishing, dimensional tolerance within ± 0.05mm

Process 3 Backside UV-curable sealer, urethane coating for the purpose of preventing warping and improving water resistance Process 4 Drying, UV drying, hot air drying

Process 5 Surface isocyanate coating or UV sealer coating

Add about 10% isocyanate to UV curable paint Process 6 Scraping of the unit or UV-curable sealer (however, it is not necessary if permeability is good)

Process 7 Dry Not required if it does not affect UV filler application

Process 8 UV filler application

UV-curable polyester paint, UV-curable acrylic paint, and in some cases, ordinary thermosetting polyester paint, urethane paint, etc.

Process 9 UV drying

Process 10 Sealer polishing

Process 11 UV curable glue coating (characterized by complete curing and UV curing semi-curing) Process 12 UV semi-curing

Process 13 transfer or lamination

As long as it is easily impregnated, the material can be any of printing paper, transfer, and resin film.

Process 14 Apply pressure with a Ε · Βcurable top coat roller

Step 15 Β.Β Curable top coat Improve smoothness with curtain coater Step 16 Ε

Through the above steps, mirror transfer coating was applied to the required surface of the car board.

Example 2

Process 2 Surface polishing, dimensional tolerance within ± 0.05mm

Process 3 Backside UV curable sealer, urethane coating for anti-slipping and water resistance improvement Process 4 Drying, UV drying, hot air drying Step 5 Make a paint containing isocyanate in a UV curable film, infiltrate the paint into the base material with the pressing force of reverse roll coater, and form a coating film on the surface

Process 6 UV drying

Process 7 Sealer polishing

Process 8 UV curable glue application

Process 9 UV semi-curing

Process 10 Transfer or lamination Here, the material is printing paper

Process 11 Ε · Βcuring type top coat

Step 12 Improve smoothness by curing type top coat force

Example 3

Process 2 Surface polishing, dimensional tolerance within ± 0.05mm

Process 3 Backside UV curable sealer, urethane coating for the purpose of warping and improving water resistance Process 4 Drying, UV drying, hot air drying

Step 5 Create a paint containing isocyanate in a UV-curable filler, infiltrate the paint into the substrate by the pressing force of the reverse roll coater, and form a coating film on the surface

Process 6 UV drying

Process 7 Sealer polishing

Process 8 Low viscosity Ε · Βcurable glue coating Process 9 semi-cured

Ε-して To keep only the glue surface uncured, hold oxygen that precludes polymerization at a concentration of 200 ppm or more at a concentration of about 5% Ε. Β Irradiate and cure Step 10 Transfer or laminating

Process 11 Β · ΒCurable type top coat Apply pressure with roller

Step 12 Improve smoothness by using a hardening type top coat force. Step 13 Complete irradiation and curing.

Example 4

The following steps were performed in order to obtain a product similar to a mirror-transferred coated product using Ε · Ε painting and transfer without using Ε · Β.

Process 1 Polishing the back side of the car board, dimensional tolerance within ± 0.05mm

Process 2 Surface polishing, dimensional tolerance within ± 0.05mm

Process 3 back urethane

Process 4 drying, hot air drying

Process 5 Urethane coating (2 liquid type)

Process 6 drying

Process 7 polishing

Process 8 Urethane feeler application

Process 9 Sealer polishing

Process 10 Urethane type adhesion sealer application

Process 11 semi-dry

Process 12 transfer or lamination

Process 13 UV-curable top coat Roller-coater for pressure application Process 14 UV-curable top coat Curtain coater

Process 15 UV drying or N ₂ gas UV drying Through the above process, mirror-transfer coating was applied to the required surface of the car board without using Ε · Β.

Example 5

In Example 1, Step 13 is a post-transfer and lamination step.

Process 14 Ε · ΒCurable Topcoat Thinner Use カーテン · Βcurable resin to lower viscosity and use curtain coater

Process 15 thinner drying

Process 16 Irradiation and curing

By doing so, mirror transfer coating was applied to the required surface of the car board. In addition, in the same process as in Examples 2 to 4, the top coat can be cured after evaporation of the thinner.

Example 6

In Examples 1 to 3, mirror transfer coating was performed in the same process using an aluminum plate instead of the car plate.

Example 7

In Example 1, a wood-based material (MDF, P.B, etc.), here a particle pod (P.B), was subjected to mirror-surface transfer coating in the same process in place of the car board.

Example 8

A comparative test was conducted on the chemical resistance performance of the mirror-transferred coating obtained by Example 1 to Example 3 and the conventional high-pressure melamine material. Table 1 shows the test results. In the table, © indicates little change, 〇 indicates slight coloring and stains, indicates color and stains, X indicates severely colored and stains remain. The test method is based on JIS A5703. Approximately 0.2 ml of the reagent is dropped on the surface, covered with a watch glass, left at room temperature for 24 hours, and cleaned with a dry cloth to observe the surface condition. Chemical resistance

Test solution (concentration) Ε · Clear High-pressure melamine Hydrochloric acid (%) X Miric acid (10%) ◎ X sulfuric acid (%) ◎ X Sulfuric acid (10%) ◎ X Glacial acetic acid (98%) ◎ ◎ Sodium hydroxide (5 %) ◎ ◎ Sodium hydroxide (10%) ◎ ◎ Acetone ◎ ◎ Hydrogen peroxide (31%) ◎ 〇 Black mouth form (99%) ◎ ◎ Ethanol ◎ ◎

Example 9

In Example 7, the particle board was subjected to mirror-transfer coating according to the specifications of Sample 1) and Sample 2) according to the process of Example 1. In addition, the conventional melamine coating was applied according to the specifications of sample 3) and sample 4). The sample specifications are as follows.

1) Particle board EB acrylic (with white luster): 15 (mm)

2) Particle board EB acrylic (white mat): 15 (mm)

3) Particle board high pressure melamine (gray): 15 (mm)

4) MDF low pressure melamine (white): 10 (mm)

Using the above samples, an antibacterial activity test was performed by the drop method. Table 2 shows the test results for Escherichia coli and Table 3 shows the test results for Staphylococcus aureus.

Antibacterial test results by the drop method

<10: Not detected Control: Polyethylene film Bacterial solution preparation solution: 1 / 500NB medium Antibacterial test results by the drop method

10: Not detected Control: Po Bacterial solution preparation solution: 1 / 500NB medium

Example 10

Heat resistance and flame resistance tests were performed using the panels manufactured in Examples 1 to 7 and subjected to the mirror surface transfer coating according to the present invention.

The heat resistance was evaluated based on no deformation or breakage after holding at 140 ° C for 4 hours.

Flame resistance was evaluated by the change in surface after the flame was applied for 30 seconds with an alcohol lamp.

In the heat resistance test, deformation was observed in the case of Example 4 where no paint was applied, but there was no deformation or peeling in the other cases. In the flame resistance test, in Example 4, the surface was blackened and carbonized when the flame was applied with an alcohol lamp for 10 seconds, but the others did not ignite, there was no burn mark, and there was no peeling or deformation.

Industrial applicability

The transfer mirror coating method, which is an example of the bonding method according to the present invention, uses a low-viscosity radical polymerization resin monomer or oligomer in the glue adhesive to reduce the viscosity, and further promotes 100% UV curing of the resin. It is characterized by using a new adhesive mixed with a small amount of photopolymerizing agent. In other words, after applying the EB / UV glue, semi-curing by UV irradiation is performed, and a layer with a certain thickness or more is cured from the surface, and at the same time, the resin added for lowering the viscosity is also cured. It can be returned, and the adhesive used in the transfer method can be uniformly and accurately applied to the substrate surface. In addition, since the adhesiveness can be improved and the workability is improved, if the stamp film is adhered by a hot stamping machine after semi-curing by UV irradiation, the smoothness after transfer or paper pasting and film pasting will be improved.硬化 Irradiation and curing. Adhesion can be completed. The transfer and reattachment speed is the same as the curing speed. Therefore, high-speed transfer and adhesion of 30m / min or more are possible.

The transfer mirror surface coating method according to the present invention has an advantage that the use of UV glue has a great effect of improving the peel strength, heat resistance, and flame resistance of a stamp film, paper sticking, or the like. Finally, it is possible to polymerize completely from the top coat on the surface to the UV-cured part by irradiation at the same time. This results in a polymer resin in which the respective layers are integrated in a dagger-like manner, resulting in an extremely high peeling strength. Further, due to radical polymerization by Β · Β, the bonding force between molecules becomes extremely strong. (4) It has a strong advantage in improving flame resistance because it is resistant to heat-induced shrinkage and does not contain oxygen that causes combustion in the cured resin.

The transfer mirror surface coating method according to the present invention can form a resin layer that satisfies all of the properties of design, stain resistance, chemical resistance, heat resistance, flame resistance, scratch resistance, and mirror surface. According to the present invention, it is possible to provide, at a low cost, a high-quality transfer mirror surface coating material that can be used not only for architectural interior materials satisfying the above characteristics but also for furniture materials having excellent design properties and mirror finish. Since a thick film can be transferred and coated on metal, an exterior material having extremely high weather resistance, heat resistance, and flame resistance can be provided.

Claims

The scope of the claims

1. An adhesive that mixes Ε · Β (electron beam) curing glue, a monomer or oligomer of low-viscosity radically polymerized resin, and an amount of polymerizing agent that does not cause complete UV (ultraviolet) curing.

2. The adhesive according to claim 1, which has a lower viscosity than the Ε · Β cured glue.

3. The adhesive according to claim 1, wherein the monomer and oligomer of the radically polymerizable resin are acrylic resins.

4. 接着 · Β (electron beam) -cured glue, low-viscosity monomer or oligomer of radically polymerized resin on the surface of the adhesive substrate, and amount of polymerizing agent that does not cause complete UV (ultraviolet) curing A high-hardness product having a high-hardness resin layer, which is bonded to the same resin-based adherend of the monomer and oligomer of the radically polymerized resin through an adhesive mixed with .

5. The high-hardness product having a high-hardness resin layer according to claim 4, wherein the monomer or oligomer of the radical polymerization resin is an acrylic resin.

6. High-hardness products with a high-hardness resin layer whose base material is one of inorganic materials, metals, and alloy materials.

7. On the surface of the adhesive substrate, glue Ε · Β (electron beam), monomer or oligomer of low-viscosity radically polymerized resin, and amount of polymerizing agent to prevent complete UV (ultraviolet) curing An adhesive method in which an adhesive mixed with the above is applied, a part of the adhesive is cured by irradiating UV light, and then the adhered material is adhered and cured by an electron beam.

8. The bonding method according to claim 7, wherein scraping is performed after a step of applying a resin or the like or a reverse roll is used to ensure flatness of the adhesive.

9. The bonding method according to claim 7, wherein the monomer and the oligomer of the radical polymerization resin are acrylic resins.

10. The bonding method according to claim 9, wherein the material to be bonded is an acryl resin, and is re-cured by E.B (electron beam) to form a high-hardness resin layer that is integrally laminated.

11. A transfer coating method in which a transfer layer and / or a patterned layer is provided on at least the required surface of the base material via an adhesive layer, and the three resin layers of the top coat on the surface are laminated. A monomer or oligomer of a low-viscosity radically polymerized resin is mixed with an amount of a polymerizing agent that does not completely cure the UV (ultraviolet), and after applying an adhesive layer whose viscosity has been reduced, UV irradiation is performed. Then, a transfer layer and / or a patterned layer is provided by transfer or lamination processing, and then, after laminating the curable resin layer as a surface layer, all layers are irradiated by irradiation. An adhesive method that cures to form a resin film that is integrally polymerized.

12. UV (ultraviolet) curing in a transfer coating method in which a transfer layer and / or a patterned layer is provided at least on the required surface of the base material via an adhesive layer and three resin layers of the top coat on the surface are laminated. After applying the adhesive layer composed of a dull, a part is cured by UV irradiation, and a transfer layer and / or a patterned layer is provided by transfer or lamination treatment. A bonding method in which after lamination as a surface layer, the entire layer is cured by irradiating light to form an integrally polymerized resin film.

13. In a transfer coating method in which a transfer layer and / or a patterned layer is provided at least on the required surface of the base material via an adhesive layer and three resin layers of a top coat on the surface are laminated, a low-viscosity Ε ·塗布 After applying the adhesive layer composed of cured glue, 一部 -irradiate to cure a part, and provide a transfer layer and / or patterned layer by transfer or lamination process, and then Ε-Βcurable resin layer After laminating as a surface layer, the adhesive layer is irradiated with heat to cure all layers to form a resin film that is integrally polymerized.

14. The resin according to any one of claims 11 to 13, wherein the resin to be used is the same resin system of a monomer and an oligomer of the radical polymerization resin, and the transfer layer and / or the patterning layer have a property that the resin can be impregnated. Adhesion method made of resin or paper.

15. In claim 14, the monomer or oligomer of the radical polymerization resin is a low molecular weight resin having a smaller molecular diameter such as a pigment, a paint, and a resin used for the transfer layer and / or the patterned layer. Bonding method.

16. The bonding method according to any one of claims 11 to 13, wherein a scraping force or a reverse roll is used after a step of applying a resin or the like to secure the flatness of the laminated material.

17. The bonding method according to any one of claims 11 to 13, wherein a UV-curable or thermosetting filler is applied to smooth the substrate.

18. The method according to any one of claims 11 to 13, wherein the surface of the substrate is coated with an isocyanate, a UV-curable sealer, or a UV-curable paint to improve the adhesion strength of the resin layer to the inorganic substrate. Adhesion method for applying paint containing isocyanate.