JP4882142B2 - Manufacturing method of decorative sheet - Google Patents

Description

試験方法及び評価方法
樹脂製膜性：加工温度１２０℃のＴダイ押出成形において加工性を評価した。
○ 加工性が良好
△ 加工可能
× 加工性が悪い
発泡層形成性：発泡シートの外観を目視評価。
○ 表面が平滑できれい
△ 表面が平滑
× 表面が凸凹している。
発泡層引っ掻き性：発泡層をツメにて引っ掻き、その部分を目視評価。
○ 変化なし
△ 表面がややケバ立つ
× 発泡層が完全にけずれる
シート折り曲げ性：常温で１８０°に急激に折り曲げ、折り曲げた部分を
目視評価
○ 変化なし
△ 小さなクラックがある
× 表面が完全に割れている
燃焼試験： ＪＩＳ−Ａ１３２１建築物の内装材料及び工法の難燃試験法によって測定した。
発熱量（Ｔｄθ）は温度時間面積（℃分）を示す。
発煙量（Ｃａ）は発煙係数を示す。
【００２９】
【発明の効果】
以上説明した如く、本発明の製造方法で製造された化粧シートは、基材層上に、発泡剤、難燃剤を含むエチレン−酢酸ビニル共重合体樹脂からなる発泡樹脂層と印刷絵柄層が順次設けられると共に、前記印刷絵柄層から前記発泡樹脂層にかけて凹凸模様が施されている化粧シートにおいて、前記エチレン−酢酸ビニル共重合体樹脂のＭＦＲが１０〜７０ｇ／１０分からなり、前記エチレン−酢酸ビニル共重合体樹脂１００重量部に対してマイカを１０〜３０重量部添加してなるため、溶融温度が低く、成膜性に優れることから、加工性が向上し安価な化粧シートとすることができる。また、表面引っ掻き性等の表面物性に優れると共に難燃性が向上し、人間や環境に優しいボリュウム感が有るとともに風合いがよく意匠性に優れた化粧シートを得ることができる。
【図面の簡単な説明】
【図１】本発明の化粧シートの実施形態の層構成図である。
【符号の説明】
１ 化粧シート
２ 基材層
３ 発泡樹脂層
４ 絵柄印刷層
５ 凹凸模様[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet used for interior decoration of buildings, surface decoration of joinery, and the like, and particularly to a decorative sheet suitable for wall covering materials that are environmentally friendly and excellent in surface physical properties.
[0002]
[Prior art]
Building interior materials such as wallpaper are required to be flame retardant from the standpoint of fire safety, and are often required to have a certain level of flame resistance by the Building Standards Act. In addition, architectural interior materials are required to have high designability in order to enhance comfort as an indoor living space. In particular, in order to have a three-dimensional design, a material that can be highly foamed as well as flexible. Is advantageous. Conventionally, materials using vinyl chloride resin have been widely used as materials that can meet such demands. However, a resin composition containing a halogen such as a vinyl chloride resin has a drawback of generating a harmful gas during a fire or incineration.
[0003]
For this reason, building interior materials made of resin that does not contain halogens have been developed. In that case, the resin itself is not flame retardant, so it is necessary to impart flame retardancy, and there is no generation of toxic gases during combustion. In general, metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used as low smoke and non-polluting flame retardants. However, these metal hydroxides need to be highly filled in order to increase the flame retardancy, and therefore the fluidity of the resin during the heat-melt extrusion process is lowered, and a sheet having a good surface state cannot be obtained. . In addition, it is conceivable to increase the processing temperature in order to increase the fluidity of the resin, but there is a problem in the stability of the production process because the foaming agent begins to decompose during processing by increasing the processing temperature. Also, the original foaming characteristics of the resin were impaired, and the volume feeling was small with a low expansion ratio.
[0004]
In addition, in order to obtain the stability of the production process, when a resin having a low melting point is used, there is no problem with the volume ratio with respect to the expansion ratio, but surface properties such as surface scratch resistance and wear resistance are obtained. There was a problem that the surface of the decorative sheet was easily broken.
[0005]
[Problems to be solved by the invention]
Therefore, the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to generate no toxic gas at the time of fire or combustion, to have a volume feeling, a good texture, and a variation. An object of the present invention is to provide a method for producing a decorative sheet having a foamed resin layer having a substantially uniform foamed cell shape and having excellent surface scratch resistance, abrasion resistance, and the like.
[0006]
[Means for Solving the Problems]
The solution of the present invention for achieving the above object is that the melt flow rate containing 10 to 30 parts by weight of mica with respect to 100 parts by weight of the foaming agent, flame retardant, and resin is 10 to 70 g on the base material layer. / 10 minutes foamed resin layer forming composition comprising ethylene-vinyl acetate copolymer resin to form a laminate by simultaneous film formation by T-die extrusion method, and the foamed resin layer forming composition surface of the laminate After the printed picture layer is provided on the sheet, the foamed resin layer forming composition is foamed in a heating foaming furnace to form a foamed resin layer, and embossing is performed from the printed picture layer side to produce a decorative sheet The method is adopted .
[0007]
With the above configuration, the melting temperature is low and the film formability is excellent, so that the processability is improved and an inexpensive decorative sheet can be obtained, and the surface physical properties such as surface scratchability are excellent, and flame retardancy is also achieved. A decorative sheet that is improved, has a feel of volume that is kind to humans and the environment, and has a good texture and excellent design. In addition, by using an ethylene-vinyl acetate copolymer resin having a higher oxygen index than polyethylene for the foamed resin layer with a large amount of resin, an inexpensive and environmentally friendly decorative sheet that does not require the use of a large amount of various flame retardants can be obtained. Obtainable.
[0008]
In addition, by using a silicone flame retardant as the flame retardant, effective flame retardancy can be obtained with a small amount of addition, and the melt tension at the time of resin melting is stabilized and the foamed cells become dense, so there is a volume feeling. It can be set as a decorative sheet .
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a layer configuration diagram of an embodiment of a decorative sheet of the present invention, where 1 is a decorative sheet, 2 is a base material layer, 3 is a foamed resin layer, 4 is a printed pattern layer, and 5 is an uneven pattern. .
[0010]
FIG. 1 shows a layer configuration diagram of an embodiment of a decorative sheet of the present invention. The decorative sheet 1 of the present invention is formed on a base layer 2 with a foaming agent, a silicone flame retardant and a T-die extruder. An unfoamed resin layer is formed by heating and extruding an olefin-based thermoplastic resin having a melt flow rate (hereinafter referred to as MFR) of 10 to 70 g / 10 min added with at least 10 to 30 parts by weight of mica, The pattern printed layer 4 is provided on the non-foamed resin layer, and then the foamed resin layer 3 is heated and foamed, and the uneven pattern 5 is applied from the pattern printed layer 4 side to the foamed resin layer 3. And by adding 10-30 weight part of mica, it can be set as the decorative sheet | seat with the volume feeling which flame retardance improved and was excellent in physical properties, such as surface scratchability and stain resistance.
[0011]
Next, the decorative sheet of the present invention will be described in more detail.
As the base material layer 2 used in the present invention, paper, flame retardant paper, non-combustible paper, organic fiber or inorganic fiber woven fabric, and non-woven fabric are used. Some materials are preferred. In addition, in consideration of combustion due to fire after construction, etc., pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanazine sulfanilate or guanazine phosphate, or calcium carbonate, aluminum hydroxide, magnesium hydroxide, etc. What is said to be a normal backing paper for wallpaper, such as an inorganic paper mixed with the above inorganic material, can be used, and its basis weight is preferably 30 to 120 g / m ² .
[0012]
Next, the foamed resin layer 3 will be described. Examples of the resin forming the foamed resin layer 3 include non-halogen thermoplastic resins such as polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene and other polyolefins, and ethylene, propylene, butene, butadiene, isoprene and other olefins. Or a copolymer of α-olefins having 4 or more carbon atoms (linear low density polyethylene), ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, Ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ionomer, or a mixture of one or more of these Resins can be mentioned. Among them, in particular, the ethylene-vinyl acetate copolymer has a different oxygen index depending on the vinyl acetate content, and the higher the vinyl acetate content, the higher the oxygen index. Therefore, as the olefinic thermoplastic resin forming the foamed resin layer 3 of the decorative sheet 1 of the present invention, an ethylene-vinyl acetate copolymer is preferable, and the content of the vinyl acetate is adjusted to 5% or more. Since the heat of combustion becomes small, it is preferable in terms of flame retardancy. Moreover, the adhesiveness to a processing machine can be suppressed appropriately by making it 45% or less, and favorable workability is obtained.
[0013]
In addition, the processing temperature when the MFR value representing the flow characteristics is 10 to 70 g / 10 min when heated and melt-extruded with a T-die extruder can be made lower than the decomposition temperature of the blowing agent used in the present invention. Is also stable and preferred. Furthermore, when the MFR value is 10 g / 10 min or less, the compounded resin becomes hard and is easily broken when folded even in the state of the foamed resin layer. On the other hand, if it is 70 g / 10 min or more, the surface becomes too soft, the foam cell layer is crushed, and the surface strength is insufficient.
[0014]
Next, as the foaming agent used for the foamed resin layer 3, a thermal expansion type capsule foaming agent encapsulating a hydrocarbon having a low boiling point can be used, but it is low in cost and has a small amount of heat of decomposition, flame retardancy and Pyrolysis-type foaming of azo compounds such as azodicarbonamide and azobisformamide from the viewpoints of being excellent in self-digestibility, stable in water, non-toxic, and capable of imparting flame retardancy to the foamed resin layer 3 Agents are preferred. Azodicarbonamide is preferable because it has a high decomposition temperature and can be lowered by using a foaming accelerator in combination. As the foaming accelerator, inorganic salt, metal soap, and acids are used. The addition amount of the foaming agent may be appropriately determined depending on the required design properties, but is generally 2 to 10 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer forming the foamed resin layer 3.
[0015]
Moreover, as a flame retardant used for the foamed resin layer 3 of the present invention, silicone-based, phosphoric acid-based, inorganic metal hydroxides and the like can be considered, which are environmentally friendly and can be effectively added in a small amount by adding a flame retardant. Those that can impart flame retardancy are preferred, and silicone flame retardants are extremely effective. Especially when high molecular weight silicone flame retardants are used, the melt tension at the time of resin melting (resin foaming) becomes stable and the foam cell. In particular, polydimethylsiloxane alone, or a mixture of a polydimethylsiloxane derivative having an epoxy group or a methacrylate group and silicon dioxide is preferable. Further, by using 100% of the silicone flame retardant, the flame retardant can be sufficiently imparted with 30 parts by weight with respect to 100 parts by weight of the resin forming the flame retardant layer, but the silicone flame retardant is expensive. For this reason, 100% of the silicone flame retardant cannot be used, and it must be used in combination with other environmentally friendly flame retardants. As a flame retardant used in combination with this silicone flame retardant, an inorganic flame retardant, specifically, a mixture of one kind or two or more kinds of inorganic substances such as mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, etc. Use in combination is appropriate for the above reasons.
[0016]
The mica (mica) added in the present invention can be easily sliced with a hexagonal plate-like aluminum silicate mineral rich in elasticity, and is added for improving the surface strength of the resin layer and imparting flame retardancy. It is an inorganic filler, and it is flame retardant by relatively reducing the amount of resin component that is concealing power and flame retardancy, which is one of the functions as a sheet, by mass filling of this component. It plays the role of improvement. If the addition amount is 10 parts by weight or less, the flame retardant effect does not appear, and if it is 30 parts by weight or more, the resin fluidity at the time of melt extrusion becomes poor. The particle diameter is preferably 3 to 10 μm.
[0017]
In addition, as the colorant used for the foamed resin layer 3, any organic or inorganic colorant that does not contain halogen can be used. In particular, in the present invention, light colors such as yellow, gray, and white are used. Titanium dioxide pigment is effective when it comes out clearly. The addition amount of the titanium dioxide pigment is preferably 10 to 20 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer resin.
[0018]
Next, the printed pattern layer 4 of the present invention can be generally formed with ink by a known printing method such as gravure printing, offset printing, silk screen printing or the like. Examples of the printed pattern include a printed pattern such as a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric figure, a character, a symbol, or a solid pattern. As an ink, a polyester resin, a polyurethane resin composed of isocyanate and polyol, an acrylic resin, a vinyl acetate resin, a cellulose resin, a polyamide resin, or the like is used as a vehicle. Inks prepared by adding pigments, solvents, various auxiliary agents and the like can be used.
[0019]
Moreover, in order to adjust the uneven | corrugated pattern surface and foaming surface of the decorative sheet 1 to desired glossiness, you may provide a glossiness adjustment layer as a decoration layer. As a method for adjusting the gloss, a method in which an ink kneaded with a matting agent such as silica is applied to the surface is mainly used. As the binder of the ink used, acrylic resin, polyurethane resin, polyester resin, epoxy resin, and transparent or translucent resin of these copolymer resins are used.
[0020]
Further, when the decorative sheet is heated using a well-known sheet or a rotary embossing machine, the uneven pattern 5 is formed with an embossed plate from the outermost layer on the base material layer. The film is formed from the printed pattern layer 4 to the foamed resin layer 3 by cooling after the above. Examples of the shape of the concavo-convex pattern 5 include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain, a hairline, and a striated groove.
[0021]
Next, the manufacturing method of the decorative sheet of the present invention will be described using the decorative sheet of the above-described embodiment as an example. First, an ethylene-vinyl acetate copolymer resin having an MFR of 10 to 70 g / 10 min containing 10 to 30 parts by weight of a foaming agent, a silicone-based flame retardant, titanium dioxide and mica on a base material layer 2 made of backing paper. The mixed resin product is heated and melt extruded to produce a laminate, and the unfoamed resin layer surface exposed from the laminate is subjected to corona discharge treatment and printed on the surface subjected to the corona discharge treatment by gravure printing. After forming the layer 4, the unfoamed resin layer is foamed in a heating foaming furnace to form the foamed resin layer 3, and the embossed plate extends from the printed pattern layer 4 side to the foamed resin layer 3. The decorative sheet 1 can be obtained by cooling after forming the uneven pattern 5. In this way, by using an ethylene-vinyl acetate copolymer resin having an MFR of 10 to 70 g / 10 min, the foaming agent is not decomposed and foamed in the heat-melt extrusion process with a T-die, and on the surface of the base material layer 2. Since it can be laminated, the printed pattern layer 4 can also be clearly formed, and by heating and foaming, a decorative sheet having a volume feeling and a good texture and excellent design can be obtained.
[0022]
【Example】
Example 1
^On a flame-retardant backing paper having a basis weight of 70 g / m ² (manufactured by Kojin Co., Ltd., WK870D), a foamed resin layer-forming composition having the following composition was simultaneously laminated by a T-die extrusion method so as to have a thickness of 100 μm. Thus, a laminate was produced. Next, after the corona discharge treatment is applied to the resin layer surface of the laminate, the corona discharge treatment surface is gravure-printed with water-based ink made of an acrylic resin (Ode AG, manufactured by The Inktec Co., Ltd.) and has a grain pattern pattern A layer was provided. Next, this was foamed in a heating foaming furnace (at 200 ° C. for 60 seconds), and embossed with a grain pattern embossed plate from the printed layer side to obtain a decorative sheet according to the present invention. .
[0023]
[Composition of foamed resin layer forming composition, unit by weight]
Resin Ethylene-vinyl acetate copolymer (MFR = 60) 100
Filler Aluminum hydroxide 50
Foaming agent ADCA 6
Pigment Titanium dioxide 15
Flame retardant Silicone 5
Mica 30
[0024]
Comparative Example 1
A decorative sheet was obtained in the same manner as in Example 1 except that the foamed resin layer-forming composition was formulated as follows.
[Composition of foamed resin layer forming composition, unit by weight]
Resin Ethylene-vinyl acetate copolymer (MFR = 60) 100
Filler Aluminum hydroxide 50
Foaming agent ADCA 6
Pigment Titanium dioxide 15
Flame retardant Silicone 5
Mica 5
[0025]
Comparative Example 2
A decorative sheet was obtained in the same manner as in Example 1 except that the foamed resin layer-forming composition was formulated as follows.
[Composition of foamed resin layer forming composition, unit by weight]
Resin Ethylene-vinyl acetate copolymer (MFR = 60) 100
Filler Aluminum hydroxide 50
Foaming agent ADCA 6
Pigment Titanium dioxide 15
Flame retardant Silicone 5
Mica 40
[0026]
Comparative Example 3
A decorative sheet was obtained in the same manner as in Example 1 except that the foamed resin layer-forming composition was formulated as follows.
[Composition of foamed resin layer forming composition, unit by weight]
Resin Ethylene-vinyl acetate copolymer (MFR = 8.5) 100
Filler Aluminum hydroxide 50
Foaming agent ADCA 6
Pigment Titanium dioxide 15
Flame retardant Silicone 5
Mica 30
[0027]
Comparative Example 4
A decorative sheet was obtained in the same manner as in Example 1 except that the foamed resin layer-forming composition was formulated as follows.
[Composition of foamed resin layer forming composition, unit by weight]
Resin Ethylene-vinyl acetate copolymer (MFR = 75) 100
Filler Aluminum hydroxide 50
Foaming agent ADCA 6
Pigment Titanium dioxide 15
Flame retardant Silicone 5
Mica 30
[0028]
[Table 1]

Test Method and Evaluation Method Resin film-formability: Workability was evaluated in T-die extrusion molding at a processing temperature of 120 ° C.
○ Good workability △ Processable × Poor workability foam layer formation: Visual evaluation of the appearance of the foam sheet.
○ The surface is smooth and clean △ The surface is smooth × The surface is uneven.
Foam layer scratchability: The foam layer is scratched with a nail, and the part is visually evaluated.
○ No change △ The surface is slightly scratched × Sheet folding property that foam layer is completely dislodged: Folded sharply at 180 ° at normal temperature and visually evaluated the folded part ○ No change △ There is a small crack × The surface is completely cracked Combustion test: JIS-A1321 It was measured by the interior material of the building and the flame retardant test method of construction method.
The calorific value (Tdθ) indicates a temperature time area (° C.).
The smoke generation amount (Ca) indicates the smoke generation coefficient.
[0029]
【Effect of the invention】
As described above, the decorative sheet produced by the production method of the present invention has a foamed resin layer and a printed pattern layer made of an ethylene-vinyl acetate copolymer resin containing a foaming agent and a flame retardant on the base material layer in order. In the decorative sheet provided with a concavo-convex pattern from the printed pattern layer to the foamed resin layer, the ethylene-vinyl acetate copolymer resin has an MFR of 10 to 70 g / 10 minutes, and the ethylene-vinyl acetate Since 10 to 30 parts by weight of mica is added to 100 parts by weight of the copolymer resin , the melting temperature is low and the film formability is excellent, so that processability is improved and an inexpensive decorative sheet can be obtained. . In addition, it is possible to obtain a decorative sheet that has excellent surface properties such as surface scratchability and flame retardancy, and has a volume feel that is friendly to humans and the environment, and has a good texture and excellent design.
[Brief description of the drawings]
FIG. 1 is a layer configuration diagram of an embodiment of a decorative sheet of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Makeup sheet 2 Base material layer 3 Foamed resin layer 4 Picture printing layer 5 Uneven pattern

Claims (1)

  On the base material layer, a foaming agent, a flame retardant, and an ethylene-vinyl acetate copolymer resin having a melt flow rate containing 10 to 30 parts by weight of mica with respect to 100 parts by weight of the resin is 10 to 70 g / 10 minutes. The foamed resin layer forming composition is formed into a laminate by simultaneously laminating the film by a T-die extrusion method, and after providing a printed pattern layer on the foamed resin layer forming composition surface of the laminate, A method for producing a decorative sheet, wherein a foamed resin layer forming composition is foamed to form a foamed resin layer and embossed from the printed pattern layer side to form an uneven pattern.

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