WO1998029165A1

WO1998029165A1 - Decorative plate for sliding member

Info

Publication number: WO1998029165A1
Application number: PCT/JP1997/004809
Authority: WO
Inventors: Yasushi Hasegawa
Original assignee: T-One Co., Ltd.
Priority date: 1996-12-26
Filing date: 1997-12-25
Publication date: 1998-07-09
Also published as: JP3995417B2

Abstract

A decorative plate for a sliding member providing a clear design without blur, a printing having high durability, high quality design coloration, a multi-color design having a high design, feature, and highly resistant to secondary heating. The decorative plate uses means comprising a plastic containing inorganic compounds in the form of ultra-fine particles having a mean primary grain size of not greater than 1νm.

Description

Technical field of decorative board for glider

Light

TECHNICAL FIELD The present invention belongs to the technical field of a decorative board for a glider which can be printed with a dye. Background art

Since decorative boards for skis and the like tend to have a complex multicolored design and printing with pigments does not provide sufficient coloring properties, printing with dyes has come to be performed. Dye printing produces more vivid colors than pigments and enhances the design of the design.

Patent Application No. 6-185086, filed by the inventor of the present invention as a conventional decorative board for skiing, for example, as a plastic decorative board for skis Invention of "Skiing decorative board and method for producing same" There is. INDUSTRIAL APPLICABILITY The present invention makes it possible to simplify the printing process and improve the working environment of a plastic decorative board for skis having a complex and multi-colored design, and to optimize printing with dyes by a printing method such as sublimation printing. As such a plastic decorative board, a dye-dyeing plastic is preferable, which has a dye-dyeing seat, has a particularly low gas permeability coefficient, and a density (specific gravity) of 1.0 or more. Resins are preferred so that the design does not easily bleed when printing with dyes.

However, the dye is heated during printing and becomes a gas, which is dispersed and diffused in the resin. For a resin with a large gas permeability coefficient, the dye is dispersed and diffused in the resin in a random direction. If it is too large, printing will be There was a problem that the result was easy bleeding, and it was not possible to obtain a plastic decorative board having a clear design without bleeding.

In particular, resins such as polyethylene are non-polar resins and have no functional groups in their molecular structure, so they cannot have affinity for dyes and have no dyeing ability. Therefore, printing with a dye easily causes bleeding or fading. In addition, since the density is less than 1.0, a dense molecular structure is not obtained, and the gas permeability coefficient is large. Therefore, there is a problem that the dispersion and diffusion of the dye are large and clear printing cannot be performed. Also, if the penetration depth of the dye by printing is made shallow to obtain a clear image, there is also a problem that the printed design is easily scratched and scraped off when the gliding tool is used, resulting in poor durability. Was.

On the other hand, in the case of plastics having no or few functional groups in the molecular structure, the dye cannot react sufficiently and the dyeing becomes insufficient, and the dye does not develop its original color. There was also a problem that it was not possible to obtain a design color development, and it was not possible to apply a multi-color design with high design properties.

Further, even if a plastic decorative board printed with a good dye is obtained in a plastic having a low gas permeability coefficient and a density of 1.0 or more, as in the case of the decorative board described above, the use of these plastic decorative boards is difficult. There is a problem that the above-mentioned dye re-sublimates and the printing is blurred during the secondary heating during the manufacturing process such as adhesive heating and molding heating during molding of plastics. No board was obtained. Disclosure of the invention

The inventor of the present invention has solved the above problems by continuing further research and accumulating experiments, and has disclosed a decorative plate for a slide which can be printed with a dye, and a decorative plate for a slide which has been printed with high quality using a dye. I got a board. That is, a first means for solving the above-mentioned problem is a decorative plate for a slide which can be printed with a dye made of a plastic containing an inorganic compound which is an ultrafine particle having an average primary particle size of lm or less. The second means is a decorative board for gliding equipment which is made of a plastic containing an inorganic compound which is an ultrafine particle having an average primary particle diameter of 1 βm or less and is printed with a dye.The third means is an average A decorative plate for a slide which can be printed with a dye made of a plastic containing zirconium oxide, which is an ultrafine particle having a primary particle size of 1 μm or less.The fourth means is that the average primary particle size is 1 μm. This is a decorative plate for gliding equipment that can be printed with a dye made of plastic containing aluminum oxide, which is ultrafine particles having a size of less than μm. In the present specification, the size of a particle refers to the size of a particle size or a wire diameter.

The fifth means is a decorative plate for a slide which can be printed with a dye made of a plastic containing an inorganic metal compound which is fine particles of zirconium oxide. The sixth means is an inorganic plate which is fine particles of zirconium oxide. A decorative plate for a sliding device, which is made of a plastic containing a metal compound and is printed with a dye, wherein the seventh means is a printable plate made of a plastic containing an inorganic metal compound which is fine particles of aluminum oxide. Eighth means is a decorative board for a sliding implement, which is made of a plastic containing an inorganic metal compound which is fine particles of aluminum oxide, and is printed with a dye. Ninth means is an oxidizing board. A dye made of plastic containing an inorganic metal compound that is fine particles of both zirconium and aluminum oxide A decorative plate for printing that can be gliding equipment. The fine particles are a force S having a size of about 200 μπι or less, and the size of the fine particles according to the fifth to ninth means is preferably 以下 Ο μππ or less, More preferably, it is 1 O / m or less.

A tenth means is a brass containing an organometallic compound of a metal chelate. An eleventh means is a decorative board for a sliding device printed with a dye comprising a plastic containing an organometallic compound of a metal chelate. A twelfth means is a printable decorative board for a slide tool made of a dye containing a plastic containing an organometallic compound of a metal acylate, and a thirteenth means is a decorative board containing an organometallic compound of a metal acylate. A fourteenth means is a decorative plate for a slide which can be printed with a dye composed of a plastic containing an organometallic compound of a metal alkoxylate. The fifteenth means is to use a sliding tool made of a plastic containing an organometallic compound of a metal alkoxylate and printed with a dye. A sixteenth means is for a printable skid with a dye consisting of a plastic containing an organometallic compound selected from a plurality of metal chelates, metal acylates and metal alkoxylates. Decorative board C

Since the plastic decorative board according to the present invention contains a compound in a plastic to be printed with a dye in advance, the plastic has a large number of functionalities irrespective of its dyeing property and regardless of the gas permeability coefficient. The presence of the group has the same effect. That is, since the contained compound acts as an affinity group for the dye that penetrates during printing, the dye can be sufficiently dyed on the surface and inside of the plastic. Therefore, it is a dyed image with clearer and higher color development without bleeding, and a highly durable plastic decorative board without bleeding, discoloration, and fading can be obtained even after the heating or the passage of time. .

Since the surface area of the particles having the same weight increases as the particle size decreases, the surface energy of the solid particles in the inorganic compound according to the present invention naturally increases, and as a result, the solid binding force increases. The amount of energy increases, and the surface activity of the solid becomes extremely large. In particular, ultra-fine particles of 1 μm or less, which are particularly small among inorganic compounds, have remarkable characteristics in their reaction activity, so that they act as an affinity group for dyes. In addition, a highly stable dyed image can be obtained.

Among inorganic metal compounds, zirconium oxide and aluminum oxide have a very high affinity for dyes, and not only ultrafine particles of the compound but also particles of fine particle size, Since it can sufficiently act as an affinity group, a high-quality dyed image can be obtained in the same manner.

Similarly, among metal-organic compounds, metal chelates, metal acrylates, and metal alkoxylates, which have a particularly high active reaction and good affinity for dyes, can be contained in plastics. It acts as an affinity group for the dye that penetrates, and a decorative board having a highly durable dyed image can be obtained.

The present inventor has focused on the physical properties of these inorganic and organic compounds, and as a result of repeated studies, it has been found that the decorative board made of plastic containing these compounds has a remarkable difference compared to the conventional one due to printing with dyes. They found that a high-quality, highly durable printed image could be obtained.

Hereinafter, based on Table 1, Examples 1 to 16 and Comparative Examples 1 to 8 in which the present invention is applied to a ski decorative board will be described in detail.

1 Species penetration of compound to be compounded Evaluation of degree of bleeding τ 曰

H. Plastic substance name ¾i diameter β m Addition amount% mm After printing After heating accelerated Comparative Example 1 UHMWPE ― ― ― 0.9 XX Comparative Example 2 HDPE ― 1 0.8 Δ X Comparative Example 3 PP ― ― ― 0.9 Δ X Comparative Example 4 UHMWPE ― ― 0.3 ◎ X Comparative Example 5 HDPE ― 1 0.3 ◎ X Example 1 0. 0 0 7 4 0.5 ◎ Example 2 UHMWPE S i 0.8 1 5 0.8 〇 o Comparative Example 6 4 .0 10.5 .8 XX Example 3 0 .0 2 4 0 .3 ◎ © Example 4 UHMWPE Ti O2 0.3 .5 10.5 .8 〇比較 Comparative Example 7 2.0 1 5 1 .0 XX Example 5 0 .0 1 1 0 0 .3 ◎ ◎

UHMWPE j 11

Comparative Example 8 2.5 0 10.9 XX Example 6 0.1 1 0 0 .5 ◎ © Example 7 UHMWPE ZrO2 1.0 .1 0 0 .8 ◎ ◎ Example 8 2.0.15 0.8 © Example 9 0. 0 1 3 0.5 .5. Example 1 0 0 .0 1 3 1 0.5 .5 〇〇

IIHMWPP

Example 1 1 0 .0 1 3 3 0 .3 ◎ ◎

A 1

Example 1 2 2.5.4 4 0.3 ◎ ◎ Example 1 3 HDPE 0.0 1 3 5 0.5 ◎ ◎ Example 1 4 PP 0.0 1 3 5 0.5 ◎ ◎ Example 1 5 UHMWPE Chelate liquid 1.2.0.5 ◎ ◎ Example 16 UHMWPE acylate liquid 2 0.5 ◎ 〇 Degree of bleeding ◎: No bleeding △: Some bleeding

Evaluation criteria 〇: Almost no bleeding X: Remarkable bleeding In Table 1, Comparative Examples 1 to 5 are examples of conventional ski decorative boards not containing any compound according to the present invention. Comparative Examples 1 and 4 are ultra-high molecular weight polyethylene resins (UHMWP E), which are 40000 molecular weight polyethylene according to Hosterlen GUR412 manufactured by Hext Co., and have a high density (specific gravity). ) Is 0.93 plastic. Comparative Examples 2 and 5 are high-density polyethylene resins (HD PE), which are polyethylene having a molecular weight of 150,000 by Hiisex 500 H manufactured by Mitsui Petrochemical Corporation and have a density of 0.96. Comparative Example 3 is a polypropylene resin (PP), which is made of polypropylene manufactured by Mitsui Ishi Oil & Chemicals, Hypol J700, and has a density of 0.91.

The method of forming a sheet as a ski decorative board using these resins will be described. In general, polyethylene resins having a molecular weight of about 500,000 or more are first molded into blocks or disks by sintered (sintering) molding. Shave or slice the block to form a sheet. In addition, general thermoplastics such as polyethylene or polypropylene resin having a molecular weight of 500,000 or less are usually sheet-formed by extrusion sheet molding. Each of the plastic sheets shown in Comparative Examples 1 to 5 is a sheet having a thickness of 1.0 X 100 X 2, ◦ 00 mm obtained by the sheet molding described above. It is used as a decorative board.

The sheet is printed with a dye as a comparative example of the present invention. The method of printing with a dye uses sublimation transfer paper that has been printed with an ink containing a dye in advance on transfer paper. Specifically, using the sublimation transfer paper by Dainippon Printex Co., Ltd. No. 13 34 Independence Check 3.55, the printing surface of the sublimation transfer paper and the printing surface of the plastic sheet are connected. Laminated and sandwiched between heated upper and lower press plates. At this time, a 4 mm thick heat-resistant felt is placed between the plastic sheet and the press plate. In addition, the sublimation transfer paper side was brought into direct contact with a press plate and heated under pressure to perform sublimation printing using dye.

The heating temperature and time in the above printing process were 160 ° C and 300 seconds for ultrahigh molecular weight polyethylene (UHMWP E) and polypropylene (PP) in Comparative Examples 1 and 3, respectively. For the high-density polyethylene (HDPE) of Comparative Example 2, the test was performed at 130 ° C. for 300 seconds. Here, the reason why the calorie heat temperature is different is that the temperature is set in consideration of thermal deformation due to each resin. In Comparative Examples 4 and 5, in order to see differences due to different heating conditions from Comparative Examples 1 and 2, both examples were performed at 130 ° C. and 150 seconds. Furthermore, pressure is intended conditions 1 3 0 ° C, 1 6 is ^{0 g / cm 2, 1 6} 0 ° intended conditions of C, 1 2 g in consideration of the thermal deformation of the sheet / cm ² at each pressure heating. After that, remove it from the press, immediately peel off the sublimation transfer paper, and hold only the plastic sheet with a cooling plate to cool and solidify. As a result, a decorative board having an image formed by transfer of the dye into the plastic member was obtained, and ski decorative boards of Comparative Examples 1 to 5 which were printed with the dye were obtained.

Next, using a magnifying glass, the penetration depth of the permeated colored image was measured, and then the finished state of printing was evaluated. Regarding the evaluation of the print quality, the “two-sidedness” of the printed part was visually observed, and a four-step evaluation was performed. The above results are shown in Table 1. In Comparative Examples 1 to 3, the print penetration depth was deep and preferred, but the degree of bleeding after printing was large and the color development was insufficient, which was not satisfactory. In Comparative Examples 4 and 5, although the printing penetration depth was formed to be shallow, and the color developability was insufficient, the degree of bleeding after printing was satisfactory.

Next, a heating acceleration test was performed to evaluate the fixing stability of printing. This is due to the fact that the dyeability inside the plastic changes due to reheating after printing. This is because it can be determined by conversion. Specifically, the printed sheet is placed in a constant temperature bath set at 80 ° C for 24 hours, then taken out, sandwiched by a cooling plate, and cooled to room temperature. The sheet was visually observed for changes in the degree of bleeding in the same manner as described above, and evaluated on a four-point scale. As shown in Table 1, the results of Comparative Examples 1 to 5 all show remarkable bleeding, and the color development is unclear and blurred, and printing with no commercial value as a ski decorative board is performed. It has changed to what it presents. It is clear that these dyes have no fixing property for printing, and will reduce the commercial value of skis due to aging during heating during ski manufacturing process, or in stock or during use. . BEST MODE FOR CARRYING OUT THE INVENTION

Next, examples of the present invention will be described. The plastic types, brands, sheet molding methods, sheet standard dimensions, and dye printing methods relating to Examples 1 to 16 and Comparative Examples 6 to 8 described below. The conditions, such as the method and method for measuring the depth of print penetration, the method for evaluating the degree of print bleeding, and the method for promoting heating, were all exactly the same as those in Comparative Examples 1 to 3 described above.

Here, Examples 1 to 16 and Comparative Examples 6 to 8 are different from Comparative Examples 1 to 3 only in that a specific compound is added to and blended with the raw material resin. The specific means of adding and compounding the specified compound is as follows. For ultra-high molecular weight polyethylene (UH MW PE), measure according to the addition amount shown in Table 1 and then use a high-speed fluid mixer (Henschel mixer). The mixture was stirred for 30 minutes at and mixed. HDPE and PP were sufficiently stirred and mixed in a mixing and stirring tumbler for 30 minutes or more. After the appropriate stirring and mixing, the decorative sheet of the present invention was obtained by sheet forming exactly the same as shown in Comparative Examples 1 to 3 described above. Examples 1 to 5 show examples of decorative panels for skis containing ultra-high molecular weight polyethylene resin containing an inorganic compound, which is an ultrafine particle having an average primary particle diameter of 1 m or less, according to the present invention. Further, Comparative Examples 6 to 8 show examples in which the particle diameter of the contained inorganic compound exceeds 1 μm.

As shown in Table 1, Examples 1 and 2 are ultrafine particles of silicon dioxide (SiO ₂ ) as inorganic compounds, and have a particle diameter of 0.007 μm and 0.8 μm, respectively. Was added to ultra high molecular weight polyethylene (UHMWPE), and the added amounts were 4% by weight and 15% by weight, respectively. In Examples 3 and 4, the inorganic metal compound was titanium oxide (TiO ₂ ), and the ultrafine particles having a particle size of 1 μm or less ( _{0.02 μm} and _0.35 m) were used. This is an example of adding and blending. Example 5 is an example in which ultrafine particles (0.01 μm) of zinc oxide (ZnO) were similarly added, and the particle size and the amount of addition were as shown in Table 1. The moldability was as good as the comparative example described above.

As a result of printing with the dye on the decorative boards of these examples, in any of the examples, the penetration depth of the print was sufficient, and there was no (almost) no blur after printing, and the sharpness was low. High quality, high quality prints with excellent color development were obtained. When the decorative plate was subjected to the same heating acceleration test as described above, there was no movement of the dye image (two blemishes), no change in color development, and a high fixing stability of the dye. It turned out to be a board.

In the same manner, in Comparative Examples 6 to 8 in which an inorganic compound having a particle size of more than 1 μm was added, as in Comparative Example 1, all the bleeding after printing by dye printing was observed. The appearance was remarkable, the coloring was poor, and a high quality decorative panel was not obtained.

The smaller the particle size of the inorganic compound to be added and the smaller the reactive activity of the solid surface becomes, the more the reactive activity of the solid surface is increased. It is considered that the dyeing effect was improved with respect to the penetration of the dye, and it was possible to obtain durable printing with no bleeding and high permeation fixation. In addition, when the same weight is added, the smaller the particle size, the larger the total surface area of the solid particles and the higher the reaction activity, so that the effect can be enhanced with ultrafine particles having a small particle size. it is conceivable that. From Examples 1 to 5, it was confirmed that good results were obtained when the average primary particle diameter of the solid particles of the inorganic compound to be contained was ultrafine particles of 1 βm or less.

However, considering the effects of unexpected deterioration in physical properties, it may be necessary to reduce the amount of inorganic compound added depending on the plastic to be added and mixed. For the above-mentioned reason, the smaller the particle size, the smaller the amount of the inorganic compound added. For example, ultrafine particles of 0.1 lm or less can reduce the addition amount sufficiently, so that it is more preferable. Ma Still more preferably, ultrafine particles having a particle size of not more than 0.02 μπα are preferable. The amount of these ultrafine particles to be added and blended is 30% by weight, as long as it does not affect the type of plastic to be blended, the required physical properties depending on the application site, and the moldability as a decorative plate. /. The following formulation is preferred. In order to further reduce the physical properties of the plastic, the content is preferably 15% by weight or less. The lower limit of the addition amount is preferably 0.5% by weight or more in consideration of the dyeing properties of the dye. However, as described above, the addition amount can be reduced by selecting the particle size of the ultrafine particles to be small, so that the addition amount can be arbitrarily adjusted. Next, examples of the inorganic compound capable of forming ultrafine particles to be added and blended include the following substances. Is an oxide, A 1 ₂ 〇 _{3, C e OC o O 3} , C r 2 O 3, F e 2 O 3, F e 3 O 4, H f O 2, M g O, M n O , M o O, n i O , n b O, n b O, P b O, R u O 2, S b O, S i OS n O 2, T h O, T i 〇 _2, UO, VO ₅ , WO, YO, Y b O, Z n O, and the like Z R_〇 _2. Is a composite oxide, 3 A 1 ₂ 〇 ₃ - 2 S i O, C O_〇 '. 8 Z n O, C O_〇 _{n A 1 O, L i 2} 0' 2 C o O 'P 2 _{0 5, 2 MO · 2 A} 1 2 O 3 • 5 S i O, 3 M g O · 4 S i O 2 · H 2 O, B a S n O 3, B a

T i O, B a Z r O, C a Z r O 3, C a S n O 3, C o F e 2 0 M n S n O, M n F e O 4, N i F e O, P b G e O, P b S n O, P b WO, S r A s O, S r G e O 3, S r S n O 3, ST e O, S r T i O, S n O - S _{_{b 2 O 3, Z n G}} e O, and the like _{Z n F e 2 O, K} 2 〇 '6 T i 0 _2. A 1 N as nitride

, BN, and the like C r N, M n N, N b N, T a N, T i N, VN, Z r N, Z r 3 N 4, S i 3 N 4. Examples of the carbide include BC, MoC, NbC, SiC, TaC, ΤhC, ΤiC, UC, WC, ZrC, and the like. It is a boride other forms bets Ru _{material, T i B 2, Z r} B, M n F, B a SO, and the like C a CO _3. Any of these substances can be preferably applied.

By the way, among the above substances, in addition to the particulate form, there are also whisker-shaped (linear) shaped substances. In this case, if the whiskers have an average primary wire diameter of Ιμππ or less, It has the same effect as the above ultrafine particles. Further, among the above-mentioned inorganic compounds, an inorganic metal compound is particularly preferred because of its high reactivity. More preferably, an inorganic metal oxide is good.

Here, the primary particle diameter and the primary wire diameter of the solid particles as referred to in the present specification mean the particle diameter of the produced particles immediately after ultrafine particles or fine particles are produced. The size range of the ultrafine particles is approximately 1 / m to 0.01 μm (1 nm), and the size range of the fine particles is 200 μππι or less. The range includes ultrafine particles.

In Examples 6 to 8, zirconium oxide was used as the inorganic metal compound to be added and blended. © beam (Z R_〇 ₂₎ is an example blended with, the Examples 6 and 7, which particle size is blended with ultra-fine particles of 0.1 and 1. 0 mu m, Example 1 of the aforementioned Good results similar to 5. However, in Example 8, unlike the results of Comparative Examples 6 to 8 described above, printing with a sufficiently high quality dye was possible even with fine particles having a particle size of more than 1 μm. Therefore, a plastic containing fine particles of zirconium oxide can be sufficiently applied as a ski decorative plate that can be printed with a dye.

Here, the zirconium oxide particles to be added to the plastic are not particularly limited as long as they have a fine particle size or less, and can be used as fine particles having a particle size of Ι μm or less, but preferably 10 μm or less. Fine particles of μm or less are good. Further, the amount of the additive is preferably 30% by weight or less, as in the above-described examples. If the amount is 15% by weight or less, the physical properties of the plastic are not significantly affected. The lower limit is preferably 0.5% by weight.

Example 9-1 4, as the inorganic metal compound to be added is an example of those using an oxidizing Aruminiu beam (A 1 ₂ 〇 _3). In Examples 9 to 11, ultra-fine particles of 1 m or less (0.013 / xm) similar to the above-described examples were added to ultra-high molecular weight polyethylene (UHMWP E) and blended. And had the same effect. Further, Example 13 is a compound added to high-density polyethylene (HD PE), and Example 14 is a compound added to polypropylene (PP). It was confirmed that other plastics also had a similar effect.

Furthermore, as shown in Example 12, it was confirmed that the aluminum oxide particles were a substance having a sufficient effect as described above even if the particles had a particle size exceeding 1 / m. Was. Therefore, as in Example 8 described above, the plastic containing the fine particles of aluminum oxide was also dye-based. It can be applied sufficiently as a printable ski decorative board. Regarding the particle size and the amount of addition, the same can be said for Example 8 described above. Aluminum oxide has α-type, -type, and γ-type, depending on its crystal structure. In particular, an aluminum oxide compound having a _γ- type crystal structure has high activity and can be preferably used.

The ultrafine particles and fine particles made of the inorganic compounds described above have a very small particle size and a very large number per unit weight as compared with ordinary particles. Performance is improved. Conventionally, decorative boards used for skis are used on the upper and lower surfaces of the core part, and paint is used to improve concealment on the back side of the decorative board separately from decorative printing so that the core part cannot be seen through. A backcoat had to be applied. However, with the ski decorative board as in the present embodiment, sufficient concealment can be imparted, so that conventional grasshopper coating work can be omitted.

Examples 15 and 16 differ from the examples described above in that an organometallic compound was added. In Example 15, as an organometallic compound, a metal chelate was added to ultrahigh molecular weight polyethylene at a ratio of 1.2% by weight, and the effect was the same as that of the aforementioned Example. Was. The metal chelate added to Example 15 is specifically aluminum aluminodisopropoxide monoethyl acetate, and is in the form of a liquid compound.However, the metal chelate can be stirred and mixed with plastic in the same manner as described above. The sheet was formed in the same manner as the above-mentioned method, and the forming was good.

Example 16 is an example in which a metal acylate was also added and blended at a ratio of 2% by weight to UHWP as an organometallic compound, and the same effect was observed as in the above-described example. . The metal used in Example 16 The sylate was prepared by adding and blending an alkoxyalkoxyaluminum dimethoxypropylate.The sylate had a liquid form in the same manner, but was formed into a sheet in the same good manner as in Example 15. .

Here, as the organometallic compound to be added and blended, a metal alkoxylate other than the metal chelates and metal acrylates shown in Examples 15 and 16 can be applied, and one or more of these can be used. By containing the resin in a plastic, a decorative plate printable with a dye can be obtained. As the metal type of the organometallic compound, zirconium, aluminum, titanium or the like is preferable. Further, as the substituent type, acetyl aceton and its derivatives are used for the chelate, and the acyl group is used for the acylate. And its derivatives, and the preferred alcoholates are aliphatic alcohols and aromatic alcohols.

The following are more specific compounds. Examples of zirconium compounds include zirconium butoxyacetyl acetate, tetra n-butoxydinorecone, dinoreconium n-butyrate, dinoreconium n-propylate, zirconium tetracetyl acetate, and the like. . Examples of the aluminum compound include aluminum diisopropoxide monoethynoleate acetate, aluminum tris (ethylinoacetate acetate), aluminum tris (acetylacetonate), and aluminum bisethyl acetate monoacetate. There are cetyl acetate, acetate alkoxyaluminum disopropylate and the like. Examples of the titanium compound include diisopropoxybis (acetylacetona) titanium, isopeptoxy (2-ethyl-1,3-hexanediolato) titanium, di (2-ethylhexoxy) bis (2-ethylethyl-1,2) 3—Hexanediolato titanium, G n—butoxybis (triethanolaminate) titanium, tetracetylacetonate titanium, hydroxybis (ratatato) titanium There is. The above organometallic compounds are in the form of a liquid or a powder, and any of them can be applied in the same manner as described above. Further, the amount of addition and mixing is preferably in the range of 0.5 to 20% by weight, more preferably 0.5 to 10% by weight.

Next, the plastic used in the present invention is not limited to those shown in the present embodiment, but can be applied to a wide range of plastics, and is not particularly specified. However, it is particularly effective for plastics with low dye-dyeability, which are conventionally plastics that cannot be printed with dyes or are insufficient plastics. Plastics with low dyeing properties include polyethylene, polypropylene, E.V.A., E.E.A., E.A.Α, polyolefin-based plastics such as ionomers, polymethinolepentene, and elastomers. One resin is an elastomeric elastomer, a polyamide elastomer, a polyester elastomer, a polyurethane elastomer, a styrene elastomer, a chloride-based elastomer, a syndiotactic 1. And 2, polybutadiene, etc., and the usefulness of the present invention is particularly remarkable, and a mixture of the above resins may be used.

On the other hand, the present invention can be applied to plastics having a high dye-dyeing property, such as polymethacryl-based, polycarbonate-based, polyamide-based, and polyester-based plastics. The compounds added and blended according to the present invention have different dyes that penetrate at the time of printing and substances that form bonds, depending on the types thereof, and thus the color development upon dyeing is necessarily different. Therefore, by selecting an appropriate compound, not only the dyeing property of the dye is improved, but also there is an effect that the degree of color development and the color tone of the penetrating dye can be changed or adjusted. Further, the method of manufacturing the decorative board manufactured in the practice of the present invention using the plastic is not limited to the method of the above-described embodiment, and any conventionally known manufacturing method can be applied. Regarding the printing method using the dye relating to the decorative plate of the present invention, in addition to the method of printing using the same sublimation transfer paper as that used in the ordinary example, silk printing and offset using the ink containing the dye After printing directly on the printing material by a general printing method such as printing, the printing part is heated (or not heated), and the dye contained in the ink is transferred to the plastic to complete printing. The decorative plate of the present invention can be applied to all printing methods for obtaining an image that penetrates plastic using a dye. In addition, various conditions and methods such as heating and pressurization during printing in the above-described examples can perform printing with excellent quality even if they are other than those described above. These conditions and methods can be arbitrarily set. Is to be determined.

As for the dyes to be used, various dyes such as disperse dyes selected from azo dyes, pyrazolipid pyridine dyes, anthraquinone dyes, and phthalocyanine dyes, and other basic dyes, acid dyes, and oil-soluble dyes can be used. Use as appropriate.

When the inorganic compound, the inorganic metal compound, and the organometallic compound in the present invention are contained in a plastic, the selection and combination of each compound may be used alone, plurally used, or used in combination. They are free, and the same effects as those of the above-described embodiment can be expected.

In each of the decorative plates according to the above embodiments, a permeation image with a dye having a sufficient depth can be obtained for plastics, and the design can be easily scraped off from external impact scratches or wear due to use. Not a thing. Also, despite the penetration image being of sufficient depth, the printed design was not clear and blurred. Similarly, the dye image had a sufficient coloring property and a high design property.

In addition, the dye image does not lose its color development upon subsequent heating, and It maintains the same sharpness as before, without any loss, and its dyeing stability is remarkable, and it has sufficient durability even during the ski manufacturing process or over time It can be concluded. Industrial applicability

As described above, according to the present invention, when printing with a dye, the contained compound acts extremely effectively as an affinity group for the dye, so that the dyeing property can be significantly improved. Therefore, it is easy to obtain a clear and high-colored dye-free image without bleeding, and there is almost no bleeding, discoloration, and fading even after secondary heating or lapse of time. It is possible to manufacture decorative panels for use.

Claims

The scope of the claims

1. A printable decorative board for a sliding implement, which is made of a plastic containing an inorganic compound which is an ultrafine particle having an average primary particle size of 1 μm or less.

2. A decorative board made of plastic containing an inorganic compound, which is an ultrafine particle having an average primary particle size of 1 μm or less, and printed with dyes.

3. A printable decorative board for a sliding implement, which is made of a plastic containing an inorganic metal compound which is fine particles of one or both of zirconium oxide and aluminum oxide.

4. A decorative board for gliding equipment made of a plastic containing an inorganic metal compound that is fine particles of one or both of zirconium oxide and aluminum oxide, and printed with a dye.

5. Dye-printable decorative board for gliders, comprising a plastic containing an organic metal compound selected from one or more of metal chelates, metal acrylates, and metal alkoxylates. .

6. A decorative board for gliding equipment, which is made of a plastic containing an organic metal compound selected from one or more of metal chelates, metal acrylates, and metal alkoxylates, and is printed with a dye.

Claims of amendment

[June 4, 1998 (04.06.98) Accepted by the International Bureau: Claims at the time of filing of the application were amended; other claims were unchanged. (1 page)]

1. (After correction) Printable decorative plate for gliding tools made of a dye, characterized by being made of a plastic containing an inorganic compound that is an ultrafine particle having an average primary particle size of 0.1 ^ m or less. .

2. (After correction) A decorative board for gliding equipment made of a plastic containing an inorganic compound that is an ultrafine particle having an average primary particle size of 0.1 ^ m or less and printed with dye.

3. (After amendment) Dye-printable cosmetics for gliders, characterized by being made of a plastic containing an inorganic metal compound which is non-sintered fine particles of one or both of zirconium oxide and aluminum oxide. Board.

4. (After correction) A decorative board for gliding equipment, which is made of a plastic containing one or both of zirconium oxide and aluminum oxide or an inorganic metal compound that is a non-sintered fine particle, and printed with a dye.

5. A printable decorative board for a sliding implement, which is made of a plastic containing an organic metal compound selected from one or more of a metal chelate, a metal acylate, and a metal alkoxylate.

-20-Amended paper (Article 19 of the Convention) Statement under Article 19 of the Convention

1.The correction that the average primary particle size is in the range of 0.1 μμπι ^ below in claims 1 and 2 is based on the fact that the addition of the ultrafine particles of the present invention allows the dye to be clearly printed on the resin. The purpose is completely different from that of JP 4-99982, JP 3-73 1 77, etc., and it is clear that the particle size of the present invention is finer than those assumed in these references. You

2. The correction of “non-sintered fine particles” in claims 3 and 4 is based on the fact that the addition of the ultrafine particles of the present invention is for the purpose of clearly printing the dye on the resin, and JP 4-99982, Since it is not intended to dissolve snow using a far-infrared ray radiating substance as in JP 6-49090, etc., the zirconium oxide and aluminum oxide of the present invention are sintered bodies (ceramics) having far-infrared ray radiating ability. Clarify that