JP2005119167A - Decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material which makes the compatibility between the surface hardness of a surface protection layer and coating film strength to impact force etc., possible, adds a permanent antistatic function, and improves weatherability. <P>SOLUTION: Fullerene or its derivative is added into at least one layer of the surface protection layer 2 comprising at least one curable resin layer formed on a substrate 1. Fullerene etc., increase the coating film strength by their high hardness, have good affinity with the resin, act as a reinforcing agent, increase the coating film strength to impact force etc., and obtain an antistatic effect by conductivity and a weatherability improvement effect by ultraviolet absorbency. Especially when the curable resin forming a layer added with fullerene etc., contains at least a radiation curable resin, the fullerene etc., and the resin form crosslinking to improve the surface hardness, the coating film strength, and the antistatic property by the self-crosslinking of the fullerene. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to interior and exterior materials such as wall materials, floor materials and ceiling materials in buildings such as houses, furniture, furniture, exterior equipment for household equipment and home appliances, interior and exterior materials for transportation equipment such as vehicles, etc. In particular, the present invention relates to a cosmetic material having high surface hardness, excellent coating film strength and weather resistance, and an antistatic function.

  As a conventional cosmetic material in the above-mentioned field, a hard resin such as ionizing radiation curable resin is used for the outermost surface protective layer, and a high hardness filler such as silica, alumina, silicon carbide, etc. is mixed. (Patent Documents 1 and 2). However, when this is done, the surface hardness is improved, but the coating film itself of the surface protective layer becomes brittle, and the coating film strength against impact force and the like tends to decrease. Further, as the crosslink density of the resin is increased, since the filler has less bonding with the resin, the resin has a weaker force for holding the filler, and the filler tends to be easily detached from the surface of the coating film. Under such circumstances, it has been a problem that it is difficult to achieve both surface hardness and coating strength.

  Moreover, as a method of adding an antistatic function to a decorative material, a method of adding a surfactant to the outermost surface protective layer is often used (Patent Documents 3 to 4). However, when the compatibility between the resin and the surfactant is poor, the antistatic effect may not be exhibited well. In addition, over time, the surfactant bleeds out from the coating film, resulting in defects such as poor adhesion, reduced stain resistance, and reduced antistatic function due to a decrease in the absolute amount of surfactant.

Prior art document information.
JP-A-8-183147 JP 11-302599 A Japanese Patent Laid-Open No. 10-250013 JP 2001-293818 A

  In view of the above problems, the present invention makes it possible to achieve both the surface hardness of the surface protective layer and the coating strength against impact force and the like, and has a permanent antistatic function and improved weather resistance. The problem is to provide materials.

  The decorative material of the present invention is a decorative material in which a surface protective layer composed of one or more curable resin layers is provided on a base material, and at least one of the one or more curable resin layers includes: It is characterized by containing fullerene or a derivative thereof.

  In particular, the curable resin layer is composed of at least two layers, and the fullerene or a derivative thereof is contained in the outermost curable resin layer.

  In particular, the curable resin layer comprises at least two layers, and the fullerene or a derivative thereof is contained in a curable resin layer other than the outermost layer.

  In particular, the curable resin constituting the curable resin layer containing the fullerene or a derivative thereof includes at least an ionizing radiation curable resin.

  Since the cosmetic material of the present invention contains fullerene or a derivative thereof (hereinafter referred to as fullerene or the like) in at least one of the surface protective layers composed of one or more curable resin layers, the hardness of the fullerene or the like. As the surface hardness of the coating is improved, fullerene is an allotrope of carbon, so it has excellent affinity with the resin, so it does not make the coating brittle, unlike the case of inorganic fillers, Rather, it works as a resin reinforcing agent and improves the resin strength such as the elongation and bending strength of the resin, so that the coating strength against impact force and the like can be improved.

  In addition, fullerene and the like have conductivity due to the π-electron system in the skeleton, so that conductivity is imparted to the coating film, and thus antistatic property is imparted to the surface protective layer. This antistatic property lasts permanently because fullerenes in the coating film do not bleed out. Furthermore, since fullerene and the like have ultraviolet absorptivity, the weather resistance of the decorative material can be improved.

  In particular, when the coating film containing fullerene or the like contains an ionizing radiation curable resin and is cured by irradiation with ionizing radiation, it is crosslinked between the ionizing radiation curable resin and a π bond in the skeleton such as fullerene. Bonds can be formed to further improve the surface strength and coating strength. Furthermore, since the conductivity is improved by self-crosslinking of fullerene or the like by irradiation with ionizing radiation, the antistatic function can be further improved.

  In this invention, the kind of base material 1 is not specifically limited, The same kind as the base material in a conventionally well-known decorative material can be used. Specific examples include thin paper, titanium paper, fine paper, resin-impregnated paper, resin-mixed paper, paper-reinforced paper, and other building materials, fiber materials such as woven fabrics, knitted fabrics, and non-woven fabrics, polyolefin resins, and polyester resins. Films or sheets made of synthetic resins such as acrylic resins, styrene resins, and polyvinyl resins, molded products, plywood, laminated materials, medium density fiberboards, particle boards, wooden substrates, glass, ceramics, gypsum boards Inorganic base materials such as calcium silicate plates, cement plates and concrete plates, and metal plates such as iron, copper, brass, aluminum and stainless steel, and molded bodies. Moreover, a mixture, a composite, a laminated body, etc. of these several types of raw materials may be sufficient. Furthermore, printing of a pattern such as a wood grain pattern may be performed.

  FIG. 1 shows a decorative sheet which is an example of the decorative material of the present invention. In this case, the base material 1 has a print D printed on the surface of an olefin-based sheet O, and an olefin is formed on the printed D surface. A clear resin layer C is formed, and a primer layer resin P is applied to the back surface of the olefin sheet O.

  On the surface of the substrate 1, that is, on the surface of the olefin-based clear resin layer C in the decorative sheet, a surface protective layer 2 composed of two layers of a recoat layer R and a topcoat layer T is formed. Each of the recoat layer R and the topcoat layer T is composed mainly of a curable resin. Examples of the curable resin include thermosetting resins such as melamine resins, urea resins, phenol resins, epoxy resins, urethane resins, acrylic resins, and polyester resins, acrylate resins, epoxy resins, and polyesters. An ionizing radiation curable resin or the like such as a resin is used alone or in a mixture of plural kinds.

Then, fullerene or the like is added to one or both of the recoat layer R and the topcoat layer T. Fullerene is an allotrope of carbon having a molecular structure in which carbon atoms are bonded in a spherical shell, and many types are known such as those having 60, 70, 78, 80, 84 carbon atoms. Yes. The most typical is the buckminsterfullerene C ₆₀ composed of 60 carbon atoms, for 5-membered ring and six-membered rings of carbon is arranged in a form soccer ball, it is also referred to as a soccer ball molecule. Fullerene to be used in the present invention may be a The C _60, it may be a fullerene having other molecular structures.

  Fullerene has the hardness next to diamond as an allotrope of carbon, and the coating film hardness can be improved by adding it to the coating resin forming the surface protective layer 2. In addition, since it is excellent in affinity with the resin, the elongation and bending strength of the resin can be improved by addition to the resin, and the coating strength against impact force and the like can be improved. In particular, when the coating resin contains an ionizing radiation curable resin, it can be cross-linked with the resin by a π bond in the skeleton of the fullerene molecule. Has a merit that the antistatic function is remarkably increased.

  In addition, using fullerene derivatives in which surface modifying groups such as alkyl groups, phenyl groups, and hydroxyl groups are bonded to some of the carbon atoms constituting the fullerene molecule, the affinity with the resin is further improved, and the coating strength It is further effective in improving the above. In particular, when the coating film resin includes a thermosetting resin such as an isocyanate curable polyurethane resin, when a fullerene derivative modified with an active hydrogen group such as a hydroxyl group, a carboxyl group, or an amino group is used, these active hydrogen groups are reduced. By forming a cross-link with the resin via the resin, it is further effective for improving the coating film strength.

  Fullerenes and the like are very fine particles, and some solvents are selected, but dispersibility is generally good. However, since the coating film becomes intensely colored when added in a large amount, it is generally desirable to suppress the amount added per 100 parts by weight of resin solids to about 30 parts by weight or less. If it is within the range, the amount added may be appropriately adjusted in accordance with the required physical properties. However, since the effect cannot be expected even if the amount is too small, it is desirable that the amount be at least 1 part by weight.

  When importance is attached to the transparency of the surface protective layer 2, the transparency is improved if the amount of addition of fullerene or the like is suppressed, but on the other hand, the effect of addition of fullerene or the like is poor. Therefore, if the surface protective layer 2 is divided into two or more layers, and fullerene or the like is added to only a part of the layers, sufficient effects can be easily obtained in terms of the physical properties of the surface protective layer 2, particularly in terms of antistatic functions. In addition to being easy, the abundance of fullerene and the like per area can be kept small, and sufficient transparency can be easily ensured.

  In the case where the surface protective layer 2 is composed of two or more layers, fullerene or the like may be added to one or more of them. For example, as shown in FIG. 1, when the surface protective layer 2 is composed of two layers of the recoat layer R and the topcoat layer T, fullerene or the like may be added only to the recoat layer R. It may be added only to the topcoat layer T or may be added to both. When giving priority to the surface hardness and antistatic function, it is advantageous to add at least to the outermost layer, that is, the topcoat layer T. However, when giving priority to surface smoothness, it is not added to the outermost layer. It is advantageous to add to the layer other than the outermost layer, that is, the recoat layer R.

  When the surface protective layer 2 is composed of three or more layers, that is, when the recoat layer R is composed of two or more layers, and when the fullerene or the like is not added to the topcoat layer T, the fullerene or the like is 2 You may add to any layer of the recoat layer R which consists of a layer or more. However, from the viewpoint of the antistatic function, the closer the fullerene layer is to the outermost layer, the higher the effect. Therefore, when adding fullerene to only one layer, the recoat layer immediately below the topcoat layer T It is desirable to add to R.

A primer resin layer P was provided on the back surface of the olefin-based sheet O to which the wood grain printing D was applied, and an olefin-based clear resin layer C was laminated on the printed D surface to prepare a base material 1 for a decorative sheet. On the surface of the clear resin layer C of the substrate 1, 10 parts by weight of a hexamethylene diisocyanate curing agent is mixed as a recoat layer R with 100 parts by weight of a polyester polyol resin, diluted to an appropriate viscosity, and then a direct natural gravure. the coating method was applied to the coating amount 2 g / m ² after drying, dried and thermally cured. Subsequently, as a top coat layer T, 15 parts by weight of fullerene C ₆₀ dispersed in advance in a solvent is added to 100 parts by weight of an electron beam curable resin (a mixed composition of NK oligo, DPHA and TMPTA). Furthermore, after applying a weather-resistant formulation and diluting to an appropriate viscosity with a diluent solvent, the coating amount after drying is applied by a direct reverse gravure method (peripheral speed ratio 150%), 10 g / m ² applied, and after drying, the irradiation dose A decorative sheet as a decorative material of the present invention was obtained by irradiating with 50 kGy electron beam and completely cured.

  In Example 1, the resin content of the topcoat layer T is divided into the electron beam curable resin, an acrylic urethane resin (a mixture of 100 parts by weight of acrylic polyol resin and 20 parts by weight of a hexamethylene diisocyanate curing agent), and A decorative sheet was obtained in the same manner as in Example 1 except that the fullerene hydroxide was used in place of the fullerene and hydroxylated fullerene was used and curing was performed at 40 ° C. for 5 days after irradiation with the electron beam. .

  In Example 1 above, the resin content of the topcoat layer T was changed to an acrylic urethane resin (a mixture of 100 parts by weight of acrylic polyol resin and 20 parts by weight of a hexamethylene diisocyanate curing agent), and hydroxylated instead of fullerene. A decorative sheet was obtained in the same manner as in Example 1 except that fullerene was used and curing at 40 ° C. was performed for 5 days instead of electron beam irradiation.

On the same base material 1 as used in Example 1, the same coating film as the recoat layer R in Example 1 was first formed as the first recoat layer R1, and the second recoat was then formed thereon. As the layer R2, the same coating film as the topcoat layer T in Example 3 above is formed, and the topcoat layer T is formed thereon as a polyurethane system comprising a mixture of 100 parts by weight of a polyurethane polyol and 10 parts by weight of an isocyanate curing agent. The resin was applied to a coating amount of 2 g / m ² after drying, and after drying, curing was performed at 40 ° C. for 5 days to obtain a decorative sheet.

<Comparative Example 1>
In Example 1, a cosmetic sheet was obtained in the same manner as in Example 1 except that fullerene was not added to the topcoat layer T.

<Comparative example 2>
In Example 1, silica powder was blended in place of fullerene, and the rest was obtained in the same manner as in Example 1 to obtain a decorative sheet.

<Evaluation>
About each decorative sheet produced as described above, the surface resistance value and weather resistance were evaluated, and each decorative sheet was attached to a medium density fiberboard with an ethylene-vinyl acetate resin adhesive (containing an isocyanate curing agent). In addition, a decorative board was produced and the surface hardness was evaluated. Each decorative sheet was bonded to a 12 mm thick plywood with the same adhesive as described above to produce a decorative board, and the impact resistance was evaluated. However, each evaluation condition is as follows.

  1. Surface hardness: conforms to the pencil hardness test specified in JIS K 5600, load 1 kg.

  2. Impact resistance: Observed indentation (peripheral cracks, etc.) when a 500 g steel ball is dropped from a height of 50 cm.

  3. Surface resistance value: The surface resistance value [Ω] when 500 V is applied is measured using a High Megameter Meter at 23 ° C. and 60% RH.

4). Weathering resistance: Using a metal weather weathering tester (manufactured by Daipla Wintes Co., Ltd.), the color fading of the printed color starts with an illuminance of 65 mW / cm ² , 20 hours of irradiation, and 4 hours of darkness for a total of 24 hours as one cycle. Measure elapsed time.

  The evaluation results are as shown in Table 1 below.

The schematic cross section of an example of the decorative material (decorative sheet) of this invention.

Explanation of symbols

1 Base material P Primer resin layer O Olefin-based sheet D Print C Olefin-based clear resin layer 2 Surface protective layer R Recoat layer T Topcoat layer

Claims (4)

  In a decorative material provided with a surface protective layer comprising one or more curable resin layers on a substrate, at least one of the one or more curable resin layers contains fullerene or a derivative thereof. A cosmetic material characterized by that.   The cosmetic material according to claim 1, wherein the curable resin layer comprises at least two layers, and the fullerene or a derivative thereof is contained in the outermost curable resin layer.   The cosmetic material according to claim 1, wherein the curable resin layer comprises at least two layers, and the fullerene or a derivative thereof is contained in a curable resin layer other than the outermost layer.   The cosmetic material according to any one of claims 1 to 3, wherein the curable resin constituting the curable resin layer containing the fullerene or a derivative thereof contains at least an ionizing radiation curable resin.

Images