JP3308504B2 - Sheet material and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet material which is printed on a substrate having voids and irregularities on the surface and has excellent adhesion between the surface layer and the substrate.

[0002]

2. Description of the Related Art The surface of nonwoven fabric, woven fabric, knitted fabric, paper, etc.
Due to the presence of the fibers, voids and irregularities are formed, which cannot be said to be smooth. For example, when two fibers are arranged on a smooth film, the fiber portion becomes a convex portion, and the space between the fibers becomes a concave portion, and irregularities are generated there. Further, when the fibers are entangled with each other, a void is generated around the intersection of the fibers or the entangled fibers. Woven fabrics, nonwoven fabrics, knitted fabrics, papers, and the like are made of fibers, so the above-described irregularities or voids are generated, and unlike the case where printing is performed on a film or sheet having a smooth surface, missing printing (printing was not possible) Part).

For this reason, conventionally, when printing on a substrate having voids or irregularities on the surface, a method of providing a synthetic resin layer so that the surface becomes smooth and printing the surface is adopted. . Further, when a surface layer (particularly, a surface layer made of an olefin-based synthetic resin) is laminated on a printed substrate, if the surface layer is laminated as it is, sufficient adhesive strength cannot be obtained. A method of laminating a primer layer or an adhesive layer on a printed substrate or performing a corona discharge treatment and laminating a surface layer thereon is employed.

[0004]

However, when an adhesive or a primer layer is provided on a substrate, there are problems such as an increase in cost and an increase in the number of manufacturing steps.

[0005]

Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and at least the surface of a substrate having voids or irregularities formed by the presence or overlap of fibers is provided on the surface. A sheet material in which a synthetic resin emulsion is applied so as not to completely fill at least a part of voids or irregularities, and after printing, a transparent or translucent surface layer is laminated, and the surface layer is A sheet material in which a part of the synthetic resin to be formed enters at least a part of voids or irregularities that are not completely buried or / and a convex portion of the base material cuts into and adheres to the surface layer; Sheet material, a sheet material in which the base material having irregularities is a fibrous base material, a sheet material for a floor material provided with an olefin-based synthetic resin layer on the back surface, and a sheet material for a floor material provided with a nonwoven fabric layer on the bottom surface. Offer Is shall.

As the base material used for the sheet material of the present invention, a woven fabric, a nonwoven fabric, a knitted fabric, a paper or the like having voids or irregularities due to fibers on the surface thereof, an embossed material thereof, A laminate or the like is used. Examples of woven fabric, nonwoven fabric, knitted fabric, paper, etc. having fine voids or irregularities include natural animal or vegetable fibers such as cotton, hemp, silk, and wool; polyester, polyamide, polyethylene, polypropylene, acrylic, Synthetic fibers such as vinylon; regenerated fibers such as rayon, suf, acetate, etc .; one or more fibers selected from glass fibers, pulp, asbestos, rock wool, and the like, or, if necessary, an inorganic filler; What consists of what mixed the synthetic resin binder etc. can be used more preferably. Further, glass-pulp mixed paper made of glass fiber and pulp can be more preferably used in terms of cost and workability. The specific roughness value of the substrate surface is preferably from 40,000 to 120,000. The intrinsic roughness value is a numerical value derived from the result of measuring the unevenness of the surface of the fibrous base material using a non-contact type surface roughness meter, and indicates a value on the surface of the fibrous base material within the measurement range (10 mm). it is the sum of the absolute value of the difference ([mu] m) and the average value Y ₀ of any point Y _i and the total Y _i.

As the emulsion used for the sheet material of the present invention, a general emulsion can be used, but ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol having good adhesion to a polyolefin resin can be used. Copolymer, ethylene-acrylic acid copolymer (EA
A), ethylene-methacrylic acid copolymer (EMA), ethylene-ethyl acrylate-maleic anhydride copolymer (EEA-MAH), polyvinyl acetate (PVAc), emulsions such as acrylic emulsions, solvent-based polyolefin resins, etc. Aqueous emulsions and solvent-based emulsions used in (1) can be suitably used. These emulsions can be used alone or as a mixture of two or more kinds and / or laminated. Also, from the viewpoint of workability,
EVA emulsions or acrylic emulsions are particularly preferred.

[0008] In the sheet material of the present invention, a method of applying an emulsion on a substrate includes a doctor knife coater, a comma doctor knife coater, a roll coater, a reverse roll coater, a screen coater, a rotary screen coater, a gravure coater, and a spray coater. Ordinary coating methods such as the above can be used. Also, after the applied synthetic resin emulsion is cured,
It is more preferable to perform flat embossing.

The solid content of the synthetic resin emulsion is preferably 5 to 60%. It is particularly preferable to use a synthetic resin emulsion having a solid content concentration of 5 to 20% by adding a thickener or the like, since the synthetic resin emulsion hardly forms a film on a substrate. The coating amount of the emulsion in a wet state is preferably 10 to 300 g / m ^{2, and} more preferably 30 to 60 g / m ^{2 in} terms of cost. Further, in the Dry state, preferably 1 to 30 g / m ^2, more preferably 3 to 7 g / m ² in terms of cost.

FIG. 1 schematically shows a partially enlarged cross-sectional view of a structure in which an emulsion is applied onto a fiber base material, dried, flat embossed, printed, and a transparent surface layer is laminated. As shown in FIG. 1, a fiber base material such as a woven fabric, a knitted fabric, or a nonwoven fabric has irregularities due to fibers. By applying the emulsion, an emulsion layer is formed on the fiber surface, and the apparent thickness of the fibers is increased. And voids are reduced, and unevenness is smoothed. For this reason, printing is difficult to drop out,
Since the voids remain, the adhesive strength with the transparent surface layer is not significantly impaired.

As the printing method, a commonly used printing method can be used, and an offset printing method, a screen printing method, a gravure printing method, a flexographic printing method, or the like can be employed.

As the transparent surface layer of the present invention, a transparent synthetic resin is used, and low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polyethylene polymerized using a metallocene catalyst ( Polyethylene such as randomized polypropylene, block polymerized polypropylene, and syndiotactic polypropylene; ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer An olefinic synthetic resin such as a copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methacrylic acid ester copolymer, or other ethylene-based copolymer or a mixture thereof is used. These resins may be used alone, or a plurality of them may be mixed and / or used. In addition, from the viewpoint of scratch resistance and flexibility, the use of a blended resin of syndiotactic polypropylene and metallocene polyethylene (hereinafter referred to as “polypropylene-polyethylene blend resin”) provides not only scratch resistance and flexibility but also heat resistance. Excellent, more preferred.

Further, pigments, antibacterial agents, antifungal agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants may be used in the emulsion coated on the synthetic resin forming the transparent surface layer and / or the substrate. Various additives such as a filler, a viscosity reducing agent, a flame retardant, a deodorant, and a foaming agent may be added.

The surface layer may be formed by laminating a film or sheet formed by an extrusion method or a calendering method on a substrate which has been subjected to an emulsion treatment by a hot-melt laminating method, a frame laminating method, or the like. Or a method in which a sheet is formed and, at the same time, a sheet is laminated on an emulsion-treated substrate (hereinafter referred to as “extrusion lamination method”).
May be).

In the sheet material of the present invention, voids and irregularities which are not completely buried on the surface of the substrate subjected to the emulsion treatment remain. And the anchoring effect increases the adhesive strength between the surface layer and the substrate. As a result, sufficient adhesive strength can be obtained without using a primer layer or an adhesive layer.

The sheet material of the present invention may be subjected to embossing or the like.

In the sheet material for flooring of the present invention, the polyolefin-based synthetic resin laminated on the back surface of the sheet material includes low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, metallocene polyethylene and the like. Polyethylene such as random-polymerized polypropylene, block-polymerized polypropylene, and syndiotactic polypropylene; ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer Coalesce, an ethylene-based copolymer such as an ethylene-methacrylic acid ester copolymer or a mixture thereof, and the like.From the viewpoint of flexibility and cost, an ethylene-vinyl acetate copolymer or metallocene polyethylene is preferably used. it can. These resins may be used alone or in combination of two or more.

In the synthetic resin layer, pigments, antibacterial agents, antifungal agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, fillers, thinners, flame retardants, deodorants, foaming agents And other additives may be added. As the filler, an inorganic filler such as calcium carbonate, aluminum hydroxide, and talc is preferable.

In the flooring sheet of the present invention, the polyolefin resin layer used may be a non-foamed layer or a foamed layer. When a foamed layer is used, cross-linked foaming using a cross-linking agent or an electron beam cross-linking method or non-cross-linked foam may be used.

When a foamed layer is used as the polyolefin-based synthetic resin layer, a thermal expansion type microcapsule and / or a thermal decomposition type chemical foaming agent are used. The thermal expansion type microcapsules are obtained by encapsulating a low-boiling hydrocarbon or the like in a shell made of a thermoplastic polymer material. The thermoplastic polymer material constituting the shell of the microcapsule includes a polymer mainly composed of a copolymer of vinylidene chloride and acrylonitrile, and a polymer mainly composed of a copolymer of acrylonitrile and (meth) acrylate. Etc. can be used. Examples of the low-boiling hydrocarbons encapsulated in the microcapsule shell include isobutane, pentane, hexane, and the like.

Further, as thermal decomposition type chemical blowing agents, azodicarbonamide (ADCA), oxybisbenzenesulfonyl hydrazide (OBSH), benzenesulfonyl hydrazide (BSH), p-toluenesulfonyl hydrazide (TSH), diazoaminobenzene (DA
B), and a pyrolytic chemical blowing agent such as azobisisobutyronitrile (AIBN). These blowing agents can be used alone, or a plurality of thermal decomposition type chemical blowing agents can be used in combination.

As a method of laminating the olefin-based synthetic resin layer, an extrusion laminating method may be used. Alternatively, a olefin-based synthetic resin sheet is prepared once, and then the surface of the synthetic resin layer is heated and melted to perform lamination. Laminating method,
You may laminate | stack using a frame lamination method. Also,
It is also possible to adhere using various adhesives and the like. Further, the sheet material for flooring of the present invention can be embossed.

The sheet material for flooring of the present invention can improve the adhesiveness at the time of construction by laminating a nonwoven fabric on the rearmost surface. As nonwoven fabric, polyester fiber,
A nonwoven fabric made of rayon fiber, glass fiber, or the like can be used. As a method of laminating the nonwoven fabric, the nonwoven fabric can be bonded using an adhesive or the like, or a hot-melt lamination method in which the back surface of the synthetic resin layer is heated and melted, or a frame lamination method may be used.

[0024]

[Experimental Examples] The printability on the base material and the adhesion between the base material and the surface layer of the sheet material or the sheet material for floor material obtained in Examples 1 to 9 were evaluated. The printability on the substrate was visually observed, and the adhesion between the substrate and the surface layer was evaluated using a tension-autograph. [Experimental Example 1] As Experimental Example 1, a specific surface roughness value of 800
00 glass mixed paper (MCP-09 manufactured by Olivet Co., Ltd.)
In order to prevent voids or irregularities from being completely filled in the surface of the nonwoven fabric made of the composition (0), the emulsion having the composition shown in Table 1 was treated with a doctor knife coater for a total of W.
In an et state, it is applied three times so as to be 40.5 g / m ² ,
After drying, flat embossing was performed using a nip roll, and printing was performed using a gravure printing machine. Thereafter, as a transparent surface layer, a metallocene polyethylene resin (Kernel KC-581, manufactured by Nippon Polychem Co., Ltd.) was laminated on the printing surface by an extrusion laminating method to form a sheet material. A foam layer made of polyethylene (Softlon, manufactured by Sekisui Corporation) was laminated on the back surface of the obtained sheet material as an olefin-based synthetic resin layer by an extrusion lamination method to prepare a sheet material for flooring. The obtained sheet material for flooring material had good adhesion between the base material and the transparent surface layer, and hardly any omission of printing was observed. [Experimental Example 2] A polypropylene-polyethylene blend resin (polypropylene: manufactured by Chisso Corporation) as a transparent surface layer
XF9520, polyethylene: EVA resin (Ultracene 751 manufactured by Tosoh Corporation) as an olefin-based synthetic resin layer using Kernel KC-581 manufactured by Nippon Polychem, weight ratio of polypropylene to polyethylene = 2: 8).
A sheet material for flooring was produced in the same manner as in Experimental Example 1 except that a non-foamed layer was used. The obtained sheet material for flooring material had good adhesion between the base material and the transparent surface layer, and hardly any omission of printing was observed. [Experimental Example 3] As Experimental Example 3, a specific surface roughness value of 800
00 glass mixed paper (MCP-06 manufactured by Olivet Co., Ltd.)
In order to not completely fill the voids or irregularities on the surface of the nonwoven fabric made of the above (0), the emulsion having the composition shown in Table 2 was set to 20.5 g / m ² in a wet state using a doctor knife coater. After coating and drying, flat embossing is performed with a nip roll, and an emulsion having the composition shown in Table 1 is coated with a roll coater in a wet state at 20.0 g / m ^2. After drying, printing was performed using a gravure printing machine. Thereafter, a metallocene polyethylene resin (Kernel KC-58 manufactured by Nippon Polychem Co., Ltd.) was used as a transparent surface layer on the printing surface.
1) was laminated by an extrusion lamination method to prepare a sheet material. Polyethylene (Softlon manufactured by Sekisui) as an olefin-based synthetic resin layer on the back of the obtained sheet material
Foam layers were laminated by an extrusion lamination method to prepare a sheet material for flooring. The obtained sheet material for flooring material had good adhesion between the base material and the transparent surface layer, and hardly any omission of printing was observed. [Experimental Example 4] A polypropylene-polyethylene blend resin (polypropylene: manufactured by Chisso Corporation) as a transparent surface layer
XF9520, polyethylene: EVA resin (Ultracene 751 manufactured by Tosoh Corporation) as an olefin-based synthetic resin layer using Kernel KC-581 manufactured by Nippon Polychem, weight ratio of polypropylene to polyethylene = 2: 8).
A floor sheet material was prepared in the same manner as in Experimental Example 3 except that a non-foamed layer was used. The obtained sheet material for flooring material had good adhesion between the base material and the transparent surface layer, and hardly any omission of printing was observed. [Experimental example 5] As an experimental example 1, a specific surface roughness value of 800
00 glass mixed paper (MCP-09 manufactured by Olivet Co., Ltd.)
In order to prevent voids or irregularities from being completely filled in the surface of the nonwoven fabric made of the composition (0), the emulsion having the composition shown in Table 1 was treated with a doctor knife coater for a total of W.
In an et state, it is applied three times so as to be 40.5 g / m ² ,
After drying, flat embossing was performed using a nip roll, and printing was performed using a gravure printing machine. Thereafter, as a transparent surface layer, a metallocene polyethylene resin (Kernel KC-581, manufactured by Nippon Polychem Co., Ltd.) was laminated on the printing surface by an extrusion laminating method to form a sheet material. The obtained sheet material had good adhesion between the base material and the transparent surface layer, excellent scratch resistance on the surface, and hardly any omission in printing. [Experimental Example 6] As Experimental Example 6, a polypropylene-polyethylene blend resin (polypropylene:
Experimental Example 5 except that XF9520 manufactured by Chisso Corporation and polyethylene: Kernel KC-581 manufactured by Nippon Polychem, weight ratio of polypropylene to polyethylene = 2: 8) were used.
A sheet material was prepared in the same manner as described above. The obtained sheet material had good adhesion between the base material and the transparent surface layer, was excellent in scratch resistance of the surface, and hardly any omission of printing was observed. [Experimental Example 7] As Experimental Example 7, a sheet material was prepared in the same manner as in Experimental Example 5, except that a transparent surface layer was formed using low-density polyethylene. The obtained sheet material had good adhesiveness between the equipment and the transparent surface layer, and hardly any omission of printing was observed. It was somewhat inferior. [Experimental Example 8] As Experimental Example 8, a sheet material was prepared in the same manner as in Experimental Example 5 except that the emulsion was not applied. The obtained sheet material had good adhesion between the base material and the transparent surface layer, and also had excellent scratch resistance on the surface, but considerable print omission was observed. [Experimental Example 9] As Experimental Example 9, except that the emulsion was applied so as not to leave any voids or irregularities on the substrate surface.
A sheet material was prepared in the same manner as in Experimental Example 5. The obtained sheet material was excellent in scratch resistance and heat resistance on the surface, and hardly any omission of printing was observed, but the adhesion between the substrate and the transparent surface layer was poor.

[0025]

[Table 1] * 1 Ethylene-vinyl acetate emulsion (manufactured by Chuo Rika Kogyo Co., Ltd., MC3800), solid concentration 45% * 2 Vissurf manufactured by Chuo Rika Kogyo Co., Ltd.

[0026]

[Table 2] * 3 Acrylic emulsion (Dainippon Ink Co., Ltd., Dicknal K-2523) solid content concentration 55% * 4 Dainippon Ink Co., Ltd., RYUDYE-W Nt c
onc117

[0027]

According to the sheet material of the present invention, since the emulsion is applied to a substrate having voids and irregularities on the surface, the smoothness of the surface is improved, and even when printing is performed on the entire surface of the substrate surface. There is almost no omission in printing, and printing is easy. Further, by applying a synthetic resin emulsion on the substrate so as not to completely fill at least a part of the voids and irregularities on the surface, the resin composition forming a transparent or translucent surface layer enters, A sheet material can be produced without increasing the adhesive strength between the substrate and the surface layer and without impairing the aesthetic appearance due to the unevenness of the substrate.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a partially enlarged cross-sectional view of one embodiment of the present invention.

FIG. 2 is a diagram schematically showing a partially enlarged cross-sectional view of one embodiment of the present invention.

FIG. 3 is a diagram schematically illustrating a layer configuration of Experimental Examples 1 and 2 of the present invention.

FIG. 4 is a diagram schematically illustrating a layer configuration of Experimental Examples 3 and 4 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Sheet material 2 ... Sheet material for flooring 11 ... Fiber (cross section) 12,22 ... Emulsion synthetic resin 13,23 ... Ink 14, 24: Transparent surface layer 21: Base layer 25: Synthetic resin foam layer 26: Non-woven fabric layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 33/00 B05D 7/24 B32B 27/32

Claims (5)

(57) [Claims] 1. A synthetic resin emulsion is applied on at least the surface of a substrate having voids or irregularities formed by the presence or overlap of fibers so as not to completely fill at least a part of the voids or irregularities. Then, after printing, a sheet material in which a transparent or translucent olefin-based synthetic resin surface layer is laminated, and a gap in which a part of the olefin-based synthetic resin forming the surface layer is not completely filled. Or, a sheet material that enters at least a part of the unevenness or / and that is adhered with a convex portion of the base material biting into the surface layer. 2. The sheet material according to claim 1, wherein the solid content of the synthetic resin emulsion applied to the substrate is 5 to 60%. 3. The floor sheet material according to claim 1, wherein an olefin-based synthetic resin layer is provided on the back surface of the base material. 4. The sheet material for flooring according to claim 3, wherein a nonwoven fabric is provided on the rearmost surface. 5. A synthetic resin emulsion is applied on at least the surface of a substrate having voids or irregularities formed by the presence or overlap of fibers so that at least a part of the voids or irregularities is not completely filled. A method for producing a sheet material, comprising drying, printing, and then laminating a transparent or translucent surface layer.