JP4759907B2 - Cosmetic material - Google Patents

Description

  The present invention relates to interior and exterior materials such as wall materials, ceiling materials, and floor materials in buildings such as houses, stores, and office buildings, building materials such as joinery and construction materials, furniture fixtures, housing equipment, and home appliances. The present invention relates to a decorative material used as an exterior material, an interior / exterior material of a transportation device such as a vehicle.

  In the past, for example, solid wood and veneer, natural stone, natural leather, and woven fabric were used as decorative materials for various applications. However, products with more stable design quality can be mass-produced at low cost. Currently, it is common to use artificial materials such as paper and synthetic resin films provided with various design patterns by printing. The pattern printed layer in such a decorative material is different from the printed material such as a normal book, and even if it is used under conditions exposed to light for many years, the design of the pattern is significantly deteriorated due to discoloration, etc. Excellent weather resistance is required so that the surface strength and interlaminar adhesion strength do not significantly decrease due to ink deterioration.

A variety of printing inks have been developed that can meet such strict requirements. Among them, a resin having an active hydrogen group capable of reacting with an isocyanate compound is used as a main agent, and both are blended using an isocyanate compound as a curing agent. Printing inks that are crosslinked and cured by the urethanization reaction between the active hydrogen group and the latter isocyanate group, using an isocyanate-cured urethane tree as a binder, can form a printing ink film with extremely excellent weather resistance. Have already been widely used in various cosmetic materials (Patent Documents 1 to 4).
Japanese Patent Publication No.55-7378 Japanese Patent Laid-Open No. 11-179858 Japanese Patent Laid-Open No. 2000-135771 However, in recent years, demands for various physical properties of cosmetic materials made of such artificial materials have become increasingly severe, and from the viewpoint of effective use of limited resources, the lifespan of houses has been extended and extended. The use of cosmetic materials has been required to extend the service life, and from the viewpoints of resource protection and high appearance design, it has been required to expand the use of printed cosmetic materials, which had been mainly used for interior applications. As the demand for improving the weather resistance of cosmetic materials is becoming stronger, even with printing inks containing the above-mentioned isocyanate-curable urethane resins as binders, there is a demand for pattern printing layers in cosmetic materials. In reality, it is becoming difficult to sufficiently satisfy the weather resistance.

For example, for floor tiles for interiors in stores, for example, those made of polyvinyl chloride resin have been the mainstream, but polyvinyl chloride resin, hydrogen chloride gas, dioxins, etc. during combustion in the event of a fire or incineration As a substitute for this, floor tiles using ionomer resin, a non-halogen thermoplastic resin having properties similar to polyvinyl chloride resin, have been proposed. Replacement of resin floor tiles is in progress (Patent Documents 5 to 8).
JP-T 9-504484 JP-A-9-207276 JP-A-10-315422 However, in the conventional floor tile made of polyvinyl chloride resin, the transparent surface layer, the pattern printing layer, and the backer layer are all made of polyvinyl chloride resin and are fused and integrated by thermal lamination. In fact, there is no problem of interlayer adhesion, but a flooring material using an ionomer resin inevitably becomes a multilayer laminate composed of different kinds of resins, so it is difficult to ensure interlayer adhesion strength.

  In connection with this problem, the present inventors have already used a printing ink having an isocyanate curable urethane resin as a binder for the pattern printing layer, and used as a primer layer on the pattern printing layer, a hydroxyl group, an amino group or a carboxyl at the terminal. It has been found that by providing a resin layer mainly composed of a mixture of an olefin-based resin having a group and an ethylene-vinyl acetate copolymer resin, sufficient interlayer adhesion strength as a floor tile can be obtained.

  Of course, the above floor tiles have excellent interlayer adhesion strength immediately after production, and almost no decrease in interlayer adhesion strength is observed even after an accelerated weathering test of about 1000 hours with a sunshine weatherometer. It can be said that it is at a certain level as a floor tile for indoor use.

  However, it was found that when the sunshine weatherometer exceeded 1000 hours, the interlaminar adhesion strength began to gradually decrease, and after 2000 hours, it decreased to less than half of the original. This is not at the level that it cannot be used immediately as a floor tile for indoor use, but it is used for a long period of time exceeding the expected life when used in a place where the floor is exposed to direct sunlight, etc. Considering such cases, it is difficult to say that the level is sufficiently satisfactory.

  Therefore, when the peeled surface of the floor tile whose interlaminar adhesion strength was reduced by the accelerated weather resistance test was investigated, the design printing layer caused cohesive failure because the isocyanate curable urethane resin that was the binder of the design printing layer was deteriorated. Turned out to be. Therefore, in order to suppress the deterioration of the interlayer adhesion strength of the floor tile over time and to ensure long-term weather resistance and durability under more severe conditions, improvement of the weather resistance of the pattern printing layer should be avoided. It is the most important issue that cannot be done.

  Also, in various decorative materials other than the floor tiles exemplified above, the deterioration of the pattern printing layer directly leads to a decrease in the interlayer adhesion strength, surface strength, etc. of the decorative material, so that the weather resistance and durability of the decorative material are reduced. It can be said that the improvement of the weather resistance of the pattern printing layer is indispensable for the improvement, which is a technical problem common to general cosmetics.

  The present invention has been made in view of the above-mentioned problems of the prior art, and the technical problem is that in a cosmetic material having at least a pattern printing layer having an isocyanate-curable urethane resin as a binder, the pattern printing layer An object of the present invention is to provide a cosmetic material with improved weather resistance and durability, which can further improve the weather resistance of the cosmetic material and maintain physical properties such as interlayer adhesion strength or surface strength of the cosmetic material for a longer period of time.

In order to solve the above problems, the decorative material of the present invention comprises an ionomer resin layer and an intermediate resin layer made of a polyolefin resin or a polyester resin. In the decorative material provided with a printing layer, the pattern printing layer is a printing ink composition comprising an isocyanate curable urethane resin used as a curing agent in which an unblocked isocyanate compound and a blocked isocyanate compound are blended. And the isocyanate curable urethane resin is crosslinked and cured by a urethanization reaction using the unblocked isocyanate compound as a crosslinking agent, and the blocked isocyanate compound is in an undissociated state. That it remains It is an.

Further, the present invention provides a backer comprising the thermoplastic resin containing an inorganic filler via a primer layer on the ionomer resin layer, another ionomer resin layer, and the pattern printing layer on the decorative material. The layer is laminated .

  As described above, the decorative material of the present invention is not only crosslinked and cured by the urethanization reaction using an isocyanate compound as a crosslinking agent, but also the crosslinked and cured isocyanate-based urethane resin that is a binder of the pattern printing layer. An undissociated blocked isocyanate compound is contained in an unreacted state inside the isocyanate-curable urethane resin.

  Although this undissociated blocked isocyanate compound hardly dissociates within the period from the production of the cosmetic material to the construction, the dissociation gradually proceeds on a long time scale of the usage period after the construction of the cosmetic material. The isocyanate compound produced by the dissociation further reacts with the already crosslinked and cured isocyanate-based urethane resin, which is a binder for the pattern printing layer, to further improve the crosslinking density.

  Therefore, even if the isocyanate curable urethane resin deteriorates and the molecular chain is broken due to long-term aging during use and the action of ultraviolet rays, it is cross-linked again by the reaction with the isocyanate compound generated by the above dissociation. As a result, the decrease in the crosslink density is suppressed, and the internal cohesive force of the picture print layer is maintained. In this way, it is possible to maintain the interlaminar adhesion strength and surface strength of the decorative material for a longer period than before.

  The specific configuration of the decorative material of the present invention is not limited at all except that it is essential to include at least a pattern printing layer. Generally, a pattern printing layer is formed on one or both sides of a suitable base material as a support for the pattern printing layer. In order to protect this pattern printing layer, a surface protective layer may be formed on the opposite side of the pattern printing layer from the substrate, or another substrate may be laminated, and either one or the other In some cases, one or more material layers are laminated on both sides to be multilayered. Of course, all layers laminated on at least one side of the pattern printing layer are all transparent or translucent, and the pattern printing layer can be observed from at least one side of the decorative material.

  There is no restriction | limiting in the material of the base material in the decorative material of this invention, The thing similar to what has been used as a base material of the conventional decorative material can be used. Specifically, for example, paper such as thin paper, titanium paper, fine paper, kraft paper, resin-impregnated paper, resin mixed paper, inter-paper reinforced paper, and fibrous base materials such as woven fabric, non-woven fabric, knitted fabric, Thermoplastic resins such as polyolefin resin, polyester resin, acrylic resin, polystyrene resin, polyvinyl resin, unsaturated polyester resin, epoxy resin, melamine resin, urea resin, phenol resin, polyurethane resin Thermosetting resins such as, synthetic resin base materials such as fiber reinforced plastic, wood single board, plywood, laminated wood, medium fiber board, wood base materials such as particle board, glass, ceramics, gypsum board, slate board , Calcium silicate board, slag gypsum board, wood wool cement board, glass fiber reinforced concrete board, lightweight cellular concrete board and other inorganic base materials, steel, brass, stainless steel, Metallic substrates such as aluminum, or a composite-based substrate or the like consisting of a plurality of types, the form also a sheet, plate, various molded articles like an interpreter, or at all. Moreover, when setting it as a multilayer laminated body, the arbitrary materials chosen from these can be used by arbitrary combinations.

  The isocyanate-curable urethane resin used as a binder for the pattern printing layer in the decorative material of the present invention is mainly composed of a resin having an active hydrogen group that can react with an isocyanate compound, and the isocyanate compound as a curing agent. In the present invention, in particular, at least a blocked isocyanate compound is blended as the isocyanate compound, and at the time of the crosslinking and curing, at least a part of the blocked isocyanate compound remains unreacted and undissociated. It needs to remain in a state.

  As the resin having an active hydrogen group capable of reacting with the main isocyanate compound, for example, a resin having an amino group, an imino group, a carboxyl group, or the like can be used. In general, a resin having a hydroxyl group, that is, a polyol compound is used. It is often done. Examples of such polyol compounds include polyester polyol compounds, polyether polyol compounds, polyurethane polyol compounds, acrylic polyol compounds, and the like. Of course, a mixture of a plurality of these may be used.

  Examples of the blocked isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like, or their burettes, adducts, isocyanurates and the like. The free isocyanate group is, for example, a phenol blocking agent such as phenol or cresol, an oxime blocking agent such as methyl ethyl ketone oxime or acetone oxime, a lactam blocking agent such as ε-caprolactam or γ-butyrolactam, ethyl acetoacetate or acetylacetone. Active methylene blocking agents such as ethyl malonate, alcohol blocking agents such as methanol and ethanol, A compound formed by blocking with a blocking agent such as an amine blocking agent, an imine blocking agent, an imide blocking agent, an imidazole blocking agent, or a mercaptan blocking agent can be used. Of course, a mixture of a plurality of these may be used.

  In order to crosslink and cure the blend of both of the above by a urethanization reaction and to leave the undissociated blocked isocyanate compound, the block isocyanate compound as a curing agent is excessively blended, and the heating temperature and heating at the time of crosslinking and curing are also included. By appropriately adjusting the processing conditions such as time, a method of dissociating only a blocked isocyanate compound in an amount corresponding to the active hydrogen group of the main agent and a crosslinking reaction, or a plurality of different dissociation temperatures as a blocked isocyanate compound as a curing agent A method in which only those having a low dissociation temperature are dissociated and subjected to a crosslinking reaction, and those having a high dissociation temperature are left in an undissociated state by performing a curing treatment at a temperature intermediate between the respective dissociation temperatures. Etc. are also conceivable.

  However, in the method as described above, the reaction amount varies due to variations in processing conditions such as heating temperature and heating time, and the physical properties of the resulting cosmetic material are likely to be unstable. Therefore, as a curing agent, a method is used in which an unblocked isocyanate compound and a blocked isocyanate compound are used in combination, and only the unblocked isocyanate compound is subjected to a crosslinking reaction to leave the blocked isocyanate compound without dissociation. For example, the reaction amount is determined by the blending ratio of the unblocked isocyanate compound and the blocked isocyanate compound, which is advantageous for stabilizing the physical properties of the resulting cosmetic material. This is because the crosslinking reaction with the unblocked isocyanate compound is completed within a few days at room temperature or a low temperature of about 50 ° C. or less, so that there is no possibility that the blocked isocyanate compound will dissociate and react during this time. In addition, when a heating process is included after the pattern printed layer is formed in the manufacturing process of the decorative material, a blocked isocyanate compound having a high dissociation temperature is used so that it hardly dissociates under the conditions of the heating temperature and time. It is desirable to do.

  Non-blocked isocyanate compounds include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like, or their burettes, adducts, isocyanurates and the like. Can be used.

  However, in consideration of weather resistance, it is desirable to use an aliphatic or alicyclic isocyanate compound that does not have an aromatic ring that causes yellowing. For example, isophorone diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylhexane diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc., or derivatives thereof. This is common for blocked and unblocked isocyanates.

  The blending amount of the unblocked isocyanate compound is preferably an amount substantially commensurate with the amount of active hydrogen groups of the resin having active hydrogen groups, but it is not always necessary to exactly match the number of active hydrogen groups. In general, the blending ratio is selected such that the ratio to the number of isocyanate groups is approximately in the range of about 1: 0.9 to 1: 1.4. In general, it is preferable to add about 1 to 10 parts by weight per 100 parts by weight of the resin having active hydrogen groups.

  The blending amount of the blocked isocyanate compound is appropriately designed depending on the degree of weather resistance and durability desired for the cosmetic material. Increasing the amount is more advantageous in terms of weather resistance and durability. In the initial state immediately after production, the binder of the pattern printing layer contains many unreacted low molecular weight components, so that the physical properties of interlayer adhesion in the initial state are reduced, or the blocked isocyanate compound is dissociated over time. In some cases, the cross-linking reaction by the isocyanate compound thus produced proceeds too much, and the cross-linking density of the binder of the picture print layer becomes extremely high, which may cause a decrease in physical properties such as interlayer adhesion. Therefore, the blending amount of the blocked isocyanate compound is preferably about twice or less than the blending amount of the unblocked isocyanate compound. In general, the blending amount is preferably about the same as that of an unblocked isocyanate compound. Generally, the blending amount is about 1 to 10 parts by weight with respect to 100 parts by weight of the resin having an active hydrogen group. preferable.

  By the way, it is possible to use a blocked isocyanate compound alone without blending any unblocked isocyanate compound and leave it in the pattern print layer without dissociating it at the time of completion of the cosmetic material. Since the binder of the printing layer is not cross-linked and cured, the initial interlayer adhesion strength is inferior, the drying property of the printing ink composition after printing is poor, and a blocking phenomenon is likely to occur during winding or stacking of printed materials. There is a problem.

  To give an example of a more specific embodiment of the decorative material of the present invention, FIG. 1 shows an ionomer resin layer 1 and an intermediate resin layer 2 made of a polyolefin resin or a polyester resin in order from the upper side. And a decorative material suitable for applications such as floor tiles, in which the pattern printing layer 3, the primer layer 4, and the backer layer 5 are laminated. This decorative material pattern print layer 3 is an isocyanate-cured urethane resin that has been crosslinked and cured by the urethanization reaction using an isocyanate compound as a crosslinking agent as described above, and contains an undissociated blocked isocyanate compound. Are formed using a binder.

  The ionomer resin used for the ionomer resin layer 1 is a resin in which organic and inorganic components are generally bonded by covalent bonds and ionic bonds. Examples of the ionomer resin particularly preferably used for the decorative material include resins in which the copolymer molecules are cross-linked with metal ions. Examples of the copolymer in this case include acrylate copolymers such as ethylene- A methacrylic acid copolymer etc. are mentioned. Examples of metal ions include ions such as Na, K, Mg, and Zn.

  In order to obtain an ionomer resin, for example, Na, K, Mg, an ethylene polymer copolymerized with a monomer having a carboxyl group in the side chain, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc. A method of neutralizing an acid group by adding a hydroxide such as Zn, an alkoxide, a lower fatty acid salt or the like can be mentioned. As a result, a structure in which carboxyl anions distributed along the molecular chain are electrostatically combined with metal cations existing between the molecules to form a kind of cross-links, and the copolymer molecules are cross-linked with metal ions. The ionomer resin can be obtained.

  The above-mentioned ionomer resin can be arbitrarily selected in terms of sheet hardness depending on the copolymer composition of the main chain, and the cross-linking by metal ions is weakened by overheating, and the bonding strength is restored by cooling. Since it has properties similar to those of a thermoplastic resin such as vinyl resin, it has an advantage that it can be easily applied to a conventional production line for decorative materials made of polyvinyl chloride resin, which has been manufactured by thermal lamination and embossing.

  The ionomer resin layer 1 is obtained by forming a sheet obtained by adding an appropriate additive to the above ionomer resin. The thickness of the ionomer resin layer 1 is not particularly limited in the present invention, but a thickness of about 200 to 1000 μm is usually appropriate.

  The ionomer resin layer 1 may be a laminate of two or more layers. In the example shown in FIG. 1, the ionomer resin layer 1 is composed of two layers of a first ionomer resin layer 11 on the surface side and a second ionomer resin layer 12 on the lower side. If comprised in this way, even if it is a case where the direct thermal lamination of the intermediate resin layer 2 which is a printing base material and the ionomer resin layer 1 is difficult, about 10-100 micrometers in thickness on the surface side of the intermediate resin layer 2 beforehand. If the thin second ionomer resin layer 12 is laminated by, for example, a dry lamination method, an extrusion lamination method, a coextrusion method, or the like, the first ionomer resin layer 12 is formed on the second ionomer resin layer 12 surface of the laminate. There is an advantage that 11 can be easily heat laminated.

  The intermediate resin layer 2 serves as a printing substrate in place of the ionomer resin layer 1 having poor solvent resistance and poor printability, and is a chemical component contained in a wax or a detergent used during use of a cosmetic material. Is provided for the purpose of blocking the penetration of chemical components, preventing penetration of the ionomer resin layer 1 and invading the pattern printing layer 3 and the primer layer 4. Preferably used.

  Examples of the polyolefin resin include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, and ethylene-propylene-butene-1 copolymer. Polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and the like can be used.

  When the pattern printing layer 3 is formed on the back surface of the intermediate resin layer 2, any known printing method can be applied. For example, a gravure printing method, an offset printing method, a flexographic printing method, a screen printing method, a transfer printing method, an inkjet printing method, and the like. Of these, the gravure printing method is the most common for decorative materials. Further, before printing the pattern printing layer 3, for example, corona discharge treatment, plasma treatment, ozone treatment, ionizing radiation treatment, flame treatment, acid or alkali treatment, etc. on the back surface of the intermediate resin layer 2 in advance. A surface treatment may be applied.

  If the thickness of the intermediate resin layer 2 is too thin, the barrier property against various chemical substances is insufficient, and if it is too thick, the flexibility and elasticity of the ionomer resin layer 1 are diminished and the properties of the cosmetic material are impaired. It is desirable to be within a range of about 100 μm.

  Various additives may be added to the ionomer resin layer 1 and the intermediate resin layer 2 as necessary, as long as the transparency is not significantly diminished. As additives, for example, ultraviolet absorbers, light stabilizers, heat stabilizers, colorants, fillers, lubricants, flame retardants, antistatic agents, antibacterial agents, antifungal agents and the like can be used in any combination.

  The primer layer 4 is provided to firmly bond the intermediate resin layer 2 and the pattern printing layer 3 and the backer layer 5 to each other, and the materials thereof are the intermediate resin layer 2, the pattern printing layer 3, and the backer layer. What is necessary is just to determine suitably considering the adhesiveness with the constituent material of the layer 5. FIG. What is necessary is that it is a hot melt type that exhibits sufficient adhesiveness under conditions of temperature and pressure for thermal lamination from the ionomer resin layer 1 to the backer layer 5, and has an adhesive strength that can withstand practical use as a cosmetic material. Is to have.

  A suitable example of the primer used for the primer layer 4 is, for example, an ethylene-vinyl acetate copolymer resin (EVA), an olefin resin, or a resin mainly composed of a mixture thereof, particularly 30 to 50 ° C. Those having the property of being dissolved in are preferable. Further, in particular, when a resin having a functional group such as a hydroxyl group, an amino group or a carboxyl group at the terminal is used as the olefin-based resin, it is between the functional group such as a carboxyl group or an ester bond contained in an adjacent layer. It is preferable because a chemical bond such as a hydrogen bond, an amide bond or an ester bond can be generated and the adhesiveness can be drastically improved.

  The formation method of the primer layer 4 is not specifically limited, It can form by applying conventionally well-known arbitrary coating methods suitably. Specific examples include a gravure coating method, a roll coating method, a knife coating method, an air knife coating method, a bar coating method, a dip coating method, a kiss coating method, a spray coating method, a die coating method, and the like. Various printing methods exemplified as the forming method can also be used.

When the primer layer 4 is a hot melt type as described above, the primer layer 4 is most preferably formed by a hot melt coating method. That is, it coats, heating the coating liquid which adjusted solid content ratio NV of resin to about 5-30%. The coating method can be carried out by arbitrarily applying any conventionally known means described above. The amount of the primer layer 4 applied (after drying) is suitably about 0.1 to 10 g / m ² , but of course is not limited to this range.

  The backer layer 5 serves as a support for the decorative material, and the same material as that used as the backer layer in the conventional similar decorative material may be used. In general, a thermoplastic resin is the main component, and specific examples of the thermoplastic resin include ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin (EEA), ethylene, and the like. Methacrylic acid copolymer resin (EMAA), ethylene-acrylic acid copolymer resin (EAA), ethylene diacrylate resin (EDA), ionomer resin and other acrylate copolymer resins, and ethylene-vinyl acetate copolymer Examples thereof include resins such as a resin (EVA), a vinyl ester copolymer resin such as an ethylene-vinyl butyrate copolymer resin (EVB), or a mixture thereof. Such a copolymer resin has an advantage that the hardness of the sheet can be arbitrarily changed by the copolymer composition.

  An inorganic filler is added to the thermoplastic resin constituting the backer layer 5 for the purpose of imparting rigidity and dimensional stability required as a support for a decorative material or reducing the manufacturing cost. It is common. Specific examples of the inorganic filler include calcium carbonate, barium sulfate, talc, mica, kaolin, calcined clay, silica, alumina, magnesia, titanium oxide, zinc oxide, magnesium silicate, potassium titanate, aluminum hydroxide, water Any combination of magnesium oxide and the like can be used. The addition amount of the inorganic filler is appropriately designed in the range of about 5 to 500 parts by weight per 100 parts by weight of the thermoplastic resin.

  In addition, various additions such as UV absorbers, light stabilizers, heat stabilizers, colorants, organic fillers, metal powders, lubricants, flame retardants, antistatic agents, antibacterial agents, antifungal agents, etc., as necessary Of course, the agents may be added in any combination. The thickness of the backer layer 5 is not particularly limited and is arbitrary. However, considering the thickness of the entire decorative material, a thickness of about 0.5 to 5 mm is usually appropriate.

  The backer layer 5 may be composed of a multilayer stack of two or more layers. In the example shown in FIG. 1, the backer layer 5 includes a surface layer 51 made of an upper ethylene diacrylate resin and a base layer 52 made of an ethylene-vinyl acetate copolymer resin containing a lower inorganic filler. . Thus, when the backer layer 5 is comprised from the multilayer laminated body, the inorganic filler does not necessarily need to be contained in all the layers, and may be contained only in one part layer.

  The method for producing the decorative material will be described. First, a laminated film of the intermediate resin layer 2 made of polyolefin resin or polyester resin and the second ionomer resin layer 12 is formed by dry lamination, extrusion lamination, Produced by a known method such as an extrusion film forming method, on the intermediate resin layer 2 surface, a main agent composed of a resin having an active hydrogen group, and a curing agent composed of a mixture of a blocked isocyanate compound and an unblocked isocyanate compound Using the printing ink composition having an isocyanate curable polyurethane resin as a binder, which is a blended composition, the pattern printing layer 3 is formed by an appropriate printing method, and the primer layer 4 is formed by coating. Alternatively, after the pattern printing layer 3 is formed on one surface of the intermediate resin layer 2, the second ionomer resin layer 12 may be laminated on the opposite surface by a dry laminating method or an extrusion laminating method.

  Next, a laminated body in which the first ionomer resin layer 11 is disposed on the second ionomer resin layer 12 surface of the laminated film and the backer layer 5 is disposed on the primer layer 4 surface, which are bonded together by a thermal lamination method. Is made. As a lamination method, there are generally a multi-stage press method using single wafers or a continuous lamination method, and any of these methods may be used for producing the above-mentioned decorative material.

  The surface of the resulting laminate may be embossed to form a concavo-convex shape in order to further improve the design. As the means for embossing, a conventionally known method of pressurizing an embossing roll or an embossing plate having an uneven surface can be used. The embossing may be performed separately from the thermal lamination described above, but it is advantageous to perform the embossing simultaneously because the manufacturing process can be shortened. For the above thermal lamination and embossing, it is possible to apply a conventional production line of a polyvinyl chloride resin decorative material as it is, and inexpensive production is possible.

  Hereinafter, specific examples and comparative examples of the decorative material of the present invention will be shown and described in more detail.

Example 1
A co-extruded film having a total thickness of 80 μm comprising a polypropylene resin layer having a thickness of 50 μm and an ionomer resin layer having a thickness of 30 μm (“HIMILAN” manufactured by Mitsui DuPont Polychemical Co., Ltd.) was prepared. Resin (main agent: hydroxyl group-containing urethane-vinyl chloride resin 100 parts by weight, curing agent: isophorone diisocyanate (IPDI) -hexamethylene diisocyanate (HMDI) isocyanate curing agent (unblocked) 3 parts by weight and hexamethylene Using a printing ink composition having a diisocyanate (HMDI) block isocyanate curing agent (3 parts by weight) as a binder, a pattern is printed by a gravure printing method (average coating amount after drying is about 1 g / m ² ), Ethylene-vinyl acetate And coalescing the resin, the coating amount after drying by gravure coater mixture main component (EVA / olefin = 1/3) and the primer coating of an olefin-based resin having a carboxyl group at the terminal with 1.5 g / m ² It was applied and dried.

  Next, an ionomer resin sheet (“HIMILAN” manufactured by Mitsui DuPont Polychemical Co., Ltd.) having a thickness of 600 μm is formed on the surface of the ionomer resin layer of the coextruded film on which the pattern printing and the primer have been applied. A surface layer surface of a backer layer made of a laminate of a surface layer made of acrylate (EDA) resin having a thickness of 80 μm and a base layer made of ethylene-vinyl acetate copolymer (EVA) resin containing an inorganic filler and made of 1 mm thick. The decorative material according to the present invention was manufactured by laminating and laminating by a continuous lamination method under a lamination temperature of 120 ° C.

Comparative Example 1
In Example 1 described above, a decorative material was prepared under the same conditions except that the blocked isocyanate curing agent was removed from the printing ink composition used for pattern printing.

Performance Evaluation The decorative material of Example 1 and Comparative Example 1 was subjected to an accelerated weather resistance test with a sunshine weatherometer, and the delamination strength of the decorative material after 500 hours, 1000 hours and 2000 hours was measured. The results were as shown in the table below. However, as for the peeling part, only after 2000 hours of Comparative Example 1 was the cohesive failure of the pattern printing layer, and all the others were delaminations between the surface layer and the base layer in the backer layer.

Measurement result of delamination strength after accelerated weathering test (unit: [N / mm])
Elapsed time 0 hours 500 hours 1000 hours 2000 hours
Example 1 3.2 3.1 3.2 3.1
Comparative Example 1 3.2 3.2 3.3 0.9 0.9

It is a sectional side view which shows embodiment of the decorative material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ionomer resin layer 11 1st ionomer resin layer 12 2nd ionomer resin layer 2 Intermediate resin layer 3 Picture printing layer 4 Primer layer 5 Backer layer 51 Surface layer 52 Base layer

Claims (2)

In a cosmetic material comprising an ionomer resin layer and an intermediate resin layer made of a polyolefin resin or a polyester resin, and a pattern printing layer having an isocyanate curable urethane resin as a binder on the intermediate layer, the pattern printing layer is , Formed by a printing ink composition having an isocyanate curable urethane resin used as a curing agent in which an unblocked isocyanate compound and a blocked isocyanate compound are blended, and the isocyanate curable urethane system The resin is crosslinked and cured by a urethanization reaction using the unblocked isocyanate compound as a crosslinking agent, and the blocked isocyanate compound remains in an undissociated state.
Furthermore, another ionomer resin layer on the ionomer resin layer, and a backer layer made of a thermoplastic resin containing an inorganic filler via a primer layer are laminated on the pattern printing layer. The cosmetic material according to claim 1 .