JP2004155208A - Decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material excellent in abrasion resistance due to an intermediate resin layer having specific dynamic viscoelasticity property (it has a peak of a loss elastic modulus below room temperature). <P>SOLUTION: The decorative material D includes the intermediate resin layer 2 composed of a coating liquid or ink, and a surface protective layer 3 composed of a crosslinked resin on a substrate 1. The temperature dependence property of the loss elastic modulus E" (measuring frequency of 10 Hz) in a dynamic viscoelasticity method of the intermediate resin layer has a peak Pa at least below room temperature Tr, and also the intermediate resin layer is arranged so as to come in contact with the surface protective layer. Further, room temperature is temperatures having width defined as 10°C to 50°C. It is preferable that a value of a storage elastic modulus E' of the intermediate resin layer is in the range of 1 x 10<SP>7</SP>to 2 x 10<SP>9</SP>Pa at the region of room temperature. It is preferable that the loss elastic modulus E" has a peak Pb at temperatures above room temperature. Paper is typically used for the substrate. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a decorative material used for a building interior material such as a wall, a surface material such as a fitting such as a door and furniture, a vehicle interior material, and the like. In particular, the present invention relates to a cosmetic material having a structure having a surface protective layer made of a cross-linked resin and having excellent wear resistance.

2. Description of the Related Art Conventionally, a decorative material such as a decorative sheet used for the above applications usually requires abrasion resistance. For this reason, a cosmetic material or the like in which the surface protective layer is formed of a two-component curable urethane resin paint, an ionizing radiation-curable resin paint, or the like is used.
(Patent Document 1).

(1) For example, in Patent Literature 1 and Patent Literature 2, etc., after forming a pattern layer on a substrate by printing, an ionizing radiation-curable resin paint such as an unsaturated polyester or acrylate is further applied as a surface protective layer. The present invention discloses a decorative material in which a coating film is formed, and the coating film is cross-linked and cured by an electron beam to form a surface protective layer made of a cross-linked resin.

(2) Further, in a case where further wear resistance is required, Patent Document 3 discloses that a spherical α-alumina or the like is used as a lubricant in an ionizing radiation curable resin forming a surface protective layer. It discloses adding spherical particles.

Japanese Patent Publication No. 49-31033 Japanese Patent Publication No. Hei 4-22694 Japanese Patent No. 2740943

  However, even when the surface protective layer is formed of a crosslinked resin as in the above (1), the wear resistance does not improve beyond a certain limit, and the wear resistance may be insufficient. For this reason, if hard inorganic particles are added as a lubricant to the resin of the surface protective layer as in (2) above, the abrasion resistance is improved, but the surface of the surface protective layer may have a rough feeling. There was a problem to do. The above (2) solves the problem that the plate and the doctor blade are easily worn by the lubricant when the surface protective layer is formed by adding the lubricant by using spherical particles as the lubricant. However, there is a problem that the use of such a special lubricant increases costs.

  That is, an object of the present invention is to impart excellent wear resistance to a decorative material.

  In order to solve the above problems, in the decorative material of the present invention, an intermediate resin layer comprising a coating liquid or an ink on a substrate, and a surface protective layer comprising a cross-linked resin in this order, the intermediate resin layer The temperature-dependent characteristic at a measurement frequency of 10 Hz of the loss elastic modulus in the dynamic viscoelasticity method is at least a temperature lower than room temperature (however, room temperature is a temperature having a width defined by 10 ° C. to 50 ° C.) And the intermediate resin layer was in contact with the surface protective layer.

  As described above, when an intermediate resin layer made of a coating liquid or ink having dynamic viscoelastic properties defined as having a peak of the loss elastic modulus on the lower temperature side than room temperature is provided in contact with the surface resin layer, the surface protective layer is provided. Excellent abrasion resistance can be obtained without adding a lubricant such as inorganic particles. This is probably because the moderately softened intermediate resin layer acts as a cushion at room temperature where wear stress is applied. That is, when an appropriate elastic restoring force acts and an external stress (wear stress) that wears the surface is applied to the surface protective layer, the intermediate resin layer thereunder disperses the external stress over a wide area (volume). As a result, it is considered that the surface protective layer is hardly abraded and the abrasion resistance is improved as a result of absorbing and relaxing by converting the heat to heat and dissipating the heat. For this reason, depending on the required degree of wear resistance, it is not necessary to add a lubricant such as inorganic particles to the surface protective layer. It is also possible to avoid plate wear.

Further, in the decorative material of the present invention, the storage elastic modulus of the intermediate resin layer at the measurement frequency of 10 Hz in the dynamic viscoelasticity method is 1 × 10 ⁷ to 10 × 10 at room temperature region. The configuration was 2 × 10 ⁹ Pa.

  Furthermore, by adopting a configuration in which the dynamic viscoelastic properties of the intermediate resin layer are specified in the storage elastic modulus as well, excellent wear resistance can be obtained without adding a lubricant such as inorganic particles to the surface protective layer. Sex can be obtained more reliably. That is, in the actual use temperature range (that is, room temperature range) of the decorative material, it is possible to prevent excessive deformation of the surface protective layer due to external stress (abrasion stress), restore the deformation, and maintain a proper surface hardness. It is considered that the elastic restoring force can be applied to the intermediate resin layer.

  Further, the decorative material of the present invention further has a temperature-dependent characteristic at a measurement frequency of 10 Hz of a loss elastic modulus in the dynamic viscoelasticity method of the intermediate resin layer which is higher than the room temperature in any one of the above constitutions. The temperature also has a peak.

  Further, as described above, by adopting a configuration in which the loss elastic modulus has a peak even above the actual use temperature range of the decorative material, the surface protective layer is excellent without adding a lubricant such as inorganic particles to the surface protective layer. Wear resistance can be obtained more reliably. It is because the peaks of the temperature dependence of the loss modulus at both below and above room temperature tend to keep the storage modulus at room temperature within a reasonable value range, and to reduce the external stress (wear). It is considered that the intermediate resin layer can be given an appropriate elastic restoring force that can prevent excessive deformation of the surface protective layer due to stress), restore the deformation, and maintain its surface hardness.

  Further, the decorative material of the present invention has a configuration in which the substrate is made of paper in addition to any one of the above-described configurations. When the base material is a paper, the decorative material is a decorative paper.

(1) According to the decorative material of the present invention, an excellent abrasion resistance is obtained by an intermediate resin layer having a specific dynamic viscoelastic property (having a peak of a loss modulus below room temperature). For this reason, depending on the required abrasion resistance, it is not necessary to add a lubricant such as inorganic particles to the surface protective layer. Wear can also be avoided.
(2) Further, by defining the dynamic viscoelastic properties of the intermediate resin layer to a specific storage elastic modulus, an appropriate elastic restoring force required for improving abrasion resistance and maintaining surface hardness can be obtained. Therefore, the effect (1) can be more reliably obtained.
(3) In addition to the above (1) or (2), the loss elastic modulus of the intermediate resin layer can be specified as a dynamic viscoelastic characteristic having a peak even at a temperature exceeding room temperature, so that the wear resistance is improved and the surface is improved. Since an appropriate elastic restoring force required for maintaining the hardness is easily obtained, the effect described in the above (1) can be more reliably obtained.
(4) Further, when the base material is in the form of paper, the decorative material is a decorative paper.

  Hereinafter, embodiments of the cosmetic material of the present invention will be described.

First, FIG. 1 (A) is a cross-sectional view showing a basic configuration of a decorative material of the present invention. The decorative material D of the present invention comprises an intermediate resin layer 2 on a substrate 1 and in contact with a surface protective layer 3. The surface protective layer 3 made of a cross-linked resin is laminated in this order. The intermediate resin layer 2 is a resin layer that is present between the base material 1 and the surface protective layer 3. The intermediate resin layer is a multilayer composed of a plurality of layers having different functions according to the application of the decorative material, various required physical properties, and the like. It is good also as composition.
For example, as in a decorative material D illustrated in the cross-sectional view of FIG. 2, an intermediate resin layer 2 having the above specific dynamic viscoelastic properties and a surface protective layer 3 made of a cross-linked resin are laminated on a substrate 1. In the configuration, the intermediate resin layer 2 is composed of three layers of a sealer layer 4, a picture layer 5, and a primer layer 6 in order from the substrate 1 side.

FIG. 1B is an explanatory view conceptually showing the specific dynamic viscoelastic property of the intermediate resin layer. FIG. 1B is a diagram obtained by measuring the temperature-dependent characteristics of the loss elastic modulus E ″ and the storage elastic modulus E ′ of the intermediate resin layer by a dynamic viscoelasticity method at a measurement frequency of 10 Hz. In the present invention, the dynamic viscoelastic property is such that at least the temperature-dependent property of the loss elastic modulus E ″ has a peak Pa below the room temperature Tr. The figure also shows the case where the temperature dependence of the loss elastic modulus E ″ preferably has a peak Pb at a temperature exceeding the room temperature Tr. In the same figure, the storage elastic modulus E ′ measured under the same conditions is shown. The temperature-dependent characteristics are also shown, and the storage elastic modulus E 'is preferably within the optimum range R where the value in the range of room temperature Tr is 1 × 10 ⁷ to 2 × 10 ⁹ Pa even in a preferable case. is there.
In this way, by specifying the loss elastic modulus E ″ or the storage elastic modulus E ′ of the intermediate resin layer under specific conditions, the viscoelastic behavior of the intermediate resin layer allows the abrasion resistance of the decorative material (surface protective layer). This improvement in wear resistance can be enjoyed in a configuration in which a lubricant is not added to the surface protective layer. However, if further improvement in wear resistance is required, the surface resistance can be improved. A lubricant or the like may be added to the protective layer.

  Hereinafter, each layer will be described in more detail in order from the substrate.

〔Base material〕
The substrate 1 is not particularly limited. For example, the shape is arbitrary, such as a sheet, a plate, and a three-dimensional object, depending on the use of the decorative material, and the material is also arbitrary. For example, examples of the sheet include paper, a resin sheet, a nonwoven fabric, and a metal foil.

  Specifically, as paper, tissue paper, kraft paper, titanium paper, woodfree paper, linter paper, baryta paper, parchment paper, glassine paper, parchment paper, paraffin paper, paperboard, coated paper, art paper, Japanese paper, or these And those impregnated with a resin such as an acrylic resin, a urethane resin, and styrene-butadiene rubber.

  Examples of the nonwoven fabric include those made of resin fibers such as polyester resin and acrylic resin, and inorganic fibers such as glass, carbon, and asbestos. Further, as the resin sheet, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin resin such as olefin-based thermoplastic elastomer, polymethyl (meth) acrylate, Acrylic resin such as polybutyl (meth) acrylate, methyl (meth) acrylate-styrene copolymer, methyl (meth) acrylate-butyl (meth) acrylate copolymer [however, (meth) acrylate means acrylate or methacrylate Such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, ethylene terephthalate-isophthalate copolymer, polyester thermoplastic elastomer, etc. From vinyl resins such as ester resins, polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol; styrene resins such as polystyrene and acrylonitrile-butadiene-styrene copolymer (ABS resin); and resins such as cellulose triacetate, cellophane, and polycarbonate. Resin sheet (film). Examples of the metal foil include a metal foil made of aluminum, iron, stainless steel, copper, or the like. Alternatively, a laminate of two or more layers of the same type or different types of sheets among the various sheets listed above may be used.

  Examples of the board include a wood board, an inorganic ceramic board, a resin board, and a metal board. Specifically, as the wood board, there are wood veneer, wood plywood, laminated wood, particle board, and the like made of wood (including bamboo) such as cedar, pine, zelkova, oak, lauan, teak, melapy, and bamboo. Density fiberboard (MDF) and the like. In addition, examples of the inorganic ceramics-based plates include gypsum plates, gypsum slag plates, calcium silicate plates, asbestos slate plates, ALC (lightweight cellular concrete) plates, cement plates such as hollow extruded cement plates, pulp cement plates, asbestos cement plates, An inorganic non-metallic plate such as a wood chip cement plate, a glass fiber reinforced concrete (GRC) plate, or a ceramic plate made of pottery, porcelain, setware, earthenware, glass, enamel, or the like can be used. Further, the resin plate is made of a thermosetting resin such as a phenol resin, a urea resin, an unsaturated polyester resin, a urethane resin, an epoxy resin, and a melamine resin, in addition to the various thermoplastic resins described as the material of the resin sheet. Resin such as phenolic resin, urea resin, unsaturated polyester resin, urethane resin, epoxy resin, melamine resin, diallyl phthalate resin, etc. impregnated and cured into glass fiber non-woven fabric, cloth, paper and other various fibrous base materials It is a resin plate such as a so-called FRP (fiber reinforced plastic) plate or the like, which is composited. Examples of the metal plate include an iron plate, a galvanized steel plate, a polyvinyl chloride sol-coated steel plate, an aluminum plate, and a copper plate.

  Examples of the three-dimensional object include columnar objects made of various materials listed in the above-mentioned plate, and three-dimensional objects having other shapes. For example, it is a pillar-shaped wood, a three-dimensional three-dimensional resin molded product, or the like.

  The decorative material becomes a decorative sheet when the base material is a sheet, and further becomes a decorative paper when the base material sheet is paper. Further, the decorative material becomes a decorative plate when the base material is a plate, and becomes a decorative member or a cosmetic product when the base material is a three-dimensional object.

(Intermediate resin layer)
The intermediate resin layer 2 is a resin layer interposed between the base material 1 and the surface protective layer 3 and having a specified dynamic viscoelastic property in the present invention. In the present invention, the intermediate resin layer made of a coating liquid or ink is provided in contact with the surface resin layer. The resin used for the intermediate resin layer is not particularly limited as long as it satisfies the above-mentioned dynamic viscoelastic properties defined in the present invention, and may be, for example, a thermoplastic resin or a curable resin. Therefore, as the resin of the intermediate resin layer, a resin that satisfies the specific dynamic viscoelastic property may be appropriately selected and used from known resin materials according to the application, required physical properties, and the like.

  As for the dynamic viscoelastic properties of the intermediate resin layer, if the loss elastic modulus E ″ (temperature-dependent property) has a peak below room temperature, the wear resistance of the decorative material by the surface protective layer is enhanced. On the other hand, the surface hardness normally required for the surface of the decorative material has a certain effect by the surface protective layer itself using the crosslinked resin, except that the loss elastic modulus E ″ is required to improve the abrasion resistance. As a result of having a peak below room temperature, if the intermediate resin layer becomes too soft in the room temperature region and affects and reduces the surface hardness, the shortage is further reduced as the dynamic viscoelastic properties of the intermediate resin layer. It can be supplemented by defining the value of the storage modulus E 'at room temperature within a specific range. In addition, by giving the loss modulus E ″ a peak exceeding room temperature, the storage modulus E ′ at room temperature can be easily kept in a specific range. Alternatively, the storage modulus E ′ is not specified. Furthermore, by giving the loss modulus E ″ a peak above room temperature (along with the peak below room temperature), the value of the storage modulus E ′ at room temperature may fall within a preferable range.

The storage modulus E 'is preferably 1 × 10 ⁷ to 2 × 10 ⁹ Pa, but is more preferably in the range of 2 × 10 ⁷ to 2 × 10 ⁹ Pa. If the storage elastic modulus E ′ is less than 1 × 10 ⁷ , the deformation of the intermediate resin layer becomes large, so that the surface hardness of the surface protective layer may be reduced and the effect of improving the wear resistance may be reduced.
Note that such dynamic viscoelastic properties are to introduce a rubber elastic element into the intermediate resin layer, but do not make the rubber elasticity perfect. The storage elastic modulus E 'of a substance generally called rubber is on the order of less than the above range. If the material is too soft like a rubber, the deformation becomes too large and the effect of improving wear resistance cannot be obtained.

  By the way, the temperature dependence of the loss elastic modulus E ″ and the storage elastic modulus E ′ of the intermediate resin layer at a measurement frequency of 10 Hz in the dynamic viscoelasticity method is measured using a commercially available dynamic viscoelasticity measuring device. For example, there is a dynamic viscoelasticity measurement device “Rheogel-E4000” manufactured by UBM Corporation (UBM). In the dynamic viscoelasticity measurement, generally, there are a bending mode, a tensile mode, a torsion mode, and a shear mode as sample deformation modes depending on how a force is applied to a measurement sample. The point is the tensile mode. In the actual measurement, the applied vibration was a sine wave of 10 Hz, the strain was 5 μm, the heating rate was 3 ° C./min, the capturing temperature was 2 ° C., and the measuring temperature range was −50 ° C. to 120 ° C. The measurement sample used was one in which a coating liquid for forming an intermediate resin layer was poured into a weighing dish made of polypropylene and having a flat bottom surface and dried to form a film of the intermediate resin layer alone. The measurement sample size is, for example, a rectangle having a thickness of about 100 μm, a length of 20 mm, and a width of 5 mm. The measurement frequency should be measured at any frequency as long as the correlation between the wear resistance and the temperature dependence of the loss modulus and the storage modulus can be clarified and the measurement is easy. May be. However, in general, in the field of organic polymers, measurement at a frequency of 10 Hz is widespread and a measuring instrument is easily available. At a frequency of 10 Hz, the correlation with the wear resistance is actually clear. A measurement frequency of 10 Hz is employed.

  In addition, as an index of the hardness of the resin at room temperature (region), it is conceivable to adopt a relationship between the so-called glass transition temperature Tg and the room temperature Tr (Tg ≦ Tr), but this does not allow an accurate product design. . As a result of various tests and studies, the loss elastic modulus E ″ and the storage elastic modulus E ′ according to the dynamic viscoelasticity method adopted by the present invention were measured by giving external stress as a function of dynamic time. The reason for this is that the abrasion phenomenon caused by external stress reflects the condition (of the cosmetic material) closer to the actual use conditions, and enables accurate product design. Since the glass transition temperature is usually obtained by a DSC (differential scanning calorimeter) measured without applying an external stress, the behavior due to dynamic external stress is not reflected in the measurement result. For example, specifically, some resins have a glass transition temperature of 18 ° C., but the peak of the loss modulus E ″ below room temperature is 67 ° C. is there. If the lower limit temperature of the room temperature is set to 20 ° C. and the glass transition temperature is lower than the room temperature, this resin can be used, but in reality, this resin does not improve the wear resistance. The fact that the temperature of the peak Pa below room temperature of the loss elastic modulus E ″ of the resin is 67 ° C., which is not lower than room temperature, is actually reflected.

  The "room temperature" in the present invention means a temperature at which the decorative material is used, and has a certain temperature. For example, the temperature is from 0 ° C to 70 ° C. The reason for this is that the environmental temperature at which the cosmetic material is used varies depending on the temperature change during the day, seasonal variation, and the region where the cosmetic material is used (a cold region, a subtropical region, etc.). In addition, the cosmetic material is usually used eventually in the interior of a structure such as a room or a car, but before construction, it is also exposed to temperature changes in a transport vehicle, a warehouse, and the like. Including, means the environmental temperature at which the cosmetic material is used. Therefore, here, the room temperature should not be defined as a unique single temperature (for example, 25 ° C.) but is defined as a temperature region having a width. However, the temperature range does not need to correspond to any and all temperature changes. The temperature range of the room temperature may be determined from the lower limit and the upper limit of the temperature to be considered in the environment where the target cosmetic material is used. The resin for the intermediate resin layer of the present invention is also selected according to the design target value in the determined temperature range. Therefore, the lower limit temperature and the upper limit temperature of room temperature may be different depending on the use of the cosmetic material. For example, when used as an interior material of an automobile, better results can be obtained by determining the characteristics of the intermediate resin layer, particularly when the room temperature is set to be higher on the upper limit side, as compared with indoor use in a house. Of course, if the resin used for the intermediate resin layer and its cost allow, the characteristics of the intermediate resin layer may be determined as room temperature within a wider temperature range in consideration of various applications. Also, in the actual product design, depending on the cost, etc., the lower limit and the upper limit of the frequency of occurrence (probability) of the temperature in the use environment and the intensity of the wear stress applied at that time and the frequency of occurrence may cause the lower limit. Also, both ends of the upper limit may be cut off in a direction in which the width of the temperature region is reduced. For example, in the case of designing for indoor use in ordinary Japan as an example, the lower limit of the room temperature is preferably set to 10 ° C. and the upper limit is set to 50 ° C. as a standard. The embodiment described below shows an example designed at this room temperature setting.

  By the way, in order for the peak of the loss modulus E ″ of the resin used in the intermediate resin layer to be lower than room temperature or to be higher than room temperature, generally, the fatty acid is added to the molecular chain structure of the resin. When the aromatic group is used, the peak temperature tends to decrease, and when the aromatic group is used, the peak temperature tends to increase.The molecular weight (degree of polymerization) of the resin has a clear peak of the loss modulus E ″. It is necessary to have a certain degree (for example, a polymerization degree of 500) or more to appear, but it is not so related to the peak temperature. As described above, the loss elastic modulus E ″ can be controlled to a desired value by appropriately designing the molecular chain structure of the resin.

  In the case where resins having different loss elastic modulus E ″ peak temperatures are mixed with each other, if both resins are completely mixed microscopically, their peaks may be fused or disappear. If the two resins are mixed in a state where they are microscopically phase-separated, the different peak temperatures may remain unchanged, so that the peak of the loss elastic modulus E ″ of the intermediate resin layer may have a peak Pa below room temperature. In order to have both the peak and the peak Pb exceeding the room temperature, two or more kinds of resins may be mixed. That is, a mixed resin in which a resin having a peak Pa lower than room temperature in the loss elastic modulus E ″ and a resin having a peak Pb exceeding room temperature may be used.

  As the resin used for the intermediate resin layer, as long as the dynamic viscoelastic properties described above are satisfied, a thermoplastic resin, a curable resin, and the like are not particularly limited, as described above. Acrylic resins, polyester resins, styrene-butadiene rubber (SBR), thermoplastic resins such as thermoplastic urethane resins, and curable resins such as two-component curable urethane resins can be used alone or as a mixture of two or more. it can. Among them, a polyester resin is preferable in that it is one of the resins whose dynamic viscoelastic properties are easily adjusted depending on the types and blends of polyhydric alcohol and polybasic acid as raw materials.

  However, it is better to use a curable resin than a thermoplastic resin for crosslinking (or to use a crosslinked resin as a curable resin rather than using a thermoplastic resin). It is preferable in that heat resistance is also improved. A known method may be used for crosslinking. For example, isocyanate is used as a crosslinking agent, or an acryloyl group is provided in a resin molecule (for example, acrylic acid, methacrylic acid, or the like is added to a polyester resin (prepolymer)). And an acrylate-based ionizing radiation-curable resin for the surface protective layer. When the surface protective layer is cured by ionizing radiation, the acryloyl group May be cured at the same time. Also, an active hydrogen-containing group such as a hydroxyl group may be provided in the resin molecule (for example, a polyester polyol, an acrylic polyol, a polyether polyol, a polycarbonate polyol, a polyurethane polyol, etc. used as a main component of a two-component curable urethane resin). Various polyols) or an isocyanate group (eg, a polyisocyanate prepolymer), and a two-component curable urethane resin for the surface protective layer. When the surface protective layer is cured by heat or the like, an intermediate resin is used. The layer may be cured at the same time. In addition, since a polyester resin usually has a hydroxyl group as a reactive residue, it can be used as a polyester polyol as a main component of a two-part curable urethane resin.

The amount of the crosslinking agent varies depending on the type of the resin, the type of the crosslinking agent, and the like, but is usually about 1 to 10 parts by mass per 100 parts by mass of the resin (base material).
Examples of the isocyanate used for the crosslinking agent include polyisocyanates such as aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate; Aliphatic (or alicyclic) isocyanates such as methylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of the above various isocyanates are also used. For example, an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, an adduct of 1,6-hexamethylene diisocyanate, and the like. In addition, from a viewpoint of weather resistance and heat-resistant yellowing, an aliphatic (or alicyclic) isocyanate is more preferable than an aromatic isocyanate.

The intermediate resin layer can be formed by a known coating film forming method such as coating and printing a coating liquid (or ink) composed of a solution in which the above resin is dissolved or a dispersion liquid in which the resin is dispersed. If the intermediate resin layer is formed on the entire surface, it can be formed by a coating method such as gravure coating or roll coating, and if it is formed in a pattern or on the entire surface, gravure printing, silk screen printing, offset printing, gravure It can be formed by a printing method such as offset printing. Even when the coating liquid (or ink) is aqueous, if the isocyanate is used as a blocked isocyanate, water as a solvent or a dispersion medium is volatilized and dried, and then further heated to release the isocyanate block, the isocyanate is used. Crosslinking is possible.
The thickness of the intermediate resin layer varies depending on applications, required physical properties, and the like, but is generally about 1 to 10 μm as a total thickness in a single-layer or multilayer structure.

  By the way, when a desired design expression is satisfied only by the two layers of the base material and the surface protective layer, the intermediate resin layer may be formed as a simple non-colored transparent resin layer without adding a coloring agent or the like. However, usually, the intermediate resin layer is formed as a layer that also performs other functions such as decoration. For example, as illustrated in FIG. 2, the intermediate resin layer 2 can be formed as a layer that also serves as various functional layers other than the purpose of improving wear resistance, such as the sealer layer 4, the picture layer 5, and the primer layer 6. Such a function layer can be used also as one kind or two or more kinds of function layers. FIG. 1 shows an example of a multi-layer configuration that also serves as three types of functional layers.

The sealer layer 4 has a structure in which the coating liquid or the ink is absorbed into the inside of the base material to reduce the film thickness or the thickness of the base material when the base material is, for example, paper or wood, and has a rough surface or permeability. This layer is provided in order to prevent formation unevenness from causing gloss unevenness of a coating film or an ink film.
Further, a coloring agent may be added to the intermediate resin layer (including a layer that also serves as various functional layers) to form a colored layer, a concealing layer, a colored concealing layer, and the like on the entire surface.
If a colorant is added to the intermediate resin layer and the intermediate resin layer is formed in a pattern, it can be made into a picture layer. However, when it is formed in a pattern, it is preferable that the layer is not excessively dispersed for the purpose of the original intermediate resin layer. In the case of a multicolor printing pattern layer, as a result of superimposing even if it is scattered as a layer of each color, it is also possible to form a layer that is not scattered as a whole but covers almost the entire surface or the entire surface.

  In the case where the intermediate resin layer has a multilayer structure, a layer in contact with the surface protective layer may be a layer also serving as a primer layer for the purpose of enhancing adhesion to the surface protective layer. The primer layer is formed not only for the purpose of enhancing the adhesion with the surface protective layer but also for the purpose of enhancing the adhesion between different layers including the base material. Therefore, when the intermediate resin layer having a multilayer structure contacts the substrate, the layer contacting the substrate can be used also as a primer layer for the substrate. For example, this is the case where the base material is generally a polyolefin resin sheet having poor adhesion.

  By the way, the intermediate resin layer may be provided between the base material and the surface protection layer. However, a layer other than the intermediate resin layer (for example, a pattern layer not used as the intermediate resin layer, a sealer layer, etc.) is also provided between the base material and the surface protection layer. In such a case, it is preferable that the intermediate resin layer be a layer immediately below the surface protection layer in contact with the surface protection layer or a layer closer to the surface protection layer because of the cushion effect of the intermediate resin layer (dynamic viscoelasticity). Is preferably provided directly to the surface protective layer. Therefore, for example, it is preferable to provide a picture layer that does not double as the intermediate resin layer between the intermediate resin layer and the substrate. In this case, when the pattern layer and the surface protective layer are in direct contact with each other and the adhesive strength is weak, the intermediate resin layer can be regarded as a primer layer between the pattern layer and the surface protective layer.

  In addition, the intermediate resin layer, in order to appropriately adjust the coating suitability, printability, or other physical properties, the specific loss modulus, and, within a range that does not inhibit the expression of storage modulus, silica, calcium carbonate, Known additives such as extenders such as barium sulfate, ultraviolet absorbers such as benzotriazole, benzophenone and fine particle cerium oxide, light stabilizers such as hindered amine radical scavengers, and heat stabilizers may be added.

  When a colorant is added to the intermediate resin layer to form a picture layer (including a solid color layer on the entire surface) or the like, a known colorant can be used as the colorant. For example, inorganic pigments such as titanium white, zinc white, carbon black, iron black, red iron oxide, cadmium red, graphite, titanium yellow, cobalt blue, and ultramarine blue, aniline black, quinacridone red, polyazo red, isoindolinone yellow, and benzidine yellow And organic pigments such as phthalocyanine blue and induslen blue, brilliant pigments such as flaky foil powders such as titanium dioxide-coated mica, shells, brass and aluminum, and other dyes are used as coloring agents.

  The pattern represented by the pattern layer also serving as the intermediate resin layer or the pattern layer not serving also is arbitrary, for example, a wood pattern, a stone pattern, a cloth pattern, a tile pattern, a brick pattern, a leather pattern, Grains, satin, letters, symbols, geometric patterns, etc.

  In the case of a picture layer that does not double as an intermediate resin layer, a known resin may be appropriately used as the binder resin in accordance with required physical properties such as adhesion to other layers. For example, for example, nitrocellulose, cellulose acetate, cellulose resin such as cellulose acetate propionate, urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin or the like alone or a mixture containing these. Used.

(Surface protective layer)
Next, the surface protective layer 3 is a layer to be the outermost surface layer of the decorative material, and may be formed of a thermoplastic resin. Resins are preferred. As the curable resin, a known resin can be used. For example, an ionizing radiation curable resin, a two-component curable urethane resin, an epoxy resin, a melamine resin, and the like are used. The surface protective layer can be formed by applying a coating liquid comprising one or more of these resins by a known coating method such as roll coating or gravure coating. Alternatively, it may be formed by full solid printing by a known printing method such as gravure printing or silk screen printing. The thickness of the surface protective layer depends on the application, required physical properties, etc., but is about 1 to 30 μm.

  The ionizing radiation-curable resin is a composition which can be cross-linked and cured by ionizing radiation. Specifically, a prepolymer (so-called prepolymer having a radical polymerizable unsaturated bond or a cationic polymerizable functional group in a molecule). A composition curable by ionizing radiation, in which an oligomer is included) and / or a monomer appropriately mixed, is preferably used. These prepolymers or monomers are used alone or as a mixture of two or more.

The above-mentioned prepolymer or monomer is, specifically, a compound having a radical polymerizable unsaturated group such as a (meth) acryloyl group, a (meth) acryloyloxy group, or a cationic polymerizable functional group such as an epoxy group in a molecule. Become. Further, a polyene / thiol prepolymer based on a combination of a polyene and a polythiol is also preferably used. In addition, for example, a (meth) acryloyl group means an acryloyl group or a methacryloyl group.
Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. can be used. A molecular weight of about 250 to 100,000 is usually used.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Further, as polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, There are also pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers.
Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of a polyurethane made of a diol and a diisocyanate.

  When crosslinking and curing with ultraviolet light or visible light, a photopolymerization initiator is further added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin.

  In addition, as the ionizing radiation, an electromagnetic wave or a charged particle having energy capable of causing a curing reaction of molecules in the ionizing radiation-curable resin (composition) is used. Usually, ultraviolet rays or electron beams are used, but it is also possible to use visible rays, X-rays, charged particle beams, and the like. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp is used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used. As the electron beam source, various electron beam accelerators such as Cockcroft-Walton type, Van degraft type, resonance transformer type, insulating core transformer type, or linear type, dynamitron type, and high frequency type are used, and 100 to 1000 keV, preferably A device that irradiates electrons having an energy of 100 to 300 keV is used.

  Further, a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer, a vinyl acetate resin, an acrylic resin, and a cellulose resin can be further added to the ionizing radiation-curable resin, if necessary.

  Further, various additives can be further added to the ionizing radiation-curable resin, if necessary. These additives include, for example, extenders (fillers) composed of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, and coloring agents such as dyes and pigments. And so on.

Further, in the decorative material of the present invention, the wear resistance is improved by the intermediate resin layer. Therefore, although the lubricant is not essential, it requires more excellent wear resistance, and the surface has a rough feel. When the influence of doctor wear, plate wear, etc. can be ignored, hard inorganic materials such as alumina (α-alumina), silica, glass, silicon carbide, boron carbide, diamond, etc. Lubricants such as a lubricant composed of particles, silicone resin, silicone oil, fluororesin, fluorine-modified oil, wood wax, montan wax, paraffin wax and the like may be further added.
In addition, the lubricant (eg, Vickers hardness, etc.) of the lubricant particles themselves is harder than the resin of the surface protective layer, and by this hardness, it has resistance to external stress and improves abrasion resistance. It is an additive based on a physical method to be used.
Further, the lubricant is an additive by a physicochemical method for improving the wear resistance by lowering the dynamic friction or the static friction coefficient by a lubricating action.

  The surface protective layer can be formed by applying a coating solution containing the above-mentioned resin by a conventionally known coating method such as roll coating or flow coating. Alternatively, it can also be formed by full-surface printing by a conventionally known printing method such as gravure printing.

(Deposited substrate)
The decorative material of the present invention (especially in the form of a decorative sheet such as decorative paper) is used as a surface decorative material to be adhered to the surface of various substrates to be adhered.
The substrate to be adhered is not particularly limited. For example, the material of the adhered substrate is an inorganic non-metal-based, metal-based, wood-based, resin-based, or the like. Specifically, in the inorganic nonmetal system, for example, papermaking cement, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium silicate, Non-ceramic ceramic materials such as gypsum and gypsum slag; and inorganic materials such as ceramics such as earthenware, ceramics, porcelain, setware, glass, and enamel. Further, in the metal system, for example, there are metal materials such as iron, aluminum, and copper. Further, in the case of woody materials, there are, for example, veneers made of cedar, cypress, oak, lauan, teak, etc., plywood, particle board, fiber board, laminated wood and the like. In the resin system, for example, there are resin materials such as polypropylene, ABS resin, and phenol resin.
The shape of the substrate to be adhered is arbitrary such as a flat plate, a curved plate, and a polygonal prism.

[Application]
The use of the cosmetic material of the present invention is not particularly limited, but includes walls, floors, ceilings and other building interior materials, doors, door frames, window frames and other fittings, rims, building members such as skirting boards, chests, Used for furniture such as cabinets.

  Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.

[Example 1]
For the purpose of test evaluation, a decorative material D as a decorative paper having a configuration as shown in FIG. 3 was prepared as follows.
First, a white colored solid with a coating amount (solid basis, the same applies hereinafter) of 5 g / m ² was applied to one surface of unbleached thin paper (unimpregnated paper) having a basis weight of 30 g / m ² as a substrate 1 in order from the substrate side. layer 7 (also said total solid layer in the picture layer), the pattern layer 5 of the red entire pattern at a coverage of 2 g / m ^2, an intermediate resin layer 2 consisting of three layers of the primer layer 6 coating amount 2 g / m ² Coating was performed sequentially with a Miya bar. The resin components of these three layers were the same. As shown in Table 1, the resin is a (saturated) polyester resin (having a hydroxyl group). The same applies in [] below. And an unsaturated polyester resin (having a hydroxyl group) [U-PES] in a ratio of 4 to 6 with respect to 100 parts by mass of a base resin, 1,6-hexamethylene diisocyanate (HMDI 2) A two-component curable urethane resin containing 3 parts by mass of an adduct was used.

The dynamic viscoelastic properties of the resin (in this case, the crosslinked cured product) were determined by measuring a single layer of the resin in a polypropylene weighing dish with a dynamic viscoelasticity measuring apparatus (manufactured by UBM, " Rheogel-E4000 "). The measurement was performed in a tensile mode, a vibration was applied with a sine wave of 10 Hz, the strain was 5 μm, the heating rate was 3 ° C./min, the capturing temperature was 2 ° C., and the measuring temperature range was −50 ° C. to 120 ° C. . As a result, the temperature-dependent specification of the loss modulus E ″ has a peak at −14 ° C. lower than room temperature (10 ° C. to 50 ° C. is set to room temperature for a series of prepared cosmetic materials), and 90 ° C. exceeding room temperature. The storage elastic modulus E 'was 7 × 10 ⁷ to 2 × 10 ⁸ Pa in the room temperature range.

Further, on the intermediate resin layer 2, a coating of an electron beam-curable resin composed of 20 parts by mass of a 4-functional urethane acrylate prepolymer, 40 parts by mass of a trifunctional urethane acrylate prepolymer, and 40 parts by mass of a polyester acrylate oligomer was applied. After coating with a miller bar so as to be 5 g / m ² , an electron beam is irradiated under the conditions of 175 keV and 30 kGy (3 Mrad) to crosslink and cure the coating film to form a surface protective layer 3 made of a crosslinked resin. The decorative material was D.

[Example 2]
In Example 1, the resin of the three-layered intermediate resin layer also serving as a sealer layer, a picture layer, and a primer layer was changed to an aqueous (saturated) polyester resin [aqueous PES] as shown in Table 1 and crosslinked. A cosmetic material was obtained in the same manner as in Example 1, except that the agent was not used. The peak temperature of the loss elastic modulus E ″ of the resin at a temperature lower than room temperature is −31 ° C., and there is no peak exceeding the room temperature. The value of the storage elastic modulus E ′ in the room temperature region is 2 × 10 ^7. ２2 × 10 ⁸ Pa.

[Example 3]
In Example 1, a cosmetic material was obtained in the same manner as in Example 1 except that only the main agent was used and the crosslinking agent was not used as shown in Table 1 as the resin of the intermediate resin layer. In addition, the peak temperature of the loss elastic modulus E ″ of the resin (which is a non-crosslinked thermoplastic resin) below room temperature was −10 ° C., and the peak temperature above room temperature was 60 ° C. Further, storage elasticity was obtained. The value of the ratio E ′ in the room temperature range was 2 × 10 ⁷ to 2 × 10 ⁸ Pa.

[Example 4]
In Example 1, as shown in Table 1, as the resin of the intermediate resin layer, the main component was only a (saturated) polyester resin [PES] (the blending of the cross-linking agent was unchanged), and the makeup was the same as in Example 1. Wood was obtained. The peak temperature below room temperature of the loss elastic modulus E ″ of the resin (which is a crosslinked resin) is −10 ° C., there is no peak exceeding room temperature, and the storage elastic modulus E ′ is a value in the room temperature region. Was selected to be 1 × 10 ⁷ to 2 × 10 ⁷ Pa.

[Example 5]
In Example 1, a cosmetic material was prepared in the same manner as in Example 1 except that an acrylic resin [AC (A)] was used (a crosslinking agent was not used) as a resin of the intermediate resin layer as shown in Table 1. Obtained. The peak temperature of the resin (which is a thermoplastic resin) having a loss modulus E ″ at a temperature lower than room temperature is 6 ° C., and there is no peak exceeding the room temperature. Was 2 × 10 ⁸ to 2 × 10 ⁹ Pa.

[Example 6]
In Example 1, as shown in Table 1, the resin of the surface protective layer was changed to the electron beam-curable resin [EB], and the crosslinking agent of the HMDI adduct was 12 parts by mass with respect to 100 parts by mass of the urethane polyol main agent. A cosmetic material was obtained in the same manner as in Example 1, except that a two-component curable urethane resin [two-component PU] was used and cured by heating.

[Comparative Example 1]
In Example 1, as the resin of the intermediate resin layer, as shown in Table 1, acrylic resin [AC (B)] (however, the resin content is different from the acrylic resin used in Example 5) and vinyl chloride- A cosmetic material was obtained in the same manner as in Example 1, except that a mixed resin with a vinyl acetate copolymer [VC-VA] at a ratio of 5 to 5 was used (a crosslinking agent was not used). The loss elastic modulus E ″ of the mixed resin (thermoplastic resin) had no peak below room temperature and a peak at 51 ° C. which was higher than room temperature. Was 6 × 10 ⁸ to 2 × 10 ⁹ Pa.

[Comparative Example 2]
In Example 1, a cosmetic material was obtained in the same manner as in Example 1 except that an acrylic urethane resin [ACU] was used as the resin of the intermediate resin layer as shown in Table 1 (a crosslinking agent was not used). . The loss modulus E ″ of the resin (thermoplastic resin) has no peak below and above room temperature, but has a peak in the room temperature region (31 ° C.). 'In the room temperature range was 2 × 10 ⁷ to 1 × 10 ⁹ Pa.

[Comparative Example 3]
A cosmetic material was obtained in the same manner as in Example 1, except that the formation of the intermediate resin layer was omitted.

(Performance evaluation)
Each decorative material of the example and the comparative example was attached to a 3 mm-thick plywood plywood as a wood substrate as an adhered substrate with a double-sided adhesive tape to form a decorative plate, and the decorative plate was evaluated. The evaluation was performed for the abrasion resistance and the solvent resistance by the following method.

(1) Abrasion resistance: Evaluated according to JIS K 6902 thermosetting decorative board and NEMA standard abrasion resistance test. Specifically, using a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.), using S42 abrasive paper with a load of both wheels of 9.81 N (1 kgf), two points of wear reduction [mg] after 10 rotations were measured, The average was evaluated.

(2) Solvent resistance: Rubbing was performed 200 times on the surface of the surface protective layer of the decorative board with a gauze impregnated with methyl ethyl ketone under a load of 0.981 N (100 gf), and the appearance change of the decorative material due to the solvent was observed. It was visually observed. Those without change were good, and those with change were bad.

As a result of the above evaluation, as shown in Table 1, the abrasion resistance of all the examples was good. However, all of the comparative examples were defective. That is, in Comparative Example 3 having no intermediate resin layer itself, there was an intermediate resin layer, and even when the storage elastic modulus E ′ was 1 × 10 ⁷ to 2 × 10 ⁹ Pa in the room temperature region, the essential loss elastic modulus E ″ was lower than room temperature. Comparative Example 2 having no peak less than or less than Comparative Example 1, or Comparative Example 1 having a peak in the loss elastic modulus E ″ but only in a temperature range exceeding room temperature.
On the other hand, in the solvent resistance, the surface protection layer was formed of a crosslinked resin in all of the examples and comparative examples, but the intermediate resin layer was formed of a thermoplastic resin. 5, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were defective. However, Examples 1, 4 and 6 in which the intermediate resin layer was formed of a crosslinked resin were good. Therefore, in applications where solvent resistance is required in addition to abrasion resistance, it is understood that the intermediate resin layer is preferably formed of a crosslinked resin.

FIG. 2 is a cross-sectional view illustrating one embodiment of the decorative material of the present invention, and an explanatory diagram conceptually illustrating dynamic viscoelastic properties (loss elastic modulus E ″ and storage elastic modulus E ′) of the intermediate resin layer. Sectional drawing which shows the other example of a form of the decorative material of this invention. Sectional drawing which shows the other example of a form of the decorative material of this invention.

Explanation of reference numerals

Reference Signs List 1 base material 2 intermediate resin layer 3 surface protective layer 4 sealer layer 5 picture layer 6 primer layer 7 colored solid ink layer D cosmetic material E 'storage elastic modulus E'
E "Loss modulus E"
Pa Peak of E ″ below room temperature Pb Peak of E ″ above room temperature R Optimal region of E ′ at room temperature (region) Tr Room temperature (region)

Claims (4)

On a base material, an intermediate resin layer made of a coating liquid or ink, and a cosmetic material having a surface protective layer made of a cross-linked resin in this order,
The temperature-dependent characteristic at a measurement frequency of 10 Hz of the loss elastic modulus in the dynamic viscoelasticity method of the intermediate resin layer is at least room temperature (however, room temperature is a temperature having a width defined from 10 ° C. to 50 ° C.) A cosmetic material having a peak at a temperature of less than and wherein said intermediate resin layer is in contact with said surface protective layer. Value at a measuring frequency of 10Hz of the storage elastic modulus in dynamic viscoelasticity method of the intermediate resin layer is ^{1 × 10 7 ~2 × 10 9} Pa at room temperature region, claim 1 decorative material according. The cosmetic material according to claim 1 or 2, wherein the temperature-dependent characteristic of the intermediate resin layer at a measurement frequency of 10 Hz of a loss elastic modulus in a dynamic viscoelasticity method further has a peak even at a temperature exceeding room temperature. The decorative material according to any one of claims 1 to 3, wherein the base material is paper.