JP2005119022A - Manufacturing method of decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily manufacturing a decorative material having emboss-processing and a surface protective layer applied to its surface, enhanced in design properties and having a surface shape regenerating the surface shape of an embossing plate faithfully according to a design without receiving the effect of the coating irregularity or the like of the surface protective layer. <P>SOLUTION: The surface protective layer 2 containing a curable resin is formed on a base material 1 of which the surface comprises at least a thermoplastic resin and, after the curable resin is cured, emboss-processing is applied to the base material 1. The curable resin may comprise an ionizing radiation curable resin or a mixed system of the ionizing radiation curable resin and a thermosetting resin. In the case of the mixed system, the ionizing radiation curable resin is cured by the irradiation with ionizing radiation to bring the surface protective layer to a semicured state and, after emboss-processing is applied, the thermosetting resin may be cured. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a decorative material used as an interior / exterior material for furniture such as an interior / exterior in a building such as a house, an exterior of a household appliance or a household appliance, and an interior / exterior material of a transportation device such as a vehicle. In particular, the present invention relates to a decorative material provided with a surface protective layer containing an ionizing radiation curable resin on the surface and embossed on the surface.

  Such a decorative material is generally embossed on the surface in order to give a three-dimensional appearance, texture, hand feeling and the like similar to wood, stone, and fabric. On the other hand, a surface protective layer made of a curable resin is generally formed on the surface of the decorative material in order to impart surface properties such as scratch resistance, abrasion resistance, solvent resistance, and weather resistance. is there. When both are used in combination, the thermoplastic resin is more suitable for embossing than the curable resin, so at least embossing is applied to the decorative material substrate whose surface is made of thermoplastic resin, and then the curable type is used. It is common to form a surface protective layer made of resin.

  However, in this method, the gloss or flatness of the surface of the decorative material is determined by the surface of the surface protective layer formed later, so that it depends on the coating liquid properties of the surface protective layer, problems in the coating system, etc. If the coating unevenness occurs or the surface protective layer does not adhere to the uniform thickness due to the surface unevenness due to the embossing, the surface shape precisely shaped by the corner embossing cannot be used as it is. There's a problem. In particular, when the embossing is mirror surface embossing, when the surface protective layer is applied and formed on the surface of the precise mirror surface of the decorative material formed by mirror surface embossing, very little coating unevenness is generated. However, when it occurs, it is very conspicuous in appearance, and it is extremely difficult to obtain a product with good design quality.

Prior art document information.
JP-A-63-151382 Japanese Patent Laid-Open No. 1-180340 JP-A-3-174279 Japanese Patent Laid-Open No. 5-92696 JP-A-9-193302 JP-A-10-74218

  The present invention is a method for producing a decorative material having an embossed surface and a surface protective layer on its surface, and is designed to faithfully reproduce the surface shape of the embossed plate without being affected by uneven coating of the surface protective layer. An object of the present invention is to provide a production method capable of easily producing a highly-designed decorative material having a normal surface shape.

  The present invention provides a cosmetic material characterized in that a surface protective layer containing a curable resin is formed on a substrate having at least a surface made of a thermoplastic resin, the curable resin is cured, and then embossed. It is a manufacturing method.

  In the manufacturing method, the surface protective layer contains at least an ionizing radiation curable resin as the curable resin, and the ionizing radiation curable resin is cured by irradiation with ionizing radiation. It is a manufacturing method.

  Moreover, in the said manufacturing method, the said surface protective layer is a manufacturing method of the cosmetics characterized by including a thermosetting resin in addition to the said ionizing radiation curable resin as said curable resin.

  Moreover, in the said manufacturing method, the weight ratio of the said ionizing radiation curable resin and the said thermosetting resin is 5: 5-1: 9, It is a manufacturing method of the cosmetics characterized by the above-mentioned.

  Further, in the above production method, the surface protection layer is semi-cured by curing the ionizing radiation curable resin by irradiation with ionizing radiation while the thermosetting resin contained in the surface protection layer is in an uncured state. After making into a state, the said embossing is given, and the said thermosetting resin is hardened after that, The said surface protective layer is hardened completely, It is a manufacturing method of the cosmetics characterized by the above-mentioned.

  In the manufacturing method, the embossing is mirror surface embossing.

  Moreover, in the said manufacturing method, another embossing is given to the surface of the base material before forming the said surface protective layer, It is a manufacturing method of the cosmetics characterized by the above-mentioned.

  Further, in the above manufacturing method, the another embossing is an embossing having a shape constituted by a concave portion and a planar convex portion, and the embossing performed after forming the surface protective layer is performed by the planar convex portion. This is a method for producing a decorative material, characterized in that the embossing is applied to only the mirror.

  In the present invention, the embossing is performed after the surface protective layer is formed, so that the effect of uneven coating of the surface protective layer can be corrected by the embossing. The surface shape as designed and faithful to the shape of the plate can be reliably provided. In particular, when mirror-like smoothness is required on the surface of the decorative material, the surface gloss of the coating surface of the surface protective layer is increased by mirror surface embossing while ensuring sufficient surface properties by the surface protective layer, A highly-designed decorative material having a mirror-like surface gloss as expected can be easily obtained.

  The base material 1 in the decorative material of the present invention may be any material as long as at least the surface is made of a thermoplastic resin excellent in embossing suitability. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and copolyester (PET-G), acrylic resins such as polymethyl methacrylate, styrene resins such as ABS, Polyamide resins such as nylon, polyvinyl resins such as polyvinyl chloride and polyvinyl acetate, ionomers, cellulose derivatives, fluorine resins such as polyvinyl fluoride, etc., or a mixture, copolymer, composite selected from these A body, a laminated body, etc. can be used.

  On the back surface of the surface layer made of the thermoplastic resin in the base material 1, another layer made of an arbitrary material may be laminated. Examples of the material include paper such as thin paper, titanium paper, kraft paper, high-quality paper, resin-impregnated paper, resin-mixed paper, inter-paper reinforced paper, synthetic fiber paper, flame-retardant paper, inorganic paper, woven fabric, knitted fabric, etc. Textile materials such as cloth and non-woven fabric, thermoplastic resins, thermosetting resins, synthetic resin materials such as fiber reinforced plastic, plywood, laminated wood, medium density fiberboard, wood based materials such as particle board, iron, copper, Metal materials such as brass, aluminum and stainless steel, inorganic materials such as glass, ceramics, gypsum board, slate board, wood wool cement board, slag cement board, glass fiber reinforced concrete board, lightweight cellular concrete board, etc. Or arbitrarily combined and laminated.

  The shape of the base material 1 is not particularly limited, for example, a film shape, a sheet shape, a flat plate shape, a prismatic shape, or any other shaped article. However, in embossing, considering the application of the roll embossing method with excellent productivity, a film shape, a sheet shape or a flat plate shape is desirable, and a continuous long film shape or sheet shape particularly excellent in continuous productivity is the most. desirable. In addition, after giving the surface protection layer 2 and the embossing to the base material 1 of such a shape, it can be suitably implemented to be molded into an arbitrary shape or laminated on the surface of another material of an arbitrary shape. it can. Additives such as pigments, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, flame retardants, antistatic agents, etc. to the whole or part of the substrate 1 Giving a pattern by printing or the like to the front surface, the back surface, or the interlayer can also be arbitrarily performed.

  The surface protective layer 2 formed on the surface of the substrate 1 is mainly composed of a curable resin such as a thermosetting resin or an ionizing radiation curable resin, and is generally in an uncured state of the curable resin. The coating liquid obtained by dissolving or dispersing an uncured liquid body or solid in an arbitrary solvent is applied to the surface of the substrate 1 by an arbitrary method. Prior to the formation of the surface protective layer 2, the surface of the substrate 1 is subjected to a surface activation treatment such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, radiation treatment, acid treatment, or alkali treatment. Or a primer layer may be formed.

  Examples of the thermosetting resin include melamine resins, urea resins, phenol resins, epoxy resins, polyurethane resins, acrylic resins, polyester resins, silicone resins, and the like. For example, (meth) acrylate resins, epoxy resins, polyester resins and the like can be used alone or in an arbitrary mixed system. Also, for example, colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, gloss adjusters, lubricants, lubricants, mold release agents, antistatic agents, anti-condensation agents, antiblocking agents, antibacterial agents, Arbitrary additives such as fungicides, insect repellents, deodorants, formaldehyde scavengers, fragrances, ion generators and photocatalysts can also be added. Furthermore, two or more layers may be formed using the same or different kinds of resins. In consideration of the surface properties of the resulting cosmetic material and the retention of the surface shape after embossing (preventing deformation and scratches), at least the outermost curable resin layer is a highly ionizing radiation curable type It is desirable to include at least a resin.

  Examples of coating methods include roll coating, knife coating, air knife coating, kiss coating, rod coating, gravure coating, micro gravure coating, die coating, lip coating, comma coating, and dip coating. Conventionally known methods such as an arbitrary coating method such as a flow coating method and a spray coating method, a gravure printing method, an offset printing method, a flexographic printing method, and a screen printing method can be arbitrarily employed.

  In the method for producing a decorative material of the present invention, the surface protective layer 2 formed on the surface of the substrate 1 is cured, and then the surface is embossed (FIG. 1). When embossing is performed before the surface protective layer 2 is cured, the surface protective layer 2 partially flows due to the pressure of the embossing. As a result, the film thickness of the surface protective layer 2 changes, and the surface protective layer 2 partially When the surface protective layer 2 is cured and then embossed, the surface is not affected by the embossing pressure. Since the protective layer 2 does not partially flow and maintains a uniform film thickness, sufficient surface properties can be maintained over the entire surface.

  For the above purpose, the surface protective layer 2 is not necessarily completely cured before embossing, and is not necessarily completely cured, and is in a semi-cured state that does not flow due to embossing pressure. There is no problem. On the contrary, if a method of embossing in a semi-cured state and then completely curing is adopted, the surface protective layer 2 at the time of embossing is obtained because the surface protective layer 2 retains an appropriate flexibility during the embossing. This is effective in preventing the occurrence of cracks and has the advantage that the surface shape of the embossed plate is shaped more faithfully on the surface of the surface protective layer 2.

  In order to make the surface protective layer 2 semi-cured, if the curable resin contained in the surface protective layer 2 is a thermosetting resin, the heating temperature for curing is set lower than usual, and / or If it is a method for setting the heating time to be small, or an ionizing radiation curable resin, it can be performed by a method for setting the irradiation energy and / or irradiation dose of ionizing radiation such as an electron beam or ultraviolet rays to be less than usual. Due to variations in conditions, the degree of semi-curing tends to vary, and thus the formability by embossing tends to vary.

  In order to avoid this problem, as the curable resin contained in the surface protective layer 2, a thermosetting resin and an ionizing radiation curable resin are used in combination, and only one of them is cured to a semi-cured state and embossed. It is advisable to employ a method in which the other is cured later and completely cured. Which one is cured first is arbitrary, but generally the curing rate is much faster in ionizing radiation curing than in heat curing, so the first curing (semi-curing) is more likely to be semi-cured by ionizing radiation curing. It is advantageous in that embossing can be carried out continuously and efficiently.

  In this case, if the ratio of the ionizing radiation curable resin is too high, the degree of curing at the time of semi-curing is high, so it is difficult to obtain the effect of embossing in a semi-cured state, so it depends on the type of resin. In general, it is desirable that the ionizing radiation curable resin be equal to or less than the thermosetting resin. On the other hand, even if the ratio of the ionizing radiation curable resin is too low, the ionizing radiation curable resin is at least a curable resin because it is substantially in an uncured state when semi-cured and cannot prevent the resin from flowing during embossing. It is desirable to occupy 10% by weight or more of the whole. That is, the weight ratio between the ionizing radiation curable resin and the thermosetting resin is preferably 5: 5 to 1: 9.

  As an embossing method applied to the surface of the surface protective layer 2, any conventionally known method such as a flat hot press embossing method or a hot roll embossing method can be employed. As an embossing plate used for this embossing, any material such as metal, resin, ceramic, etc. may be used as a plate making method, as well as a conventionally known mechanical engraving method, photosensitive resin method, etching method, electroforming method, Any of thermal spraying, electron beam engraving, laser engraving, etc. may be used. In general, the etching method using a metal such as copper or nickel or electroforming is often used, and the surface is often subjected to hard chrome plating for the purpose of improving durability. In the case of a mirror embossing plate, various polishing methods such as a buff polishing method and a lapping polishing method can also be used.

  There is no particular limitation on the surface shape 3 formed by embossing, for example, wood grain shape, wood grain conduit shape, stone cleaved surface shape, cloth shape, Japanese paper shape, grained shape, satin shape, line shape, geometric shape, etc. The shape used for a conventionally known decorative material can be employed.

  The surface shape 3 where the effects of the present invention are particularly remarkably exhibited is a mirror surface. That is, when the surface of the base material 1 is subjected to mirror surface embossing using a mirror surface embossing plate to form the surface of the base material 1 into a precise mirror surface, and then the surface protective layer 2 is applied and formed. When coating defects such as extremely small coating streaks, bumps (protrusions), dents (concaves), and unevenness (film thickness difference) occur locally, the flatness and smoothness of the entire surface are extremely high. For this reason, the defect portion is emphasized more than is actually recognized by the observer, and very few coating defects result in the design characteristics of the cosmetic material being greatly reduced. On the other hand, according to the present invention, if the surface protective layer 2 is coated and cured (including semi-cured) and then subjected to mirror embossing, unevenness due to slight coating defects on the surface protective layer 2 is also smoothed. Since it is flattened and is not recognized as a defect by the observer, there is an advantage that a highly-designed cosmetic material having a high mirror surface gloss can be easily obtained.

  In addition, according to the method of the present invention, the surface protective layer 2 is hardened at least to such an extent that it does not flow during embossing, and then embossed. It may be difficult to shape a large shape or a shape with a short irregularity period. In such a case, an embossing process may be performed in advance on the surface of the substrate 1 before the surface protective layer 2 is formed, and the embossing may be performed again after the surface protective layer 2 is formed and cured.

  In the above case, the shape of the embossing applied first and the shape of the embossing applied later may be the same shape or may be different. In other words, no matter how precise the shape is formed by the embossing performed first, the surface shape is further changed by the subsequent coating of the surface protective layer 2 or the embossing performed later. It doesn't make much sense to pursue the shape accuracy of embossing. Therefore, in the embossing that is performed first, the surface protective layer 2 can be followed by shaping only a shape element having a large degree of deformation that is difficult to follow after the formation and curing of the surface protective layer 2, that is, a rough shape. A shape element having a small degree of deformation, that is, a precise shape may be shaped by embossing performed later. Note that the embossing performed later does not necessarily have to cover the entire surface of the surface protective layer 2, and may be performed only on a portion requiring precise shape processing.

  This method is particularly effective when the surface shape required for the decorative material to be manufactured is a shape composed of the concave portion 31 and the flat convex portion 32 (FIG. 2). That is, first, the surface of the base material 1 before the surface protective layer 2 is formed is embossed in a shape composed of the concave portions 31 and the flat convex portions 32, and the surface protective layer 2 is attached here. After forming and curing (including semi-curing), the mirror surface embossing plate is pressed so that only the surface of the planar convex portion 32 is brought into contact with the surface of the planar convex portion 32, and only the surface of the planar convex portion 32 is pressed. Mirror surface embossing may be performed.

  In this way, even if the surface shape includes a fine and deep concave portion 31, such as a wood grain conduit shape, the concave portion 31 is formed by the previous embossing without being disturbed by the hardened surface protective layer 2. When the surface protective layer 2 is applied and formed on the surface including the concave portion 31 formed in this manner, the presence of the concave portion 31 causes the top surface of the planar convex portion 32 to be formed. Even if coating unevenness may occur in the surface protective layer 2, the unevenness due to the coating unevenness is corrected by the subsequent mirror embossing, so that it has a fine and deep recess 31 and a planar protrusion. A decorative material having excellent specular design and having a mirror-like high gloss 32 can be easily produced. Further, as a secondary effect, the corner portion between the concave portion 31 and the planar convex portion 32 whose corners are likely to be rounded by one embossing is sharpened by mirror embossing to be performed later. There is also an effect that the outline becomes clear and the three-dimensional design feeling is further improved.

  In the case of the above method, the surface of the planar convex portion 32 formed by the previous embossing process does not necessarily have a specular gloss shape, and is a fine rough surface shape having an uneven shape that is finer and shallower than the concave portion 31. It may be. On the contrary, by doing so, it is possible to prevent the occurrence of pinholes due to the repelling of the coating liquid when the surface protective layer 2 is applied and formed on the surface of the mirror-like base material 1, or the base material by the anchoring effect. Interference due to interference between reflected light at the upper and lower interfaces of the surface protective layer 2 in the planar convex portion 32 which has been improved to be a mirror-like smooth surface after embossing later It can also be said that it is more desirable because it can also prevent the occurrence of fringes (Newton rings).

  The previous embossing in the above method can be performed by an arbitrary method such as a planar hot press embossing method and a hot roll embossing method, as in the case of the embossing after the description. In particular, when the thermoplastic resin layer of at least the surface portion of the substrate 1 is molded by an extrusion molding method or an injection molding method of a molten thermoplastic resin, the extruded molten resin is cooled and solidified and simultaneously on the surface of the cooling roll. It is also possible to use an extrusion molding simultaneous embossing method for shaping the formed surface shape, or an injection molding simultaneous embossing method for shaping the surface shape formed on the inner surface of the mold at the same time as injecting molten resin into the mold. In this case, the surface shape can be shaped more faithfully to the original pattern than the above methods.

A primer layer was provided on the back surface of the olefin-based sheet subjected to wood grain printing, and an olefin-based clear resin layer was laminated on the printed surface to prepare a base material for a decorative sheet. The surface of the base material, that is, the surface of the olefin-based clear resin layer is coated with 50 parts by weight of a mixed resin of a fiber-based resin and a polyurethane polyol resin as a first layer and 10 parts by weight of a hexamethylene diisocyanate-based curing agent. The liquid is applied to a coating amount of 2 g / m ² after drying by a direct natural gravure coating method to form a primer layer, followed by 40 parts by weight of a urethane acrylate UV curable resin and acrylic polyol as the second layer. Mixing resin with 60 parts by weight of resin, blending 10 parts by weight of hexamethylene diisocyanate-based curing agent, and further drying the coating liquid with weather resistance prescription by direct reverse gravure coating method (peripheral speed ratio 100%) by coating the coating weight 10 g / m ² after forming a surface protective layer is irradiated with ultraviolet rays using a high-pressure mercury lamp The surface protection layer is semi-cured by curing the external line curable resin, and immediately after that, the sheet is preheated to a surface temperature of 120 ° C. with an infrared heater, and a grained conduit shape (conduit groove shape) is formed with an embossed plate having a surface temperature of 80 ° C. The surface protective layer is completely cured by heating and drying at 40 ° C., and the decorative sheet of the present invention is the decorative sheet. Was made.

A primer layer is provided on the back surface of the olefin-based sheet subjected to wood grain printing, and an olefin-based clear resin layer is melt-extruded and laminated on the printed surface. The substrate for decorative sheets was produced by shaping an embossing of a concave portion having a shape and a flat convex portion having a fine rough surface. A hexamethylene diisocyanate curing agent 10 is added to a mixed resin of 50 parts by weight of a polyurethane polyol resin having a polycarbonate skeleton and 50 parts by weight of a polyester polyol resin as a first layer on the surface of the base material, that is, the surface of the olefin-based clear resin layer. A coating solution containing parts by weight is applied to a coating amount of 2 g / m ² after drying by a direct natural gravure coating method to form a primer layer, followed by a urethane acrylate UV curable resin as the second layer. A mixed liquid of 30 parts by weight and 70 parts by weight of acrylic polyol resin is blended with 20 parts by weight of an equivalent amount of hexamethylene diisocyanate-based curing agent, and a coating solution that is further subjected to weathering prescription is applied to a direct reverse gravure coating method (periphery). coating the coating weight 10 g / ^{m 2} after dried by speed 150% ratio) The surface protective layer is formed, and the surface protective layer is semi-cured by irradiating ultraviolet rays with a high-pressure mercury lamp to cure the ultraviolet curable resin, and immediately after that, the sheet is preheated to a surface temperature of 120 ° C. with an infrared heater. The mirror sheet embossing plate having a surface temperature of 80 ° C. is subjected to mirror surface embossing only on the planar convex portion, and then the surface protective layer is completely cured by heating and drying at 40 ° C., and the decorative sheet as the cosmetic material of the present invention Was made.

[Comparative Example 1]
In Example 1 above, as a surface protective layer of the second layer, an equivalent 20 parts by weight of a hexamethylene diisocyanate curing agent was blended with 100 parts by weight of an acrylic polyol resin, and further a weathering formulation was used. A decorative sheet was produced under the same conditions as in Example 1 except that the ultraviolet irradiation after the formation of the surface protective layer was omitted.

[Comparative Example 2]
In Example 2 above, the same coating solution as that used in Comparative Example 1 was used as the surface protective layer of the second layer, except that ultraviolet irradiation after the formation of the surface protective layer was omitted. A decorative sheet was produced under the same conditions as in Example 2.

[Comparative Example 3]
A decorative sheet was produced under the same conditions as in Comparative Example 2 except that the mirror surface embossing was omitted in Comparative Example 2.

[Evaluation]
The decorative sheets of Examples 1 and 2 and Comparative Examples 1 to 3 were attached to the surface of a commercially available medium density fiberboard using an ethylene-vinyl acetate copolymer resin emulsion adhesive (containing an isocyanate curing agent). Each decorative board obtained by pressing was evaluated for design properties (sensory evaluation), gloss value (60 ° reflection), and solvent resistance (lacquer thinner 24 hour coating). The results are shown in Table 1 below.

Sectional drawing which shows an example of the decorative material of this invention. Sectional drawing which shows another example of the decorative material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Surface protection layer 3 Surface shape 31 by embossing Recess 32 Flat convex part

Claims (8)

  A method for producing a cosmetic material, comprising: forming a surface protective layer containing a curable resin on a base material having at least a surface made of a thermoplastic resin, curing the curable resin, and then embossing.   The said surface protective layer contains at least ionizing radiation curable resin as said curable resin, The said ionizing radiation curable resin is hardened by irradiation of ionizing radiation, The manufacturing of the cosmetics of Claim 1 characterized by the above-mentioned. Method.   The said surface protective layer contains the thermosetting resin as said curable resin in addition to the said ionizing radiation curable resin, The manufacturing method of the cosmetics of Claim 2 characterized by the above-mentioned.   The method for producing a cosmetic material according to claim 3, wherein a weight ratio of the ionizing radiation curable resin to the thermosetting resin is 5: 5 to 1: 9.   The thermosetting resin contained in the surface protective layer is left in an uncured state, and the ionizing radiation curable resin is cured by irradiation with ionizing radiation, thereby making the surface protective layer semi-cured, and then embossing. The method for producing a cosmetic material according to claim 3 or 4, wherein the surface protective layer is completely cured by applying a process and thereafter curing the thermosetting resin.   The said embossing is mirror surface embossing, The manufacturing method of the cosmetics in any one of Claims 1-5 characterized by the above-mentioned.   The embossing process is given to the surface of the base material before forming the said surface protective layer, The manufacturing method of the cosmetics in any one of Claims 1-6 characterized by the above-mentioned.   The another embossing is an embossing having a shape composed of a concave portion and a planar convex portion, and the embossing performed after the formation of the surface protective layer is a mirror embossing performed only on the planar convex portion. The method for producing a decorative material according to claim 7, wherein the cosmetic material is provided.

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