WO2013133314A1 - メラミン樹脂化粧板および仕上げ表面の改修方法 - Google Patents
メラミン樹脂化粧板および仕上げ表面の改修方法 Download PDFInfo
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- WO2013133314A1 WO2013133314A1 PCT/JP2013/056113 JP2013056113W WO2013133314A1 WO 2013133314 A1 WO2013133314 A1 WO 2013133314A1 JP 2013056113 W JP2013056113 W JP 2013056113W WO 2013133314 A1 WO2013133314 A1 WO 2013133314A1
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- WO
- WIPO (PCT)
- Prior art keywords
- melamine resin
- decorative board
- layer
- resin
- resin decorative
- Prior art date
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Definitions
- the present invention is used, for example, in a repair method for renewing the exterior appearance of a vehicle interior by laminating a melamine resin decorative plate on a finished surface of an existing interior decorative panel or a partition top panel of a railway vehicle or the like.
- the present invention relates to a melamine resin decorative plate and a method of repairing a finished surface.
- the melamine resin decorative board in particular, has a hard surface, is excellent in heat resistance and contamination resistance, and is a material having a high decorative surface durability (maintenance of aesthetics). Widely used as a material.
- the problem to be solved by the present invention is that while utilizing the high durability of the melamine resin decorative board, the number of steps required for high incombustibility, lightening, panel warpage reduction, stabilization of crack resistance, repair work and Melamine resin decorative board and finishing surface renovation method that can reduce the burden of refurbishment costs while at the same time reducing the time and easily renovating the existing finished surface, and thus effectively reducing industrial waste Is to provide.
- the present invention has been invented in order to solve the following problems.
- the melamine resin decorative plate is originally a highly durable material and has a sufficient product life.
- the interior of vehicles constructed 15 to 20 years ago has recently reached a time when new refurbishment is required, and the disposal of industrial waste that arises due to the need for this refurbishment will continue in the future. Is expected to become an important issue, so appropriate measures are desired.
- melamine resin decorative boards are among various decorative materials for vehicles, and have excellent long-term durability and design properties. It was more desirable.
- melamine resin decorative boards were applied as part of interior and exterior materials for vehicles that require long-term changes in temperature and humidity, as well as weather resistance in harsh usage environments close to semi-outdoor environments. There is a case. In this case, it was difficult to suppress the dimensional change rate due to the warp caused by the high elastic stress of the melamine resin decorative board, so it was not possible to properly laminate the melamine resin decorative board at present. is there.
- a melamine resin decorative sheet having a small dimensional change and excellent room temperature workability has been proposed (see Patent Document 1).
- vehicle material a vehicle material combustion test
- an aluminum-based melamine resin metal decorative board of an existing material that itself has the vehicle material combustion test “non-combustibility” may be laminated with an adhesive.
- this method it is very difficult to cut the decorative plate in accordance with the existing panel shape and size, and to perform the bonding operation on site. As a result, although a large number of steps were required, there was a high risk of problems such as panel warpage after refurbishment and peeling of the adhesive surface, so it was not an appropriate method.
- Patent Document 2 proposes a method of laminating a melamine resin decorative board without replacing the decorative panel itself.
- this method has a limit on the non-combustibility of a single unit, and higher degree of non-combustibility is necessary in consideration of application not only for vehicles but also for underground shopping centers and public facilities.
- demands for weight reduction, reduction of panel warpage, stabilization of crack resistance, on-site workability, etc. have become stricter, and the actual situation is that a finishing surface repair method that satisfies these requirements has not been realized. Met.
- the adhesive layer is composed of an adhesive layer base material carrying a solid content of a thermosetting resin.
- the solid content of the thermoplastic emulsion resin includes emulsion resin particles having an average particle size of 30 to 100 nm.
- thermoplastic emulsion resin water-insoluble.
- urethane-acrylic composite particles are an aqueous clear type having a core-shell structure having an acrylic component as a core and a urethane component as a shell.
- a method for refurbishing a finished surface by laminating a melamine resin decorative board on an existing finished surface, and refurbishing the finished surface The melamine resin decorative board has a structure in which a surface layer and a core material layer are laminated, The surface layer has a surface layer base supporting a resin containing a melamine resin on the first surface side serving as a design surface and supporting the solid content of the thermoplastic emulsion resin on the second surface side in contact with the core material layer. Consists of surface layer material made of material, The method for repairing a finished surface, wherein the core layer is composed of a heat dissipating material layer.
- the present invention while utilizing the high durability of the melamine resin decorative board, it reduces the number of steps and time required for high nonflammability, lighter weight, reduction of panel warpage, stabilization of crack resistance, repair work.
- a method for repairing a melamine resin decorative board and a finished surface which can easily renovate an existing finished surface, reduce the burden of repair costs, and effectively reduce industrial waste.
- FIG. 1 shows a state of a finishing surface repair method using the melamine resin decorative board of the present invention.
- the repair method is applied to a finished surface of an existing vehicle decorative panel 1 or the like.
- the melamine resin decorative board 10 is laminated and the finished surface is newly installed.
- the melamine resin decorative board 10 is laminated on the finished surface of the existing vehicular decorative panel 1 with an adhesive such as an adhesive tape 2 as shown in FIG.
- This pressure-sensitive adhesive is sufficient so that the pressure-sensitive adhesive becomes a heat-insulating layer during combustion and does not cause diffusion of combustion heat and raise the combustion temperature on the combustion surface to promote ignition / flame. It is desirable to use a material that is as thin as possible while having adhesive strength.
- the lamination of the melamine resin decorative board 10 is performed by removing dirt and foreign matter adhering to the finished surface of the existing vehicular decorative panel 1 and stabilizing the adhesive quality in order to stabilize the adhesion quality. To do.
- the melamine resin decorative board used in the finishing surface modification method according to the first embodiment of the present invention is a melamine resin decorative board having a structure in which a surface layer and a core material layer are laminated, and the surface layer has a design.
- a surface layer material comprising a surface layer base material supporting a resin containing a melamine resin on the first surface side which is a surface and supporting the solid content of the thermoplastic emulsion resin on the second surface side in contact with the core material layer
- the core material layer is composed of a heat dissipating material layer.
- FIG. 2 shows a configuration of the melamine resin decorative board 12 including the surface layer 15 and the core material layer 16.
- an adhesive layer 17 may be provided between the surface layer 15 and the core material layer 16.
- FIG. 4 shows an example of the manufacturing method of a melamine resin decorative board.
- the melamine resin decorative board 12 is obtained by superposing a surface layer material 15A and a core material layer material 16A, and laminating them by heating and pressing.
- the surface layer 15 is composed of a surface layer material 15A, and the surface layer material 15A is disposed on the design surface (exposed surface) side of the melamine resin decorative board 12 of the present embodiment.
- 15 A of surface layer materials carry
- the surface layer base material supports the resin, the resin adheres to the surface of the base material (carrier) or is impregnated in the voids inside the base material, and is supported after the surface layer material is molded. It means that it is in a state that makes it possible to express the performance of the resin.
- the resin may not be uniformly distributed on the surface of the base material and the inside of the base material.
- the surface layer base material is a sheet-like base material having a design surface formed on the first surface side 151.
- the material of the surface layer substrate is not particularly limited, but preferably, pulp, linter, synthetic fiber, glass fiber, or the like can be used, and if necessary, a titanium oxide-containing decorative paper containing a pigment such as titanium oxide. Etc. can be used.
- the basis weight of the surface layer substrate is not particularly limited, but is preferably 40 to 150 g / m 2 . If the basis weight is less than the lower limit, the coating treatment is difficult due to the problem of cutting and wrinkling in the resin impregnation step, and the resin impregnation amount to be supported on each of the first surface and the second surface is adjusted. It is also difficult to do.
- the surface layer material 15A used in the present embodiment is formed by supporting a resin containing a melamine resin on the first surface side 151 of the surface layer base material. Thereby, surface hardness suitable for the surface of the 1st surface side 151 of surface layer material 15A, ie, the surface of a melamine resin decorative board, can be given.
- a melamine resin For example, what is obtained by making melamine and formaldehyde react under neutrality or weak alkali can be used.
- reaction molar ratio of formaldehyde to melamine (the value of (molar amount of formaldehyde) / (molar amount of melamine), hereinafter may be simply referred to as “reaction molar ratio”) is not particularly limited. A value obtained by reacting at a value of ⁇ 4.0, preferably 1.0 to 2.0, more preferably 1.1 to 1.8 can be suitably used. When the reaction molar ratio is less than the lower limit, unreacted components increase, resulting in a decrease in storage stability and cost. When the reaction molar ratio exceeds the upper limit, the resin flexibility after curing becomes significant.
- a melamine resin what is contained individually by 1 type can also be used, and what mixed and contained 2 or more types of melamine resin from which reaction molar ratio, a weight average molecular weight, etc. differ can also be used.
- a melamine resin a commercially available thing, such as a melamine resin by Sumitomo Chemical Co., Ltd., can also be used.
- the weight average molecular weight of the melamine resin is not particularly limited, but is preferably 200 to 500, and particularly preferably 250 to 350. When the molecular weight is smaller than the lower limit value, the amount of unreacted components increases, so that the storage stability is lowered.
- the weight average molecular weight can be measured, for example, by GPC (gel permeation chromatography, standard substance: converted to polystyrene).
- the method of supporting the resin containing the melamine resin on the first surface side 151 of the surface layer base material is not particularly limited, but a resin varnish in which the resin is dissolved in a solvent is used, for example, a spray device, a shower device, Examples thereof include a method in which coating is performed using a known apparatus such as a kiss coater or a comma coater, followed by heating and drying at about 80 to 130 ° C.
- the surface layer base material hereinafter also referred to as resin-impregnated paper
- the surface layer base material after the resin varnish is applied and dried by heating, when the weight of the entire resin-impregnated paper is 100% by mass, It is preferable that 2 to 6% by mass of a volatile component (solvent) remains.
- the solvent for dissolving the resin containing the melamine resin is not particularly limited, and examples thereof include water and methanol. Of these, water is preferred. Moreover, you may use a poor solvent in the range which does not exert a bad influence.
- the solid content of the resin varnish (all components excluding the solvent) is not particularly limited, but is preferably 30 to 70% by mass, and particularly preferably 45 to 60% by mass of the resin varnish. Thereby, the impregnation property to the base material of the resin varnish can be improved.
- the solid content of the thermoplastic emulsion resin is supported on the second surface side 152 opposite to the design surface of the surface layer base material.
- the thermoplastic emulsion resin includes a thermoplastic resin but is dispersed in a solvent to become an emulsion state.
- the solid content of the thermoplastic emulsion resin means a component obtained by removing the solvent from the thermoplastic emulsion resin.
- the solid content of the thermoplastic emulsion resin contains components present as emulsion resin particles, has adhesive properties with metals and various materials, and imparts flexibility to the melamine resin decorative board. Therefore, the solid content of the thermoplastic emulsion resin is carried on the second surface side 152, whereby the adhesive strength between the surface layer 15 and the core material layer 16 can be improved, and the bending of the melamine resin decorative board can be performed. Workability can be improved.
- the solid content of the thermoplastic emulsion resin is not particularly limited.
- grains of a thermoplastic resin are mentioned.
- urethane acrylic composite particles are preferable.
- the urethane-acrylic composite particles mean those having a heterogeneous structure of an acrylic resin and a urethane resin in a single particle. Since each of the urethane resin and the acrylic resin has high adhesive strength with the core material layer, good adhesive strength with the core material layer can be expressed by using urethane acrylic composite particles.
- the urethane resin is particularly excellent in toughness, elasticity, and flexibility, and the acrylic resin is particularly excellent in transparency, durability, weather resistance, chemical resistance, and film forming property.
- heterophase structure means a structure in which a plurality of phases composed of different types of resins are present in one particle, and examples thereof include a core-shell structure, a localized structure, and a sea-island structure.
- the arrangement state between the particles when the urethane acrylic composite particles are supported on the first surface side 151 of the surface layer material 15A is not particularly limited, and examples thereof include a linear structure. The structure of the particles and the arrangement state between the particles can be confirmed by, for example, a scanning electron microscope (SEM).
- the urethane acrylic composite particles are particularly preferably an aqueous clear type having a core-shell structure in which an acrylic component is a core and a urethane component is a shell. If the urethane-acrylic composite particles have the above-described core-shell structure, the surface outline becomes a urethane composition when supported on the second surface side 152 of the surface layer material 15A, so the second surface side 152 of the surface layer material 15A. While having the characteristics of both a urethane resin and an acrylic resin, the characteristics of the urethane resin are imparted to the outer shell.
- aqueous clear means that the resin solution is water-soluble, the coating film after the moisture is removed is non-aqueous, and the resin solution is transparent enough to clearly distinguish the underlying pattern. Means. Since the resin carried on the second surface side 152 of the surface layer material 15A is an aqueous clear type, the influence of the surface layer on the color tone of the design surface can be suppressed. In addition, as solid content of a thermoplastic emulsion resin, the thing containing one of these alone can also be used, and the thing containing 2 or more types of different thermoplastic resins can also be used.
- the solid content of the thermoplastic emulsion resin may contain a small amount of a thickener, a penetration accelerator, an antifoaming agent, etc., if necessary.
- the solid content of the thermoplastic emulsion resin preferably includes emulsion resin particles having an average particle diameter of 30 to 100 nm, and the average particle diameter of the emulsion resin particles is particularly preferably 60 to 90 nm.
- the solid content of the thermoplastic emulsion resin is preferably water-insoluble. As a result, the solid content of the thermoplastic emulsion resin is transferred to the first surface side 151 of the surface layer material 15A and mixed with the melamine resin supported on the first surface side 151, so that the first surface It can prevent that the surface performance by the melamine resin of the side 151 is impaired.
- the method of supporting the solid content of the thermoplastic emulsion resin on the second surface side 152 of the surface layer base material is not particularly limited, and a resin containing a melamine resin is applied to the first surface side 151 of the surface layer base material. It can carry out similarly to the above-mentioned method to carry
- the resin-impregnated paper after heat drying preferably contains 2 to 6% by mass of volatile matter when the total weight of the resin-impregnated paper is 100% by mass. This facilitates the handling of the resin-impregnated paper and improves the design appearance and surface gloss of the decorative board by improving the resin flow of the melamine resin carried on the first surface side 151 at the time of thermoforming. Because it becomes.
- thermoplastic emulsion resin Although it does not specifically limit as a solvent used for the said thermoplastic emulsion resin, For example, water etc. are mentioned. Moreover, you may use a poor solvent in the range which does not exert a bad influence.
- the solid content (all components excluding the solvent) of the thermoplastic emulsion resin is not particularly limited, but is preferably 25 to 60% by mass, particularly preferably 30 to 45% by mass, of the thermoplastic emulsion resin. Thereby, the impregnation property to the base material of the said thermoplastic emulsion resin can be improved.
- the decorative melamine resin board 12 of the present embodiment is formed by laminating the core material layer 16 on the second surface side 152 of the surface layer 15. It is preferable to use a heat dissipating material having a thermal conductivity of 10 W / m ⁇ K or more for the core layer used in the present embodiment.
- Examples of heat dissipating materials having a thermal conductivity of 10 W / m ⁇ K or more include silver (420 W / m ⁇ K), copper (398), gold (320), aluminum (236), silicon (168), brass (106 ) And metals such as iron (84) can be mainly used, but a resin sheet containing heat conductive particles such as boron nitride can also be used if the thermal conductivity satisfies the conditions.
- an aluminum layer made of aluminum is preferably used as the core material layer in terms of thermal conductivity, workability, and versatility.
- An aluminum foil or an aluminum plate can be applied to the aluminum layer used here, and heat resistance, nonflammability, rigidity, and the like can be imparted to the melamine decorative board.
- the thickness of the aluminum layer is preferably 0.2 mm or more. Thereby, sufficient heat resistance and nonflammability can be imparted to the decorative board. When the thickness of the aluminum layer becomes thinner than the lower limit value, sufficient nonflammability cannot be obtained depending on the base.
- the upper limit of the thickness is not particularly limited, but the heat resistance and incombustibility increase as the thickness increases, but the thickness and weight of the decorative melamine board increase and the cost increases, so the design in the final product In addition, it is preferably set within an allowable range, and is preferably 0.5 mm or less.
- the aluminum layer is preferably one that has been primed with an epoxy resin on one or both sides. Thereby, the adhesive strength between the surface layer material or the pressure-sensitive adhesive and the aluminum layer can be further improved.
- the melamine resin decorative board 12 may have an adhesive layer between the surface layer 15 and the core material layer 16.
- the adhesive layer one that serves as an adhesive such as a primer, an adhesive, an adhesive film, or a glass cloth prepreg can be used as one or more layers. Any of these may be general-purpose ones. Moreover, even if there is no adhesion effect, for example, a glass cloth can be used as a material having better adhesion than adherends.
- the glass cloth has good adhesion between the thermoplastic emulsion resin carried on the second surface side 152 of the surface layer and each of the primer-treated core material layers, and the second surface side of the surface layer and the primer Adhesiveness is greatly improved compared to direct contact with the treated core material layer. Thereby, the adhesive force of the surface layer and core material layer of a melamine resin decorative board can be strengthened.
- the glass cloth used for the glass cloth or the prepreg base material is not particularly limited, and examples thereof include a glass woven cloth and a glass non-woven cloth. Among them, a glass woven cloth is preferable in terms of nonflammability and strength. Moreover, as glass which comprises a glass cloth, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned, for example. Among these, T glass is preferable. Thereby, the thermal expansion coefficient of a glass cloth can be made small. In addition to glass cloth, non-woven fabric, core paper, titanium paper, carbon fiber cloth, aramid fiber cloth, and the like may be used.
- the prepreg is not particularly limited.
- a prepreg obtained by impregnating the above glass cloth with a resin composition containing a thermoplastic resin or the like can be used.
- the resin composition is not particularly limited as long as the interlayer adhesion strength between the surface layer 15 and the core material layer 16 is sufficient for forming the melamine resin decorative board 12, but among them, a thermoplastic resin is solid.
- the content is preferably 2 to 20% by mass, and particularly preferably 3 to 8% by mass. Thereby, the interlaminar adhesive strength between the surface layer 15 and the core material layer 16 can be improved without deteriorating high incombustibility and bending workability.
- the thermoplastic resin is not particularly limited, and examples thereof include an acrylic resin, a urethane resin, an ethylene vinyl acetate resin, and a styrene butadiene rubber (SBR). Among them, an acrylic resin and a urethane resin are preferable, and the thermoplastic resin preferably contains an acrylic resin and / or a urethane resin.
- the prepreg can be produced by a conventionally known method.
- the prepreg can be obtained by impregnating a glass cloth similar to the glass cloth described above with a varnish obtained by dissolving the resin composition in a solvent and drying the glass cloth.
- the melamine resin decorative board 12 is obtained by superposing the above-described surface layer material 15A and the core material layer material 16A in a predetermined order, and laminating them by heating and pressing.
- the conditions for heat-press molding the melamine resin decorative board 12 are not particularly limited, but for example, it can be carried out at a temperature of 130 to 150 ° C., a pressure of 2 to 8 MPa, and a time of 3 to 60 minutes.
- a mirror finish can be obtained by superimposing a mirror finish plate on the first surface side of the surface layer material 15A, and embossing can be achieved by superimposing an emboss plate or an emboss film. It can be finished.
- the melamine resin decorative board used in the present embodiment preferably has an overall thickness of 0.6 mm or less, more preferably 0.5 mm or less.
- the melamine resin decorative board of this embodiment can be bent with a minimum bending radius of 15 mmR or less at normal temperature (usually about 20 to 30 ° C.), but is not particularly limited.
- the minimum bend radius R is the minimum at which 100% non-defective product can be obtained without causing defects such as cracking even if the room temperature bending process is repeatedly performed in one direction along a mold having a curved portion with a radius R. Means the radius R of the mold.
- the finishing surface modification method of the present embodiment is a method of laminating a melamine resin decorative board on an existing finishing surface and newly refurbishing the finishing surface, and is not particularly limited. After the laminated melamine resin decorative board is laminated on the finished surface, the melamine resin decorative board can be repaired by a method of pressurizing, heating or thermocompression bonding.
- the finish surface modification method of the present embodiment the melamine resin decorative plate obtained by pressurizing and pressing the melamine resin decorative plate with a roll or after the melamine resin decorative plate is laminated on the finished surface, Defoaming treatment is preferably performed by pressurizing, heating, or thermocompression bonding.
- the adhesion layer may be previously provided in the back surface of the melamine resin decorative board.
- a melamine resin decorative board is laminated on an existing finished surface, and the finished surface is newly installed. For this reason, it is possible to easily refurbish the finished surface in a short time by utilizing the long-term durability and design characteristics of the melamine resin decorative board without replacing the existing decorative panel, and at the same time, wasteful resources There is no need to dispose of it, and there is a real advantage that environmental protection and industrial waste countermeasures can be effectively realized.
- a melamine resin decorative board used in a method for refinishing a finished surface according to a second embodiment of the present invention is a melamine resin decorative board having a structure in which a surface layer and a core material layer are laminated via an adhesive layer.
- the layer comprises a surface layer base material carrying a resin containing a melamine resin on the first surface side which is a design surface and carrying a solid content of the thermoplastic emulsion resin on the second surface side in contact with the core material layer.
- the adhesive layer is composed of an adhesive layer material composed of an adhesive layer base material carrying a solid content of a thermosetting resin
- the core material layer is composed of a heat dissipating material layer.
- FIG. 3 shows a configuration of the melamine resin decorative board 12 having a structure in which the surface layer 15 and the core material layer 16 are laminated via the adhesive layer 17.
- FIG. 6 shows an example of the manufacturing method of the melamine resin decorative board 12 in FIG. 6 .
- the melamine resin decorative board 12 is obtained by laminating the surface layer material 15A and the core material layer material 16A via the adhesive layer material 17A, and laminating them by heating and pressing. It is done.
- the surface layer 15 is composed of a surface layer material 15A, and the surface layer material 15A is disposed on the design surface (exposed surface) side of the melamine resin decorative board 12 of the present embodiment.
- 15 A of surface layer materials carry
- the surface layer 15 in the second embodiment can be the same as that in the first embodiment.
- the melamine resin decorative board 12 of the present embodiment is formed by laminating the core material layer 16 on the second surface side 152 of the surface layer 15 via the adhesive layer 17.
- a heat dissipating material having a thermal conductivity of 10 W / m ⁇ K or more for the core layer used in the present embodiment.
- Examples of the heat dissipating material having a thermal conductivity of 10 W / m ⁇ K or more include silver (420 W / m ⁇ K), copper (398), gold (320), aluminum (236), silicon (168), brass (106 ) And metals such as iron (84) can be mainly used, but a resin sheet containing thermal conductive particles such as boron nitride can also be used if the thermal conductivity satisfies the conditions.
- an aluminum layer made of aluminum is preferably used as the core material layer in terms of thermal conductivity, workability, and versatility.
- An aluminum foil or an aluminum plate can be applied to the aluminum layer used here, and heat resistance, nonflammability, rigidity, etc. can be imparted to the melamine decorative board.
- the thickness of this aluminum layer is preferably 0.2 mm or more. Thereby, sufficient heat resistance and nonflammability can be imparted to the decorative board.
- the upper limit of the thickness is not particularly limited, but the heat resistance and incombustibility increase as the thickness increases, but the thickness and weight of the decorative melamine board increase and the cost increases, so the design in the final product In addition, it is preferably set within an allowable range, and is preferably 0.5 mm or less.
- the aluminum layer is subjected to a treatment for removing an oxide film such as sanding or chromate treatment on one side or both sides, or a primer treatment.
- the resin used for the primer treatment is not particularly limited, and examples thereof include an epoxy resin system, a urethane resin system, a polyester resin system, an acrylic resin system, a mixture thereof, and a copolymer. Thereby, the adhesive strength between the surface layer material or the pressure-sensitive adhesive and the aluminum layer can be further improved.
- the melamine resin decorative board 12 has an adhesive layer 17 between the surface layer 15 and the core material layer 16.
- an adhesive layer material composed of an adhesive layer base material carrying a solid content of a thermosetting resin can be used as one or two or more layers.
- thermosetting resins include, but are not limited to, phenol resins, epoxy resins, oxetane resins, (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, urea resins, maleimide resins, and the like. From the viewpoints of nonflammability, heat resistance and adhesion, a phenol resin is preferable.
- the adhesive layer base material include, but are not limited to, glass cloth, non-woven fabric, core paper, titanium paper, carbon fiber cloth, aramid fiber cloth, and the like. Glass cloth is preferred.
- the glass cloth is not particularly limited, and examples thereof include a glass woven fabric and a glass nonwoven fabric. Among these, a glass woven fabric is preferable from the viewpoint of nonflammability and strength.
- examples of the glass constituting the glass cloth include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, and H glass.
- T glass is preferable. Thereby, the thermal expansion coefficient of an adhesive layer can be made small.
- the amount of the thermosetting resin carried on the adhesive layer base material is not particularly limited, but is preferably 1 to 20% by mass, particularly preferably 2 to 10% by mass in the solid content in the adhesive layer. .
- the interlaminar adhesive strength between the surface layer 15 and the core material layer 16 can be improved without reducing high incombustibility and bending workability.
- the phenol resin is not particularly limited.
- the phenol resin is obtained by reacting phenols and aldehydes in an alkaline or acidic catalyst, and has at least one phenolic hydroxyl group in the aromatic ring. Can be used.
- phenol resin for example, by phenol resin, cresol resin, resorcin resin, xylenol resin, naphthol resin, bisphenol A resin, aralkyl phenol resin, biphenyl aralkyl phenol resin, cashew nut oil which has phenolic hydroxyl group, etc.
- modified phenolic resins include modified phenolic resins.
- xylene-modified phenol resins containing substances having phenolic hydroxyl groups and various modified phenol resins such as phenol-modified rosin, oil-modified phenol resins modified with terpene oil, rubber-modified phenol resins modified with rubber, etc. can do.
- the method for reacting the phenols with the aldehydes is not particularly limited, and a known method can be employed.
- the reaction molar ratio of aldehydes to phenols (value of (molar amount of aldehydes) / (molar amount of phenols)) is not particularly limited, but is preferably 1.0 to 2.0, more preferably 1. Those obtained by reacting as 1 to 1.4 can be preferably used.
- strength and adhesiveness will worsen, and there exists a possibility that curvature may become large when there are many.
- phenols used for obtaining the phenol resin those having a phenolic hydroxyl group in the aromatic ring are preferable as the phenols, and may further have a substituent other than the phenolic hydroxyl group.
- cresols such as phenol, o-cresol, m-cresol, p-cresol, mixed cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- Xylenol such as xylenol and 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol and p-ethylphenol, butylphenol such as isopropylphenol, butylphenol and p-tert-butylphenol, p-tert-amylphenol Alkylphenols such as p-octylphenol, p-n
- aldehydes used to obtain the phenol resin include formaldehyde, paraformaldehyde, glyoxal, trioxal, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyl.
- Examples include aldehyde, caproaldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, paraxylene dimethyl ether and the like. These may be used alone or in combination of two or more.
- the catalyst for obtaining the phenol resin is not particularly limited, and examples thereof include an acid catalyst, a base catalyst, and a transition metal salt catalyst.
- the acid catalyst that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acids, and organic acids such as oxalic acid, p-toluenesulfonic acid, and organic phosphonic acid.
- the base catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, ammonia, alkylamine and the like. These amines can be used.
- the transition metal salt catalyst include zinc oxalate and zinc acetate.
- the method of supporting the solid content of the thermosetting resin on the adhesive layer base material such as glass cloth is not particularly limited, and examples thereof include a method of applying a thermosetting resin dissolved in a solvent and heating and drying. .
- the adhesive layer material after heating and drying (adhesive layer base material supported by the thermosetting resin) has a volatile content of 1 to 6% by mass when the total weight of the adhesive layer material is 100% by mass. Preferably it remains.
- the solvent used for dissolving the thermosetting resin is not particularly limited, and examples thereof include methanol.
- the thermosetting resin is diluted 5 to 14 times and the varnish solid content is adjusted to 3 to 10% by mass.
- the method etc. which apply the applied coating liquid are mentioned. Thereby, the impregnation property to the adhesive layer base material of a thermosetting resin can be improved.
- the melamine resin decorative board 12 is obtained by superimposing the above-described surface layer material 15A and core material layer material 16A via an adhesive layer 17, and laminating them by heating and pressing.
- the conditions for heat-press molding of the melamine resin decorative board 12 are not particularly limited, but for example, it can be carried out at a temperature of 130 to 150 ° C., a pressure of 2 to 8 MPa, and a time of 3 to 60 minutes.
- a mirror finish can be obtained by superimposing a mirror finish plate on the first surface side of the surface layer material 15A, and embossing can be achieved by superimposing an emboss plate or an emboss film. It can be finished.
- the overall thickness of the decorative melamine resin plate used in the present embodiment is preferably 0.6 mm or less, and more preferably 0.5 mm or less.
- the overall thickness of the decorative melamine resin plate used in the present embodiment is preferably 0.6 mm or less, and more preferably 0.5 mm or less.
- the melamine resin decorative board of this embodiment can be bent with a minimum bending radius of 15 mmR or less at room temperature (usually about 20 to 30 ° C.), but is not particularly limited.
- the minimum bend radius R is the minimum at which 100% non-defective product can be obtained without causing defects such as cracking even if the room temperature bending process is repeatedly performed in one direction along a mold having a curved portion with a radius R. Means the radius R of the mold.
- the finishing surface modification method of the present embodiment is a method of laminating a melamine resin decorative board on an existing finishing surface and newly refurbishing the finishing surface, and is not particularly limited. After the laminated melamine resin decorative board is laminated on the finished surface, the melamine resin decorative board can be repaired by a method of pressurizing, heating or thermocompression bonding.
- the finish surface modification method of the present embodiment the melamine resin decorative plate obtained by pressurizing and pressing the melamine resin decorative plate with a roll or after the melamine resin decorative plate is laminated on the finished surface, Defoaming treatment is preferably performed by pressurizing, heating, or thermocompression bonding.
- the adhesion layer may be previously provided in the back surface of the melamine resin decorative board.
- a melamine resin decorative board is laminated on an existing finished surface, and the finished surface is newly installed. For this reason, it is possible to easily refurbish the finished surface in a short time by utilizing the long-term durability and design characteristics of the melamine resin decorative board without replacing the existing decorative panel, and at the same time, wasteful resources There is no need to dispose of it, and there is a real advantage that environmental protection and industrial waste countermeasures can be effectively realized.
- the melamine resin decorative board 10 used in the present invention was formed by the following method. Using a titanium oxide-containing decorative paper (Dai Nippon Printing Co., Ltd.) having a basis weight of 80 g / m 2 as the surface layer base material, an emulsion of urethane acrylic composite particles (on the second surface side of the titanium oxide-containing decorative paper) “SU-100” manufactured by Chuo Rika Kogyo Co., Ltd., average particle size: 84 nm, dispersion medium: water) was applied to a solid content of 34 g / m 2, and then the first surface side of the decorative paper ( After coating 50 g / m 2 with melamine resin (reaction molar ratio 1.4, resin solid content 50% by mass) on the design surface side), it was dried for 90 seconds in a hot air dryer at 120 ° C., and the resin ratio was 51 %, A surface layer material having a volatile content of 3% was obtained.
- a titanium oxide-containing decorative paper (Dai
- the melamine resin is prepared by adding raw material melamine and formalin to a reaction kettle at a predetermined blending ratio, adding a catalyst, raising the temperature to the boiling point, performing a reflux reaction, and confirming that melamine dissolution is complete, and when the reaction end point is reached.
- the resin solid content was adjusted by dehydration and synthesized by a method of cooling.
- a structural high-adhesive acrylic adhesive having a base material of 5 ⁇ m and a polyester fabric woven fabric made of ultra-light and ultra-thin fibers.
- the tape 2 was laminated by roll pressing with a roll linear pressure of 40 N / cm, to obtain a melamine resin decorative board 10 with a back surface paste.
- This melamine resin decorative board 10 is deaerated from one side with a metal hand roll to a 1.6 mm thick metal base melamine resin decorative board (base aluminum is 1.2 mm) which is generally used as an interior material for vehicles.
- the presser foot was stuck together.
- an iron heated to a surface temperature of 180 to 200 ° C. was used to heat and finish from the surface side so that the bonded melamine resin decorative board 10 was not damaged.
- the iron contact time was pressed so as to contact the hot-pressed surface for 5 to 10 seconds / location.
- Example 2 The melamine resin decorative board 10 used in the present invention was formed by the following method.
- a surface layer material having a resin ratio of 51% and a volatile content of 3% was obtained in the same manner as in Example 1.
- a glass cloth having a basis weight of 104 g / m 2 manufactured by Nanya Taiwan: product number Nanya-2116 was used as the adhesive layer, and an emulsion of urethane acrylic composite particles (“SU-100” manufactured by Chuo Rika Kogyo Co., Ltd.), average particle diameter : 84 nm, dispersion medium: water) was coated with a kiss coater method so that the solid content was 5 g / m 2, and then dried with a hot air dryer at 120 ° C.
- the resin ratio was 5%
- the volatile content was An adhesive layer material with a rate of 0.5% was obtained.
- the surface layer material, the adhesive layer material obtained above, and an aluminum foil having a thickness of 0.3 mm whose surface is subjected to primer treatment with an epoxy resin are placed on the adhesive layer material on the second surface side of the surface layer material, Furthermore, the primer-treated surfaces of aluminum foil were superposed and heated and pressed under conditions of 140 ° C. and 5 MPa for 10 minutes to obtain a sample having a thickness of 0.5 mm.
- a melamine resin decorative board 10 with a back surface paste was produced and bonded to an interior material for a vehicle.
- Example 3 For the surface layer base material, a surface layer material having a resin ratio of 51% and a volatile content of 3% was obtained in the same manner as in Example 1. The surface layer material obtained above and an aluminum foil with a thickness of 0.1 mm whose surface has been subjected to primer treatment with an epoxy resin, the primer treatment surface of the aluminum foil is superimposed on the second surface side of the surface layer material, A sample having a thickness of 0.3 mm was obtained by heating and pressing under conditions of 140 ° C. and 8 MPa for 20 minutes. Next, in the same manner as in Example 1, a melamine resin decorative board 10 with a back surface paste was produced and bonded to an interior material for a vehicle.
- a water-soluble melamine resin for post home having a molar ratio of formaldehyde to melamine of 1.6, a number average molecular weight of 230, a viscosity of 40 cps / 20 ° C., and an aqueous acrylic resin emulsion having a solid content of 45% and a viscosity of 35 cps / 20 ° C. in a weight ratio of 100: 35.
- the viscosity was adjusted to 20 cps / 25 ° C. with water, and then a catalyst was added to obtain a melamine varnish for impregnation.
- This varnish was impregnated into a titanium oxide-containing decorative paper (Dai Nippon Printing Co., Ltd.) having a basis weight of 80 g / m 2 and dried by heating to obtain a surface layer material having a resin amount of 55% and a volatile content of 6%. .
- the surface layer material obtained above and an aluminum foil having a thickness of 0.3 mm, the surface of which has been primed with an epoxy resin, are placed on the surface layer material side so as to be the primer-treated surface of the aluminum foil, 145 ° C., 10 MPa.
- a sample with a thickness of 0.5 mm was obtained by heating and pressing under the above conditions for 10 minutes.
- a melamine resin decorative board 10 with a back surface paste was produced and bonded to an interior material for a vehicle.
- Comparative Example 2 Use 0.2mm olefin sheet (vinyl chloride resin printed sheet) as the surface layer material, 0.3mm thick aluminum foil with urethane adhesive on the surface, and aluminum foil adhesive coated surface on the surface layer material side And cured at 80 ° C. for 30 minutes to obtain a sample having a thickness of 0.5 mm.
- a melamine resin decorative board 10 with a back surface paste was produced and bonded to an interior material for a vehicle.
- Example 3 the thickness of aluminum was thin, and heat dissipation was not sufficient. For this reason, in the vehicle material fuel test, a fire blister was caused and it was judged as flame retardant.
- Comparative Example 1 since the melamine resin was used as the resin to be supported on the second surface side of the surface layer without using the solid content of the thermoplastic emulsion resin, the melamine decorative board was inferior in room temperature bending workability. In Comparative Example 2, since olefin was used for the surface layer, surface properties such as surface hardness and contamination resistance were inferior.
- Example 4 A melamine resin decorative board was formed by the following method. Using a titanium oxide-containing decorative paper (Dai Nippon Printing Co., Ltd.) having a basis weight of 80 g / m 2 as the surface layer base material, an emulsion of urethane acrylic composite particles (on the second surface side of the titanium oxide-containing decorative paper) “SU-100” manufactured by Chuo Rika Kogyo Co., Ltd., average particle size: 84 nm, dispersion medium: water) was applied to a solid content of 34 g / m 2, and then the first surface side of the decorative paper ( After coating 50 g / m 2 with melamine resin (reaction molar ratio 1.4, resin solid content 50% by mass) on the design surface side), it was dried for 90 seconds in a hot air dryer at 120 ° C., and the resin ratio was 51 %, A surface layer material having a volatile content of 3% was obtained.
- a titanium oxide-containing decorative paper (Dai Nippon Print
- the melamine resin is prepared by adding raw material melamine and formalin to a reaction kettle at a predetermined blending ratio, adding a catalyst, raising the temperature to the boiling point, performing a reflux reaction, and confirming that melamine dissolution is complete, and when the reaction end point is reached.
- the resin solid content was adjusted by dehydration and synthesized by a method of cooling.
- a glass cloth having a grammage of 104 g / m 2 (Nanya, Taiwan, Nanya-2116) was used as the adhesive layer base material, and phenol resin (PR-204G, manufactured by Sumitomo Bakelite Co., Ltd.) was diluted 10-fold with a methanol solvent.
- An adhesive layer material was placed on the surface side of the aluminum foil, and the primer-treated surface of the aluminum foil was further superposed, followed by heating and pressing under conditions of 140 ° C. and 5 MPa for 10 minutes to obtain a melamine resin decorative board having a thickness of 0.5 mm. .
- Example 3 a surface layer material having a resin ratio of 51% and a volatile content of 3% was obtained in the same manner as in Example 4. Moreover, also about the adhesive layer material, when the weight of the whole adhesive layer material was made into 100 mass% by the method similar to Example 4, the adhesive layer material with which 3 mass% phenol resin remained was obtained.
- the surface layer material and the adhesive layer material obtained above are superimposed on the second surface side of the surface layer material, and heated and pressure-molded at 140 ° C. and 8 MPa for 20 minutes to form a core material A melamine resin decorative board having a thickness of 0.2 mm without a layer was obtained.
- Example 4 a melamine resin decorative board with back surface glue was prepared and bonded to an interior material for a vehicle.
- Example 4 a surface layer material having a resin ratio of 51% and a volatile content of 3% was obtained in the same manner as in Example 4.
- the obtained surface layer material and an aluminum foil having a thickness of 0.3 mm whose surface is subjected to primer treatment with an epoxy resin (Nippe Power Binding manufactured by Nippon Paint Co., Ltd.) are placed on the second surface side of the surface layer material.
- the primer-treated surfaces were superimposed and subjected to heat and pressure molding at 140 ° C. and 5 MPa for 10 minutes to obtain a 0.4 mm thick melamine resin decorative board without an adhesive layer.
- Example 4 a melamine resin decorative board with back surface glue was prepared and bonded to an interior material for a vehicle.
- Thickness of the surface layer material obtained above glass cloth having a basis weight of 104 g / m 2 (Taiwan Nanya, Nanya-2116) and the surface subjected to primer treatment with epoxy resin (Nippe Power Bind, Nippon Paint Co., Ltd.) Place a glass cloth on the second surface side of the surface layer material with 0.3 mm aluminum foil, and further overlay the primer-treated surface of the aluminum foil, and heat and pressure mold for 20 minutes at 140 ° C. and 8 MPa. A melamine resin decorative board having a thickness of 0.5 mm having a glass cloth layer instead of the adhesive layer was obtained.
- Example 4 a melamine resin decorative board with back surface glue was prepared and bonded to an interior material for a vehicle.
- the obtained varnish was impregnated with a titanium oxide-containing decorative paper (Dai Nippon Printing Co., Ltd.) having a basis weight of 80 g / m 2 as a surface layer base material, and then dried for 90 seconds with a hot air dryer at 120 ° C.
- a surface layer material having a resin ratio of 55% and a volatile content ratio of 6% was obtained.
- an adhesive layer material in which 3% by mass of the phenol resin remained was obtained in the same manner as in Example 4 when the weight of the entire adhesive layer material was 100% by mass.
- the adhesive layer material is placed on the surface side of the aluminum foil, and the primer-treated surface of the aluminum foil is further superposed, heated and pressure-molded for 10 minutes at 140 ° C. and 5 MPa, and the surface layer has a resin composition of 0.5 mm with a different thickness.
- a melamine resin decorative board was obtained.
- Example 4 a melamine resin decorative board with back surface glue was prepared and bonded to an interior material for a vehicle.
- Example 4 a resin decorative plate with a back surface paste was produced and bonded to an interior material for a vehicle.
- Example 4 was excellent in all of the boiling test, the 160 ° C. durability test, the vehicle material fuel test, and the bending formability. On the other hand, in Comparative Example 3 without the core material layer, the heat dissipating property was not sufficient. Moreover, in Comparative Example 4 having neither an adhesive layer nor a glass cloth layer, since the buffering action by the adhesive layer or the glass cloth layer disappeared, swelling occurred in the boiling test and the 160 ° C. durability test. Further, in Comparative Example 5 having a glass cloth layer instead of the adhesive layer, the adhesion was not sufficient, and part of the peeling occurred in the 160 ° C. durability test.
- Comparative Example 6 in which the thermoplastic emulsion resin was not supported on the second surface side of the surface layer, the surface layer was not sufficiently flexible, and thus the surface layer was cracked in the bending formability test. Further, in Comparative Example 7 in which melamine is not used as the surface layer material, the heat resistance and the flame resistance of the surface layer itself were not sufficient, which resulted in inferior results in the boiling test, the 160 ° C. durability test, and the vehicle material fuel test. It was.
- the present invention can be applied, for example, to the refurbishment of interior materials or exterior materials for ships, etc., as well as for the modification of interior materials or exterior materials for vehicles that require non-combustibility, such as railways and automobiles.
- the decorative board can be applied not only as a modification but also as a decorative panel as a new product.
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Abstract
Description
本願は、2012年3月7日に日本に出願された特願2012-050148号、及び2013年1月10日に日本に出願された特願2013-002889号に基づき優先権を主張し、その内容をここに援用する。
[1] 表面層と芯材層とが積層された構造を有し、
前記表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、前記芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、
前記芯材層は、熱放散性材料層で構成されることを特徴とするメラミン樹脂化粧板。
[2] 前記熱放散性材料層は金属層である[1]記載のメラミン樹脂化粧板。
[3] 前記金属層はアルミニウム層である[2]記載のメラミン樹脂化粧板。
[4] 前記表面層と芯材層との間にさらに接着層を有する、[1]~[3]のいずれか1項に記載のメラミン樹脂化粧板。
[5] 前記接着層が、熱硬化性樹脂の固形分を担持する接着層基材で構成される、[4]に記載のメラミン樹脂化粧板。
[6] 前記接着層基板が、ガラスクロスである、[5]に記載のメラミン樹脂化粧板。
[7] 前記熱可塑性エマルジョン樹脂の固形分は、平均粒径が30~100nmのエマルジョン樹脂粒子を含む、[1]~[6]のいずれか1項に記載のメラミン樹脂化粧板。
[8] 前記熱可塑性エマルジョン樹脂の固形分は、非水溶性である、[1]~[7]のいずれか1項に記載のメラミン樹脂化粧板。
[9] 前記熱可塑性エマルジョン樹脂の固形分は、単一粒子内にアクリル樹脂とウレタン樹脂との異相構造を有するウレタンアクリル複合粒子を含む、[1]~[8]のいずれか1項に記載のメラミン樹脂化粧板。
[10] 前記ウレタンアクリル複合粒子は、アクリル成分をコアとし、ウレタン成分をシェルとするコアシェル構造を有する水性クリヤータイプである、[9]に記載のメラミン樹脂化粧板。
[11] 常温(20~30℃)での最小曲げ半径が15mmR以下の曲げ加工性を有する、[1]~[10]のいずれか1項に記載のメラミン樹脂化粧板。
[12] 常温(20~30℃)での最小曲げ半径が10mmR以下の曲げ加工性を有する、[11]に記載のメラミン樹脂化粧板。
[13] 既存の仕上げ表面にメラミン樹脂化粧板を積層して、前記仕上げ表面を新装する仕上げ表面の改修方法であって、
前記メラミン樹脂化粧板は、表面層と芯材層とが積層された構造を有し、
前記表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、前記芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、
前記芯材層は、熱放散性材料層で構成されることを特徴とする仕上げ表面の改修方法。
[14] [1]~[12]のいずれかに記載されたメラミン樹脂化粧板を脱泡処理することを特徴とする、[13]に記載の仕上げ表面の改修方法。
[15] [14]に記載された仕上げ表面の改修方法であって、メラミン樹脂化粧板を成形後にロールにより前記仕上げ表面に加圧することにより、又は、前記メラミン樹脂化粧板を前記仕上げ表面に積層した後に前記メラミン樹脂化粧板を加圧、加熱若しくは熱圧着することにより、脱泡処理することを特徴とする仕上げ表面の改修方法。
[16] [1]~[15]のいずれかに記載された仕上げ表面の改修方法であって、前記メラミン樹脂化粧板は、裏面に予め粘着層が設けられていることを特徴とする仕上げ表面の改修方法。
[17] [1]~[16]のいずれかに記載された仕上げ表面の改修方法であって、前記仕上げ表面が、車両又は船舶の内装材又は外装材の仕上げ表面であることを特徴とする仕上げ表面の改修方法。
本発明の第1の実施形態による仕上げ表面の改修方法に用いるメラミン樹脂化粧板は、表面層と芯材層とが積層された構造を有するメラミン樹脂化粧板であって、前記表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、前記芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、前記芯材層は、熱放散性材料層で構成されることを特徴とする。
本実施形態のメラミン樹脂化粧板の構成の一例として、図2に、表面層15と芯材層16とから成るメラミン樹脂化粧板12の構成を示す。なお、図3に示すように表面層15と芯材層16との間に接着層17を有していても良い。また、メラミン樹脂化粧板の製造方法の一例として、図4に、メラミン樹脂化粧板12の製造方法の一例を示す。図4に示す例では、メラミン樹脂化粧板12は、表面層材料15Aと芯材層材料16Aとを重ね合わせ、これを加熱加圧成形して積層することにより得られる。
表面層15は、表面層材料15Aで構成され、この表面層材料15Aは、本実施形態のメラミン樹脂化粧板12の意匠面(露出される側の面)側に配置される。表面層材料15Aは、意匠面となる第1の面側151にメラミン樹脂を含有する樹脂を担持し、前記芯材層16と接する第2の面側152に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなるものである。
なお、本明細書において表面層基材が樹脂を担持するとは、樹脂が基材(担体)の表面に付着し、又は、基材内部の空隙部に含浸され、表面層材料の成形後に担持させた樹脂の性能を発現することを可能にする状態であることを意味する。なお、樹脂は基材の表面及び基材の内部に均一に分布していなくてもよい。
前記表面層基材の坪量は特に限定されないが、40~150g/m2であることが好ましい。坪量が前記下限値未満であると、樹脂含浸工程での切れ、しわの問題から、塗工処理が困難であり、さらに第1の面と第2の面それぞれに担持させる樹脂含浸量を調整する事も困難である。一方、坪量が前記上限値を超えると、表面層基材が担持する樹脂の含浸量にムラが生じ、メラミン樹脂化粧板12の柔軟性を低下させると共に、生産性低下、コスト高の原因となるため好ましくない。
メラミン樹脂としては、特に限定されないが、例えば、メラミンとホルムアルデヒドを中性又は弱アルカリ下において反応させて得られるものを用いることができる。メラミンに対するホルムアルデヒドの反応モル比((ホルムアルデヒドのモル量)/(メラミンのモル量)の値であり、以下、単に「反応モル比」ということがある。)は、特に限定されないが、1.0~4.0、好ましくは1.0~2.0、さらに好ましくは1.1~1.8として、反応させて得られたものを好適に用いることができる。反応モル比が前記下限値未満であると、未反応成分が増加し保存性低下、コスト高となり、前記上限値を超えると硬化後の樹脂柔軟性低下が著しくなる。なお、メラミン樹脂としては、1種類が単独で含まれるもの用いることもできるし、反応モル比や重量平均分子量等が異なる2種類以上のメラミン樹脂を混合して含むものを用いることもできる。
また、メラミン樹脂としては、住友化学(株)製のメラミン樹脂等、市販のものを用いることもできる。
なお、熱可塑性エマルジョン樹脂の固形分としては、これらの中の1種類が単独で含まれるもの用いることもできるし、異なる2種類以上の熱可塑性樹脂を混合して含むもの用いることもできる。
前記熱可塑性エマルジョン樹脂の固形分(溶剤を除く全成分)は、特に限定されないが、前記熱可塑性エマルジョン樹脂の25~60質量%が好ましく、特に30~45質量%が好ましい。これにより、前記熱可塑性エマルジョン樹脂の基材への含浸性を向上できる。
本実施形態のメラミン樹脂化粧板12は、表面層15の第2の面側152に、芯材層16を積層してなる。
本実施形態に用いる芯材層は、熱伝導率が10W/m・K以上の熱放散性材料を用いることが好ましい。
熱伝導率が10W/m・K以上の熱放散性材料としては、銀(420W/m・K)、銅(398)、金(320)、アルミニウム(236)、シリコン(168)、真鍮(106)、鉄(84)等の金属類を主に用いることができるが、チッ化ホウ素等の熱伝導粒子を含有する樹脂シート等も熱伝導率が条件を満たせば用いることもできる。これらの中でも、熱伝導率と加工性、汎用性の点からアルミニウムからなるアルミニウム層が芯材層として好ましく用いられる。
ここで用いられるアルミニウム層は、アルミニウム箔又はアルミニウム板を適用することができ、メラミン化粧板に、耐熱性、不燃性、剛性などを付与することができる。
このアルミニウム層の厚みとしては、0.2mm以上とすることが好ましい。これにより、化粧板に充分な耐熱性、不燃性を付与することができる。アルミニウム層の厚みが下限値より薄くなると、下地によっては充分な不燃性が得られなくなる。また、厚みの上限については、特に限定されないが、厚みが大きいほど耐熱性、不燃性は向上するが、メラミン化粧板の厚みと重量が増大すると共に、コストも嵩むため、最終的な製品における設計上、許容される範囲で設定することが好ましく、0.5mm以下にすることが好ましい。
メラミン樹脂化粧板12は、表面層15と芯材層16との間に接着層を有していても良い。
前記接着層としては、プライマー、接着剤、接着フィルム又はガラスクロスプリプレグ等の接着剤の役割をするものを1層又は2層以上の構成として用いることができる。これらはいずれも汎用のものを用いることができる。また、接着効果は無くとも、被着体同士よりも密着の良いものとして例えばガラスクロスを用いることができる。ガラスクロスは、表面層の第2の面側152に担持される熱可塑性エマルジョン樹脂と、プライマー処理した芯材層のそれぞれとの密着性が良好であり、表面層の第2の面側とプライマー処理した芯材層とを直接接するよりも接着性が大きく向上する。これにより、メラミン樹脂化粧板の表面層と芯材層との接着力を強化することができる。
また、ガラスクロスを構成するガラスとしては、例えばEガラス、Cガラス、Aガラス、Sガラス、Dガラス、NEガラス、Tガラス、Hガラス等が挙げられる。これらの中でもTガラスが好ましい。これにより、ガラスクロスの熱膨張係数を小さくすることができる。
また、ガラスクロス以外にも、不織布、コア紙、チタン紙、カーボンファイバークロス、アラミド繊維クロスなどを用いてもよい。
メラミン樹脂化粧板12は、上述した表面層材料15Aと芯材層材料16Aとを、所定の順序で重ね合わせ、これを加熱加圧成形して積層することにより得られる。
メラミン樹脂化粧板12を加熱加圧成形する条件としては特に限定されないが、一例を挙げると、温度130~150℃、圧力2~8MPa、時間3~60分間で実施することができる。
また、メラミン樹脂化粧板12の成形時に、表面層材料15Aの第1の面側に、鏡面仕上げ板を重ねることにより鏡面仕上げとすることができ、エンボス板又はエンボスフィルム等を重ねることにより、エンボス仕上げとすることができる。
本実施形態のメラミン樹脂化粧板は、常温(通常20~30℃程度)での最小曲げ半径が15mmR以下の曲げ加工が可能であるが、特に限定はされない。最小曲げ半径Rとは、半径Rの湾曲部を有する型に沿わせて、一方方向に行う常温曲げ加工を繰り返し実施しても、割れ等の不具合を生じず、100%の良品が得られる最小の型の半径Rを意味する。
本実施形態の仕上げ表面の改修方法は、既存の仕上げ表面に、メラミン樹脂化粧板を積層して、仕上げ表面を新装する方法であり、特に限定されないが、例えば、加熱加圧成形して得られたメラミン樹脂化粧板を仕上げ表面に積層した後、メラミン樹脂化粧板を加圧、加熱もしくは熱圧着する方法により、改修することができる。本実施形態の仕上げ表面の改修方法では、加熱加圧成形して得られたメラミン樹脂化粧板をロールにより加圧することにより、又は、メラミン樹脂化粧板を仕上げ表面に積層した後、メラミン樹脂化粧板を加圧、加熱もしくは熱圧着することにより、脱泡処理することが好ましい。また、メラミン樹脂化粧板の裏面には、予め粘着層が設けられていてもよい。
本発明の第2の実施形態による仕上げ表面の改修方法に用いるメラミン樹脂化粧板は、表面層と芯材層とが接着層を介して積層された構造を有するメラミン樹脂化粧板であって、表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、接着層は、熱硬化性樹脂の固形分を担持する接着層基材からなる接着層材料で構成され、芯材層は、熱放散性材料層で構成されることを特徴とする。
以下、本実施形態の仕上げ表面の改修方法に用いるメラミン樹脂化粧板について、図をもとに詳細に説明する。
表面層15は、表面層材料15Aで構成され、この表面層材料15Aは、本実施形態のメラミン樹脂化粧板12の意匠面(露出される側の面)側に配置される。表面層材料15Aは、意匠面となる第1の面側151にメラミン樹脂を含有する樹脂を担持し、接着層17と接する第2の面側152に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなるものである。
第2の実施形態における表面層15は、第1の実施形態におけるものと同様のものを用いることができる。
本実施形態のメラミン樹脂化粧板12は、表面層15の第2の面側152に、接着層17を介して芯材層16を積層してなる。
メラミン樹脂化粧板12は、表面層15と芯材層16との間に接着層17を有している。
メラミン樹脂化粧板12は、上述した表面層材料15Aと芯材層材料16Aとを接着層17を介して重ね合わせ、これを加熱加圧成形して積層することにより得られる。
本実施形態の仕上げ表面の改修方法は、既存の仕上げ表面に、メラミン樹脂化粧板を積層して、仕上げ表面を新装する方法であり、特に限定されないが、例えば、加熱加圧成形して得られたメラミン樹脂化粧板を仕上げ表面に積層した後、メラミン樹脂化粧板を加圧、加熱もしくは熱圧着する方法により、改修することができる。本実施形態の仕上げ表面の改修方法では、加熱加圧成形して得られたメラミン樹脂化粧板をロールにより加圧することにより、又は、メラミン樹脂化粧板を仕上げ表面に積層した後、メラミン樹脂化粧板を加圧、加熱もしくは熱圧着することにより、脱泡処理することが好ましい。また、メラミン樹脂化粧板の裏面には、予め粘着層が設けられていてもよい。
本発明に用いるメラミン樹脂化粧板10を以下の方法にて形成した。表面層基材として坪量80g/m2の酸化チタン含有化粧紙(大日本印刷(株)製)を用い、前記酸化チタン含有化粧紙の第2の面側に、ウレタンアクリル複合粒子のエマルジョン(中央理化工業社製「SU-100」、平均粒径:84nm、分散媒:水)を固形分で34g/m2となるように塗工し、続いて前記化粧紙の第1の面側(意匠面側)に、メラミン樹脂(反応モル比1.4、樹脂固形分50質量%)で50g/m2塗工した後、120℃の熱風乾燥機にて90秒乾燥し、樹脂比率が51%、揮発分率3%の表面層材料を得た。なお、前記メラミン樹脂は反応釜に原料メラミンとホルマリンを所定配合比率で仕込み触媒添加後、沸点まで昇温して還流反応し、メラミン溶解が完了した事を確認した上で、反応終点に達したら脱水処理にて樹脂固形分を調整し冷却する方法により合成した。
上記で得られた表面層材料と、表面をエポキシ樹脂によるプライマー処理を施した厚み0.3mmのアルミニウム箔とを、表面層材料の第2の面側にアルミニウム箔のプライマー処理面を重ね合わせ、140℃、8MPaの条件で20分間加熱加圧成形して、厚さ0.4mmの試料を得た。
本発明に用いるメラミン樹脂化粧板10を以下の方法にて形成した。
表面層基材については、実施例1と同様の方法で樹脂比率が51%、揮発分率3%の表面層材料を得た。次に、接着層として、坪量104g/m2のガラスクロス(台湾ナンヤ製:品番ナンヤ-2116)を用い、ウレタンアクリル複合粒子のエマルジョン(中央理化工業社製「SU-100」、平均粒径:84nm、分散媒:水)をキスコーター方式にて固形分で5g/m2となるように塗工した後、120℃の熱風乾燥機にて90秒乾燥し、樹脂比率が5%、揮発分率0.5%の接着層材料を得た。
上記で得られた表面層材料、接着層材料と、表面をエポキシ樹脂によるプライマー処理を施した厚み0.3mmのアルミニウム箔とを、表面層材料の第2の面側に接着層材料に置き、更にアルミニウム箔のプライマー処理面を重ね合わせ、140℃、5MPaの条件で10分間加熱加圧成形して、厚さ0.5mmの試料を得た。
次いで実施例1と同様にして、裏面糊付きメラミン樹脂化粧板10を作製し、車両用の内装材への貼り合せを行った。
表面層基材については、実施例1と同様の方法で樹脂比率が51%、揮発分率3%の表面層材料を得た。
上記で得られた表面層材料と、表面をエポキシ樹脂によるプライマー処理を施した厚み0.1mmのアルミニウム箔とを、表面層材料の第2の面側にアルミニウム箔のプライマー処理面を重ね合わせ、140℃、8MPaの条件で20分間加熱加圧成形して、厚さ0.3mmの試料を得た。
次いで実施例1と同様にして、裏面糊付きメラミン樹脂化粧板10を作製し、車両用の内装材への貼り合せを行った。
メラミンに対するホルムアルデヒドのモル比1.6、数平均分子量230、粘度40cps/20℃のポストホーム用水溶性メラミン樹脂に固形分45%、粘度35cps/20℃の水性アクリル樹脂エマルジョンを重量比で100:35の比率で混合し、水により粘度20cps/25℃に調整した後、触媒を添加し含浸用メラミンワニスを得た。
このワニスを、坪量80g/m2の酸化チタン含有化粧紙(大日本印刷(株)製)に含浸し、加熱乾燥して、樹脂量55%、揮発分6%の表面層材料を得た。
上記で得られた表面層材料と表面をエポキシ樹脂によるプライマー処理を施した厚み0.3mmのアルミニウム箔とを、表面層材料側にアルミニウム箔のプライマー処理面になるように置き、145℃、10MPaの条件で10分間加熱加圧成形して、厚さ0.5mmの試料を得た。
次いで実施例1と同様にして、裏面糊付きメラミン樹脂化粧板10を作製し、車両用の内装材への貼り合せを行った。
表面層材料に0.2mmオレフィンシート(塩化ビニル樹脂印刷シート)を用い、表面にウレタン系接着剤を施した厚み0.3mmのアルミニウム箔とを、表面層材料側にアルミニウム箔の接着剤塗布面になるように置き、80℃、30分で硬化させ、厚さ0.5mmの試料を得た。
次いで実施例1と同様にして、裏面糊付きメラミン樹脂化粧板10を作製し、車両用の内装材への貼り合せを行った。
比較例1では、表面層の第2の面側に担持させる樹脂として、熱可塑性エマルジョン樹脂の固形分を用いずに、メラミン樹脂を用いたため、メラミン化粧板は常温曲げ加工性に劣った。
比較例2では、表面層にオレフィンを用いたため、表面硬度、耐汚染性などの表面特性が劣った。
1.建築不燃性能試験
日本建築総合試験場の業務標準「防耐火性能試験・評価業務方法書」4.10 不燃性能試験・評価方法における、(2)ii)4.10.2 の発熱性試験・評価方法 及び 4.10.3 のガス有害性試験・評価方法、により実施した。
上記業務標準「防耐火性能試験・評価業務方法書」の上記項目には、建築基準法第2条第9号(不燃材料)の規定に基づく認定に係わる性能評価方法について記載されている。
2.鉄道車両用材料燃焼試験(車材燃試)
「鉄道に関する技術上の基準を定める省令」 (平成13年12月25日国土交通省令 第151号)の第83条の定めにしたがって行われる「鉄道車両用材料燃焼試験」に準拠して実施。
3.曲げ成形性試験
JIS K6902の曲げ成形性試験(A法)に準拠し、室温、15mmRにて外曲げ及び内曲げ成形を行い、化粧シート表面の割れの有無を確認した。
4.表面鉛筆硬度
JIS K5401の塗膜鉛筆引っ掻き試験による。
5.耐汚染性試験
JIS K6902の耐汚染性試験(試薬A)による。
メラミン樹脂化粧板を以下の方法にて形成した。
表面層基材として坪量80g/m2の酸化チタン含有化粧紙(大日本印刷(株)製)を用い、前記酸化チタン含有化粧紙の第2の面側に、ウレタンアクリル複合粒子のエマルジョン(中央理化工業社製「SU-100」、平均粒径:84nm、分散媒:水)を固形分で34g/m2となるように塗工し、続いて前記化粧紙の第1の面側(意匠面側)に、メラミン樹脂(反応モル比1.4、樹脂固形分50質量%)で50g/m2塗工した後、120℃の熱風乾燥機にて90秒乾燥し、樹脂比率が51%、揮発分率3%の表面層材料を得た。なお、前記メラミン樹脂は反応釜に原料メラミンとホルマリンを所定配合比率で仕込み触媒添加後、沸点まで昇温して還流反応し、メラミン溶解が完了した事を確認した上で、反応終点に達したら脱水処理にて樹脂固形分を調整し冷却する方法により合成した。
表面層材料については、実施例4と同様の方法で樹脂比率が51%、揮発分率3%の表面層材料を得た。また、接着層材料についても、実施例4と同様の方法で接着層材料全体の重さを100質量%としたときに、3質量%のフェノール樹脂が残存する接着層材料を得た。
表面層材料については、実施例4と同様の方法で樹脂比率が51%、揮発分率3%の表面層材料を得た。得られた表面層材料と、表面をエポキシ樹脂(日本ペイント株式会社製ニッペパワーバインド)によるプライマー処理を施した厚み0.3mmのアルミニウム箔とを、表面層材料の第2の面側にアルミニウム箔のプライマー処理面を重ね合わせ、140℃、5MPaの条件で10分間加熱加圧成形して、接着層のない厚さ0.4mmのメラミン樹脂化粧板を得た。
表面層材料については、実施例4と同様の方法で樹脂比率が51%、揮発分率3%の表面層材料を得た。
メラミンに対するホルムアルデヒドのモル比1.6、数平均分子量230、粘度40cps/20℃のポストホーム用水溶性メラミン樹脂に固形分45%、粘度35cps/20℃の水性アクリル樹脂エマルジョンを重量比で100:35の比率で混合し、水により粘度20cps/25℃に調整した後、触媒を添加し含浸用メラミンワニスを得た。
得られたワニスを、表面層基材としての坪量80g/m2の酸化チタン含有化粧紙(大日本印刷(株)製)に含浸した後、120℃の熱風乾燥機にて90秒乾燥し、樹脂比率が55%、揮発分率6%の表面層材料を得た。
表面層材料として0.2mmオレフィンシート(塩化ビニル樹脂印刷シート)を用い、芯材層材料として表面にウレタン系接着剤を施した厚み0.3mmのアルミニウム箔を用い、表面層材料にアルミニウム箔の接着剤塗布面を重ね合わせ、80℃、30分で硬化させ、表面層材料が異なり、かつ接着層がない、厚さ0.5mmの樹脂化粧板を得た。
一方、芯材層のない比較例3では、熱放散性が十分でなかったため、車材燃試で火膨れを起こし難燃の判定となった。
また、接着層もガラスクロス層もない比較例4では、接着層又はガラスクロス層による緩衝作用がなくなったため、煮沸試験及び160℃耐久性試験で膨れが発生した。
また、接着層の代わりにガラスクロス層を有する比較例5では、密着が十分でなかったため、160℃耐久性試験で一部剥離が発生した。
また、表面層の第2の面側に熱可塑性エマルジョン樹脂が担持されていない比較例6では、表面層の柔軟性が充分ではなかったため、曲げ成形性試験で表面層に割れが発生した。
また、表面層材料としてメラミンが用いられていない比較例7では、表面層自体の耐熱性と耐燃性が十分でなかたため、煮沸試験、160℃耐久性試験及び車材燃試で劣る結果となった。
1.煮沸試験
熱湯(100℃)に100mm角の試験片を2時間浸漬後、外観を確認し、膨れ、剥離が全く生じないものを○、生じるものを×とした。
100mm角の試験片を160℃のオーブンで24時間加熱後、外観を確認し、膨れ、剥離が全く生じないものを○、生じるものを×とした。
「鉄道に関する技術上の基準を定める省令」(平成13年12月25日国土交通省令 第151号)の第83条の定めにしたがって行われる「鉄道車両用材料燃焼試験」に準拠して実施。
JIS K 6902の曲げ成形性試験(A法)に準拠し、室温(23℃)、15mmRにて外曲げ及び内曲げ成形を行い、化粧板表面の割れの有無を確認した。
2 粘着テープ
3 塩化ビニルシート
10、12 メラミン樹脂化粧板
15 表面層
15A 表面層材料
151 第1の面側
152 第2の面側
16 芯材層
16A 芯材層材料
17 接着層
17A 接着層材料
Claims (17)
- 表面層と芯材層とが積層された構造を有し、
前記表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、前記芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、
前記芯材層は、熱放散性材料層で構成されることを特徴とするメラミン樹脂化粧板。 - 前記熱放散性材料層は金属層である請求項1記載のメラミン樹脂化粧板。
- 前記金属層はアルミニウム層である請求項2記載のメラミン樹脂化粧板。
- 前記表面層と芯材層との間にさらに接着層を有する、請求項1~3のいずれか1項に記載のメラミン樹脂化粧板。
- 前記接着層が、熱硬化性樹脂の固形分を担持する接着層基材で構成される、請求項4に記載のメラミン樹脂化粧板。
- 前記接着層基板が、ガラスクロスである、請求項5に記載のメラミン樹脂化粧板。
- 前記熱可塑性エマルジョン樹脂の固形分は、平均粒径が30~100nmのエマルジョン樹脂粒子を含む、請求項1~6のいずれか1項に記載のメラミン樹脂化粧板。
- 前記熱可塑性エマルジョン樹脂の固形分は、非水溶性である、請求項1~7のいずれか1項に記載のメラミン樹脂化粧板。
- 前記熱可塑性エマルジョン樹脂の固形分は、単一粒子内にアクリル樹脂とウレタン樹脂との異相構造を有するウレタンアクリル複合粒子を含む、請求項1~8のいずれか1項に記載のメラミン樹脂化粧板。
- 前記ウレタンアクリル複合粒子は、アクリル成分をコアとし、ウレタン成分をシェルとするコアシェル構造を有する水性クリヤータイプである、請求項9に記載のメラミン樹脂化粧板。
- 常温20~30℃での最小曲げ半径が15mmR以下の曲げ加工性を有する、請求項1~10のいずれか1項に記載のメラミン樹脂化粧板。
- 常温20~30℃での最小曲げ半径が10mmR以下の曲げ加工性を有する、請求項11に記載のメラミン樹脂化粧板。
- 既存の仕上げ表面にメラミン樹脂化粧板を積層して、前記仕上げ表面を新装する仕上げ表面の改修方法であって、
前記メラミン樹脂化粧板は、表面層と芯材層とが積層された構造を有し、
前記表面層は、意匠面となる第1の面側にメラミン樹脂を含有する樹脂を担持し、前記芯材層と接する第2の面側に熱可塑性エマルジョン樹脂の固形分を担持する表面層基材からなる表面層材料で構成され、
前記芯材層は、熱放散性材料層で構成されることを特徴とする仕上げ表面の改修方法。 - 請求項1~12のいずれか1項に記載されたメラミン樹脂化粧板を脱泡処理することを特徴とする、請求項13に記載の仕上げ表面の改修方法。
- 請求項14に記載された仕上げ表面の改修方法であって、前記メラミン樹脂化粧板を成形後にロールにより前記仕上げ表面に加圧することにより、又は、前記メラミン樹脂化粧板を前記仕上げ表面に積層した後に前記メラミン樹脂化粧板を加圧、加熱若しくは熱圧着することにより、脱泡処理することを特徴とする仕上げ表面の改修方法。
- 請求項13~15のいずれか1項に記載された仕上げ表面の改修方法であって、前記メラミン樹脂化粧板は、裏面に予め粘着層が設けられていることを特徴とする仕上げ表面の改修方法。
- 請求項1~16のいずれか1項に記載された仕上げ表面の改修方法であって、前記仕上げ表面が、車両又は船舶の内装材又は外装材の仕上げ表面であることを特徴とする仕上げ表面の改修方法。
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US14/382,719 US9707740B2 (en) | 2012-03-07 | 2013-03-06 | Melamine resin decorative sheet and method of refurbishing finished surface |
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US11077639B2 (en) | 2016-08-19 | 2021-08-03 | Wilsonart Llc | Surfacing materials and method of manufacture |
US11745475B2 (en) | 2016-08-19 | 2023-09-05 | Wilsonart Llc | Surfacing materials and method of manufacture |
US10933608B2 (en) | 2016-08-19 | 2021-03-02 | Wilsonart Llc | Surfacing materials and method of manufacture |
US11020948B2 (en) | 2017-09-28 | 2021-06-01 | Wilsonart Llc | High pressure decorative laminate having a top layer of energy cured acrylated urethane polymer |
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CN112900151A (zh) * | 2019-11-19 | 2021-06-04 | 佛山市西钢装饰材料有限公司 | 一种三聚氰胺软化纸及其制作工艺 |
TW202140676A (zh) * | 2020-04-22 | 2021-11-01 | 日商愛克工業股份有限公司 | 組成物、轉印片、三聚氰胺裝飾板及三聚氰胺裝飾板的製造方法 |
CN114960294A (zh) * | 2022-06-01 | 2022-08-30 | 上海贝辉木业有限公司 | 一种耐龟裂的浸渍纸及其制备方法 |
KR102501116B1 (ko) * | 2022-07-07 | 2023-02-20 | 한상담 | 글루 페이퍼, lpm 함침 페이퍼, 이들을 포함하는 무기질 친환경 가공보드 및 이의 제조방법 |
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