JP4300973B2 - Decorative sheet manufacturing method and decorative plate - Google Patents

Description

  The present invention relates to a method for producing a decorative sheet having a printed pattern layer, and a decorative board obtained by bonding a decorative sheet produced according to the production method onto a woody, inorganic or metal base material using an adhesive. It is about.

  Conventionally, the decorative sheet used on the surface of the decorative board, which has been used for interior doors, closets, kitchen doors, inner wall materials, home appliance cover materials, etc., has good printability and has a degree of hardness due to the addition of a plasticizer. Adjustable and selectable hardness according to the application, good embossability, strong adhesive strength between layers when laminating, good machinability, cutting processing such as router processing on decorative board using decorative sheet Polyvinyl chloride decorative sheets, which are printed with a wood grain pattern or abstract pattern on a polyvinyl chloride sheet, are widely used. I came.

  However, the above-mentioned polyvinyl chloride-based decorative sheet may generate toxic gas when burned. Due to the human influence at the time of incineration of waste and concerns about environmental conservation, the polyvinyl chloride-based decorative sheet Instead, users are strongly demanded to develop a decorative sheet using a material that does not generate toxic gas when burned.

  Therefore, in recent years, a printed pattern layer is applied mainly on a non-polyvinyl chloride resin such as polyolefin, polyethylene terephthalate, polyester, polyvinyl alcohol, acrylic, or a sheet of paper using a printing technique, In order to protect the printed pattern layer, a non-polyvinyl chloride type decorative sheet, which is also made by laminating a non-polyvinyl chloride type transparent sheet on the printed pattern layer side, is an alternative to the polyvinyl chloride type decorative sheet. It is starting to be used. Of these, in particular, there are many multilayer decorative sheets made of polypropylene as the main material from the viewpoint of having the required quality required for decorative sheets, that is, heat resistance, scratch resistance, appropriate flexibility, etc., and also in view of economy. It is used.

  However, in the multi-layer decorative sheet by the laminate method using polypropylene as a main material, it is difficult to say that polypropylene itself is a material having good affinity with other materials, especially in a long-term weather test and a test after a heat test, There arises a problem that the adhesion strength of the laminated portion is lowered. In particular, in order to improve the adhesion strength of the laminated part, a method of performing ozone treatment at the time of melt extrusion lamination of polypropylene is known (see Patent Documents 1 and 2). Even if the effect of improvement is not sufficiently obtained, or even if the peel strength immediately after production is significantly improved by adjusting the processing conditions than in the case of no treatment, if a long-term weather resistance test or heat resistance test is performed, The problem is that the peel strength is lowered.

The following is prior art document information related to the present invention.
Japanese Patent No. 3058023 Japanese Patent No. 3089957

  The present invention has been made in view of the drawbacks of the related art, and in a multilayer decorative sheet using polypropylene as a main material, the deterioration of the peel strength after a long-term weather resistance test and heat resistance test of the multilayer decorative sheet is suppressed. A decorative sheet manufacturing method capable of improving durability performance, and a decorative sheet obtained by bonding a decorative sheet manufactured according to the manufacturing method on a woody, inorganic or metal base material using an adhesive It is a problem to obtain.

The present invention according to claim 1 is a non-polyvinyl chloride material in which a transparent polypropylene resin is melt-extruded and subjected to ozone treatment on one side, and then the surface subjected to ozone treatment is provided with a printed pattern layer in advance. In the manufacturing method of a decorative sheet in which a transparent polypropylene resin layer is formed by laminating in a molten state toward the printed pattern layer surface of the base material sheet, the ozone treatment amount is the ozone concentration generated from the ozone generator is D, When the ozone flow rate is F, the width of the sheet for ozone treatment is W, the line speed of the sheet is V, and the ozone concentration attenuation rate is α,
Ozone treatment amount = α × D × F / (W × V)
Satisfies the above formula, the ozone treatment amount is decorative sheet manufacturing method of which is characterized in that in the range of ^{1 × 10 -6 g / m 2} ~10 × 10 -6 g / m 2.

  The present invention according to claim 2 is characterized in that the decorative sheet produced according to the production method according to claim 1 is bonded to a woody, inorganic or metal base material using an adhesive. It is a decorative board.

  According to the production method of the present invention, by optimizing the ozone treatment amount, the normal peel strength is high, and even after a long-term weather resistance test or heat resistance test, the treatment is performed at a conventional general treatment amount. A decorative sheet excellent in durability, including weather resistance and heat resistance, that can maintain a higher peel strength than that in the case of the above can be obtained.

  Furthermore, in this invention, since the polyvinyl chloride resin is not used at all, it has the advantage that the decorative sheet which does not worry about an environmental problem can be obtained.

  The decorative sheet manufacturing method of the present invention and the structure of the decorative sheet manufactured by the manufacturing method of the present invention will be described below with reference to the drawings, but the present invention is of course not limited thereto.

  The manufacturing method of the decorative sheet in the present invention is performed by a laminating process as shown in FIG. A transparent polypropylene resin 2 melted by a screw is laminated on the surface of a base material sheet 1 made of a non-polyvinyl chloride material having a printed pattern layer applied by a known printing method by an extrusion laminating method using a T-die 3. To do. At this time, for the purpose of improving the design of the decorative sheet by applying an uneven embossed pattern on the surface of the decorative sheet, an embossed pattern is applied to the cooling roll 4 in advance and embossing may be performed simultaneously with extrusion lamination. Is possible. The transparent polypropylene resin 2 thus laminated on the base sheet 1 in a molten state is cooled and solidified by the cooling roll 4, and further peeled from the cooling roll 4 by the peeling roll 5, whereby the transparent polypropylene resin layer is formed on the base sheet 1. A decorative sheet having a multilayer structure in which 7 is laminated can be obtained.

  Here, immediately before laminating, the molten transparent polypropylene resin is melted by blowing ozone gas from the ozone blowing port 6 onto the laminated portion of the transparent polypropylene resin 2 extruded from the T-die 3 in the molten state and the base sheet 1. It is a well-known technique that the degree of oxidation of the surface of 2 is increased and activated, and an effect of improving the adhesion after lamination is obtained (see Patent Documents 1 and 2 above). However, if excessive ozone treatment is performed, the surface of the transparent polypropylene resin 2 melted by ozone is excessively oxidized, and the resin deteriorates in the surface layer. As a result, peeling may occur in the transparent polypropylene resin layer 7 having a deteriorated lamination interface at the time of measuring the peel strength after manufacturing the decorative sheet, and a desired strength may not be obtained. Moreover, even if the desired strength is obtained, the degradation of the surface layer of the ozone-treated resin further proceeds due to the influence of ultraviolet rays, heat, etc. in the actual usage environment of the subsequent decorative sheet, so that the peel strength is reduced. In some cases, floating or peeling between laminate layers may occur relatively early.

  Even with the same ozone treatment amount, the degree of surface layer deterioration varies depending on the type of resin to be extruded and laminated. Polypropylene resin, which is widely used as a non-polyvinyl chloride resin used for decorative sheets, is made by ozone treatment compared to other resins such as polyethylene and acrylic that are relatively often used as decorative sheet materials. There is a tendency to cause deterioration of the surface layer. Therefore, it is necessary to appropriately determine the optimum ozonation conditions according to the material used for extrusion lamination.

  Ozone treatment is performed by spraying ozone generated from an ozone generator, but ozone itself is very unstable under normal circumstances, and from the generator through piping and ozone spraying port 6 to the laminate surface. In the meantime, ozone concentration decays. The degree of attenuation is affected by the length of the pipe in addition to the environmental conditions, so when performing numerical control of the ozone concentration, the ozone concentration in the vicinity of the ozone treatment unit should be measured in real time or impossible. For example, it is possible to measure the ozone concentration in a place as close as possible to the ozone treatment unit while changing the output concentration of the ozone generator in advance, and to grasp the attenuation rate of the ozone concentration obtained from the measurement data in advance. desirable.

  In the quantification of the ozone treatment amount, the ozone concentration generated from the ozone generator is D, the ozone flow rate is F, the width of the sheet for ozone treatment is W, the line speed of the sheet is V, the ozone concentration attenuation rate is α, In this case, a value calculated by α × D × F / (W × V) may be managed as the ozone treatment amount. If it is possible to measure the ozone concentration in the vicinity of the ozone treatment unit, it is better to define and manage the ozone treatment amount by D '× F / (W × V), where the ozone concentration is D ′. . When changing the width and line speed of the sheet for ozone treatment, a constant ozone treatment state can be maintained by adjusting the ozone treatment amount by adjusting the ozone concentration and the ozone flow rate.

  Various additives are added to the transparent polypropylene resin 2 to be subjected to ozone treatment in order to improve physical properties. In particular, for use in decorative sheets, in order to improve durability, particularly weather resistance, addition of an ultraviolet absorber, a light stabilizer and the like to the transparent polypropylene resin layer 5 is an essential condition. It becomes possible to delay the progress of the deterioration of the ozone-treated resin surface layer due to ultraviolet rays in the use environment.

  The added ultraviolet absorber is not particularly limited in its components and addition amount as long as it has a desired ultraviolet absorption effect and does not significantly affect the properties other than the weather resistance of the decorative sheet. For example, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -benzotriazole, etc. Benzotriazole-based ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, benzophenes such as 2,2′-dihydroxy-4-methoxybenzophenone Non-based ultraviolet absorbers, triazine-based ultraviolet absorbers such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, cerium oxide, oxidation One or two or more inorganic ultraviolet absorbers such as titanium can be added in any combination.

  The light stabilizer is not particularly limited as long as it has a desired ultraviolet absorption effect and does not significantly affect the properties other than the weather resistance of the decorative sheet. For example, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4- Piperidinyl) imino}], N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidinyl) amino ] -6-chloro-1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) ) -2-n-butyl Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ronate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate Hindered amine light stabilizers such as rate, benzoate light stabilizers such as 2,4-di-t-butylphenyl-3,5-di-T-butyl-4-hydroxybenzoate, bis- (2,2,6 1, 6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like, and one or more of them can be used in any combination.

  In addition, a heat stabilizer, a flame retardant, an anti-blocking agent, and the like are added as necessary to improve durability and impart functionality of the decorative sheet. Thermal stabilizers are pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy -3,5-di-t-butylanilino) -1,3,5-triazine, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl- 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid Hindered phenol antioxidants such as 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) ) And the like, and phosphorous antioxidants typified by tris (2,4-di-t-butylphenyl) phosphite can be used alone or in combination of two or more. .

  Examples of the flame retardant include inorganic compounds such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, and magnesium carbonate, and phosphate ester flame retardants, but there are no particular limitations on the components. However, since it is a non-polyvinyl chloride decorative sheet considering the environment, it is necessary to refrain from using halogen-based flame retardants.

  As the anti-blocking agent, an inorganic anti-blocking agent such as aluminum silicate, silicon oxide, hydrotalcite and calcium carbonate, an organic anti-blocking agent such as fatty acid amide, and the like are optionally added.

  Furthermore, in addition to further improving the laminate interlayer strength after the weather resistance test of the decorative sheet, in addition to improving the design properties, protecting the printed pattern layer, improving wear resistance, chemical resistance, scratch resistance, etc. For the purpose of imparting a glossy surface, the surface protective layer is generally laminated on the outermost layer portion of the decorative sheet on the transparent polypropylene resin layer 7 side. The material of the surface protective layer is not particularly defined as long as it has sufficient adhesion to the transparent polypropylene resin layer 7 in addition to the above physical properties, but it can be added by adding an ultraviolet absorber or a light stabilizer. A polyurethane-based resin having a weather resistance formulation is particularly preferably used. In addition, the weather resistance performance is almost proportional to the thickness of the surface protective layer, and the thicker the surface protective layer, the higher the weather resistance performance including peel strength, but considering the required performance as a decorative sheet, design properties, economy, etc. However, it is desirable to select appropriately within the thickness range of 3 to 30 μm.

In accordance with the production method as described above, the present inventors desirably applied a transparent polypropylene resin 2 that has been subjected to weathering prescription by appropriately adding an ultraviolet absorber, a light stabilizer, or the like to a non-polychlorinated resin having a printed pattern layer. More preferably, the amount of ozone treatment applied to the transparent polypropylene resin 2 when extruding and laminating on the surface of the base material sheet 1 made of a vinyl material is within the range of 1 to 10 × 10 ⁻⁶ g / m ^2. By laminating a surface protective layer with weather resistance formulation by adding an ultraviolet absorber or light stabilizer on the transparent polypropylene resin layer 7, the decrease in peel strength at the normal state and after being affected by ultraviolet rays and heat is minimized. I found out that it can be suppressed to the limit. At an ozone treatment amount of 10 × 10 ⁻⁶ g / m ² or more, the peel strength in the normal state is sufficiently expressed, but the peel strength is significantly lowered after being affected by ultraviolet rays and heat. In addition, at an ozone treatment amount of 1 × 10 ⁻⁶ g / m ² or less, normal strength does not appear due to an insufficient oxidation treatment amount.

  Further, the transparent polypropylene resin layer 7 in the decorative sheet is formed by coextrusion of a non-modified polypropylene resin subjected to weathering prescription and a maleic acid-modified polypropylene resin so that the maleic acid-modified polypropylene resin is formed on the base sheet 1 side. It has been found that the effect of further improving the peel strength can be obtained by using such a layer structure.

  As maleic acid-modified polypropylene resins, Admer made by Mitsui Chemical Co., Ltd., Modic made by Mitsubishi Chemical Co., Ltd., etc. are marketed, and polypropylene grade resins suitable for laminating use may be appropriately used. As the base material of the maleic acid-modified resin, in addition to polypropylene resin, polyethylene resin and ethylene- (meth) acrylic acid copolymer resin are generally used, but when these resins are used, heat resistance, particularly When heat of 80 ° C. or higher is applied, the adhesion performance of the co-extruded interface between the unmodified polypropylene resin and the maleic acid-modified resin is lowered, and the peel strength is significantly lowered.

  In recent times when solvent-free is required, reactive hot melt adhesives are beginning to be used when laminating decorative sheets on wood-based, inorganic or metal-based substrates. In use, a method in which the hot melt adhesive is heated to around 100 to 140 ° C. and applied to the back surface of the sheet and then bonded to the base material is often employed. Therefore, although temporarily high-temperature heat is applied to the decorative sheet, the maleic acid-modified resin used for the decorative sheet is a polypropylene-based one that has excellent heat-resistant adhesive strength with unmodified polypropylene resin. Better to do.

  Further, by providing an anchor coat layer made of a two-component isocyanate-curable polyurethane resin between the transparent polypropylene resin layer 7 to which the above various additives are added and the base sheet 1 having a printed pattern layer. Further, the adhesion between the printed pattern layer and the transparent polypropylene resin layer is further improved, and it is possible to obtain a further effect of improving the peel strength.

  In order to further improve the design feeling of the decorative sheet obtained in the present invention, the formation of a concave pattern on the transparent polypropylene resin layer 7 is widely performed, and as a method therefor, a normal hot-pressure embossing method is used. It's okay. However, in the case of using the extrusion laminating method as in the present invention, a convex pattern is provided on the surface of the cooling roll 4 for cooling and solidifying the melted transparent polypropylene resin 2, and the extruded resin is used as the cooling roll 4 and the press roll. Embossing and using a method of forming a concave pattern on the surface of the transparent polypropylene resin layer 7 can simplify the manufacturing process and increase the degree of freedom and fidelity of the embossed shape. is there.

  In addition, a primer layer may be provided on the back surface of the base sheet 1 as necessary in order to improve the adhesion strength with the woody boards, inorganic boards or metal plates of the decorative sheet. With respect to this primer layer, sufficient adhesion strength with the base material sheet 1 is obtained, and between the base material sheet 1 at the time of lamination and the wooden board, inorganic board, metal plate, etc. As long as there is no floating or the like, it is not particularly limited, but it is preferable to use a polyurethane resin type.

  Hereinafter, it demonstrates further by the Example and comparative example of the manufacturing method of the decorative sheet of this invention.

As transparent polypropylene resin, 0.2% by weight of phenolic antioxidant, 0.5% by weight of hindered amine light stabilizer, 0.5% by weight of benzotriazole UV absorber, 0.2% of antiblocking agent %, Respectively, using a transparent homopolypropylene resin having a melt flow rate of 18 g / 10 min as defined in JIS K 6760, and 70% by weight of a maleic acid-modified random polypropylene resin modified with maleic anhydride to an ethylene rubber 30% by weight of a resin with a melt flow rate of 11 g / 10 min, a gravure printing method on which a wood grain pattern layer is printed on one side and a polyurethane resin primer layer is printed on the other side On the grain pattern printed pattern side of a polypropylene sheet with a width of 70 μm and a width of 1300 mm (= 1.3 m), The thickness of the transparent homopolypropylene resin layer was 70 μm, the thickness of the maleic acid-modified resin layer was 10 μm, and lamination was performed at a line speed of 60 m / min (= 3600 m / hr) using a coextrusion laminating method. Furthermore, in order to increase the adhesion between the maleic acid-modified resin and the printed pattern layer, curing is performed by mixing a main component mainly composed of polyester polyol with hexamethylene diisocyanate and isophorone diisocyanate as isocyanate components in a ratio of 1: 1. An anchor coating agent obtained by mixing the agent at a ratio of 4: 1 was applied to the surface of the printed pattern layer using a gravure coating method with a thickness of about 1 μm. Further, immediately before the lamination, an ozone bar having an outlet width of 1300 mm was used between the maleic acid-modified resin and the anchor coat layer with ozone gas at an ozone concentration of 3 g / Nm ³ and an ozone flow rate of 5 Nm ³ / hr in the vicinity of the outlet. And sprayed. The ozone treatment amount at this time is calculated as 3.2 × 10 ⁻⁶ g / m ² by the following formula.

Ozone treatment amount [ kg / m ² ] = (ozone concentration [g / Nm ³ ] × ozone flow rate [Nm ³ / hr]) / (material width [m] × line speed [m / hr])
On the outermost surface of the laminate sheet thus obtained on the transparent homopolypropylene resin layer side, a two-component curable urethane resin surface protective agent to which a light stabilizer and an ultraviolet absorber are added is formed to a thickness of about 6 μm using a gravure coating method. The decorative sheet was manufactured by coating.

  A decorative sheet was produced using the same method as in Example 1 except that the anchor coating agent was not applied.

  A decorative sheet was produced in the same manner as in Example 2 except that the maleic acid-modified resin layer was not provided and the thickness of the transparent homopolypropylene resin layer was 80 μm.

[Comparative Example 1]
The ozone concentration 10 g / Nm ^3, except that the ozone flow rate 12Nm ³ / hr was prepared a decorative sheet using the same method as in Example 1. The ozone treatment amount at this time is calculated as 2.6 × 10 ⁻⁵ g / m ² by the above formula.

[Comparative Example 2]
The ozone concentration 1 g / Nm ^3, except that the ozone flow rate ^{3 Nm} 3 / hr was prepared a decorative sheet using the same method as in Example 1. The ozone treatment amount at this time is calculated as 6.4 × 10 ⁻⁷ g / m ² by the above formula.

A decorative sheet was produced by laminating decorative sheets produced according to the production conditions of Examples 1 to 3 and Comparative Examples 1 and 2 on a wooden base material, and the peel strength was measured in a normal state. Furthermore, using the decorative panels, a sample heated for 7 days in an oven at 90 ° C. and a sample subjected to ultraviolet irradiation at an illuminance of 65 mW / cm ² for 5 days using a metal weather tester manufactured by Daipura Wintes Co., Ltd. Then, the peel strength was measured for each. The results are shown in Table 1 below.

表１からわかるように、オゾン処理量が適正な範囲内にある実施例１〜３の製造条件で製造した化粧シートを用いた化粧板においては、常態の剥離強度が高いのはもちろん、９０℃５日間の加熱試験やメタルウェザー試験機での５日間に渡る耐候性（紫外線照射）試験を行った後も剥離強度の低下は最小限に抑えられている。一方、オゾン処理量を適正範囲よりも増加させた比較例１においては、常態での剥離強度は発現するが、オゾン処理による樹脂の劣化が進行し過ぎているために、加熱試験や耐候性試験を行った後の剥離強度の低下の度合いが実施例１と比較して大きい。またオゾン処理量を適正範囲よりも低減させた比較例２においては、反応に寄与する官能基の数が少ない為に、常態の剥離強度自体が十分には発現しない。また、オゾン処理条件を適正な範囲内にした実施例１〜３の中では、マレイン酸変性樹脂を使用した実施例１及び２が、マレイン酸変性樹脂を使用していない実施例３と比較して、各剥離強度の値が高く、その中でも特に、アンカーコート層を設けてある実施例１の各剥離強度の値が、他の条件の剥離強度と比較して、相対的に最も高い。

As can be seen from Table 1, in the decorative board using the decorative sheet manufactured under the manufacturing conditions of Examples 1 to 3 in which the ozone treatment amount is within an appropriate range, the peel strength of the normal state is high as well as 90 ° C. Even after a 5-day heating test and a 5-day weather resistance (ultraviolet irradiation) test using a metal weather tester, the decrease in peel strength is kept to a minimum. On the other hand, in Comparative Example 1 in which the amount of ozone treatment was increased from an appropriate range, although the peel strength in the normal state is expressed, since the deterioration of the resin due to the ozone treatment has progressed excessively, a heating test and a weather resistance test are performed. The degree of decrease in peel strength after performing is larger than that in Example 1. Further, in Comparative Example 2 in which the ozone treatment amount is reduced from the appropriate range, the normal peel strength itself is not sufficiently developed because the number of functional groups contributing to the reaction is small. Among Examples 1 to 3 in which the ozone treatment conditions are within an appropriate range, Examples 1 and 2 using a maleic acid-modified resin are compared with Example 3 using no maleic acid-modified resin. Each peel strength value is high, and among them, the peel strength value in Example 1 in which the anchor coat layer is provided is relatively highest as compared with the peel strength under other conditions.

The sectional side view which shows the manufacturing method of the decorative sheet by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Melted transparent polypropylene resin 3 ... T die 4 ... Cooling roll 5 ... Peeling roll 6 ... Ozone spraying port 7 ... Transparent polypropylene resin layer

Claims (2)

A transparent polypropylene resin is melt-extruded and subjected to ozone treatment on one side, and then the surface subjected to the ozone treatment is printed on the surface of the printed pattern layer of the non-polyvinyl chloride-based material provided with a printed pattern layer in advance. In the process for producing a decorative sheet that is laminated in a molten state to form a transparent polypropylene resin layer,
The amount of ozone treatment is
When the ozone concentration generated from the ozone generator is D, the ozone flow rate is F, the width of the sheet for ozone treatment is W, the line speed of the sheet is V, and the ozone concentration attenuation rate is α,
Ozone treatment amount = α × D × F / (W × V)
Satisfy the above formula,
The ozone treatment amount decorative sheet manufacturing method of according to claim <br/> be in the range of ^{1 × 10 -6 g / m 2} ~10 × 10 -6 g / m 2. A decorative sheet produced by adhering a decorative sheet manufactured according to the manufacturing method according to claim 1 on a woody, inorganic or metallic base material using an adhesive.

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