JP3167673B2 - Non-halogen floor material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flooring material.

[0002]

2. Description of the Related Art Floor materials made of vinyl chloride resins such as polyvinyl chloride have been widely used as floor materials for buildings. On the other hand, in recent years, it has been studied to use a floor material made of a synthetic resin, rubber, or the like that does not contain halogen, instead of the floor material made of the vinyl chloride resin.

[0003]

As the above-mentioned synthetic resins containing no halogen, olefin resins and acrylic resins have been attracting attention. However, olefin-based resins and acrylic-based resins have the same problems as workability and various problems that it is difficult to obtain a material that satisfies various properties required for flooring materials. It was difficult to obtain a non-halogen floor material having the above-mentioned properties.

[0004] The present invention solves the above-mentioned problems, and has no problem in workability, and in terms of various properties required as a flooring material, is equal to or better than a flooring material made of a vinyl chloride resin. The present invention provides a non-halogen floor material which is excellent in water resistance.

[0005]

Means for Solving the Problems The non-halogen flooring material of the present invention made to solve the above-mentioned problems comprises at least a fibrous base material, a synthetic resin emulsion or a rubber latex containing no halogen on the fibrous base material. The intermediate layer formed by applying and drying and solidifying, a printed pattern applied on the intermediate layer, a synthetic resin emulsion or rubber latex containing no halogen is applied on the intermediate layer provided with the printed pattern.
It comprises a transparent top layer formed by drying and solidifying, and a non-foamed non-foamed backing layer formed on the back surface of the fibrous base material.

As the fibrous base material used in the present invention, natural animal or vegetable fibers conventionally used as flooring base materials; asbestos; glass fibers;
Rock wool; pulp; one or more inorganic or organic fibers selected from polyethylene, polypropylene, polyamide, acrylic, polyester, and other synthetic fibers; if necessary, an inorganic filler, a synthetic resin binder, and the like are added. A woven fabric, a knitted fabric, a nonwoven fabric, a paper, a laminate thereof, or the like can be used, but an organic fiber nonwoven fabric having particularly excellent dimensional stability; a glass fiber-mixed nonwoven fabric such as a glass / pulp mixed nonwoven fabric; a glass paper; Alternatively, among these laminates, those that are unlikely to cause swelling, shrinkage, and reduction in mechanical strength with water are preferable.

[0007] The synthetic resin contained in the synthetic resin emulsion forming the undercoat layer includes, for example, one or more acrylic resins selected from acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, and the like. Acrylic resins such as homopolymers or copolymers of monomers, or copolymers of other monomers copolymerizable with the above acrylic monomers; acrylic-styrene copolymer resins; ethylene One or a mixture of two or more resins selected from vinyl acetate copolymer resin; water-soluble polyester resin; and the like can be used.

[0008] The synthetic resin contained in the synthetic resin emulsion forming the undercoat layer includes a glass transition point (Tg point).
However, it is desirable to select one at -30 ° C to 30 ° C.
In addition, as long as the properties of the obtained flooring material and the workability of the post-process are not impaired, a synthetic resin having a glass transition point of more than 30 ° C is mixed with a synthetic resin having a glass transition point of 30 ° C or less. No problem.

The glass transition point is a second-order transition point, and the segments of the molecules constituting the polymer substance can start to rotate or vibrate, although the relative positional relationship is not broken as a whole. At a temperature lower than that, the polymer substance is frozen and becomes glassy.

[0010] In the non-halogen floor material of the present invention, SBR latex, MBR latex, NBR latex, IIR latex may be used in place of the above synthetic resin emulsion.
The intermediate layer may be formed of one or a mixture of two or more rubber latexes such as latex.

The synthetic resin emulsion or rubber latex forming the intermediate layer of the non-halogen floor material of the present invention contains 50 to 300 parts by weight, more preferably 150 to 300 parts by weight, per 100 parts by weight of the synthetic resin or rubber solids.
It is desirable to add ~ 250 parts by weight of inorganic filler.
By adding this inorganic filler, stickiness is prevented, and the printability at the time of forming a printed pattern described later is improved, and the solid content concentration of the synthetic resin emulsion or rubber latex is increased. Drying and solidification of rubber latex, in a short time,
There is also an advantage that it can be performed reliably.

The inorganic filler to be added to the synthetic resin emulsion or rubber latex for forming the undercoat layer includes:
For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, silica, alumina,
Commonly used inorganic fillers such as calcium aluminate, silicic acid, talc, and clay, and hollow balloons such as glass balloons, shirasu balloons, and synthetic resin balloons can be used. When a hollow balloon such as a glass balloon is used as the inorganic filler, cost reduction and weight reduction of the floor material can be achieved. In addition, as the inorganic filler,
Average particle size is 0.5 to 10 μm, more preferably 1 to 4 μm
It is desirable to use one of about m.

When the intermediate layer of the non-halogen floor material of the present invention is formed of a synthetic resin emulsion, as described below, 50 to 50 parts by weight per 100 parts by weight of the solid content of the synthetic resin.
By selecting and using an emulsion of a synthetic resin having a glass transition point of −30 ° C. to 30 ° C. to which 300 parts by weight of an inorganic filler has been added, the cold resistance required for the flooring material is satisfied and the surface is It is possible to improve printability when forming a print pattern while suppressing stickiness.

According to the knowledge of the present inventors, when an emulsion mainly composed of a synthetic resin having a glass transition point of more than 30 ° C. is used, the obtained undercoat layer is inferior in cold resistance, and is about 0 ° C. There is a concern that cracks may occur when the film is bent under the conditions described above. However, when a synthetic resin emulsion having a glass transition point of 30 ° C. or less is used, the surface of the obtained intermediate layer is sticky and a printed pattern is formed. It becomes difficult. On the other hand, this stickiness can be suppressed by adding an inorganic filler, but when an inorganic filler is added in an excessive amount, a new problem that the obtained undercoat layer becomes brittle occurs.

That is, in the present invention, by forming an intermediate layer using an emulsion of a synthetic resin having a glass transition point of 30 ° C. or lower, the cold resistance required for the flooring material is satisfied, and By adding an inorganic filler to the synthetic resin emulsion, it is possible to suppress the stickiness of the surface of the obtained undercoat layer.However, when an emulsion of a synthetic resin having a glass transition point of 30 ° C. or lower is used, It is necessary to add 50 parts by weight or more of an inorganic filler per 100 parts by weight of the synthetic resin solid content in order to suppress the stickiness of the obtained intermediate coating layer. If it is added in excess of 300 parts by weight per part, the resulting intermediate layer becomes brittle, so that the amount of the inorganic filler added is 100 parts by weight of the solid content of the synthetic resin. Even when the amount is 300 parts by weight or less, it is necessary to select and use a synthetic resin capable of sufficiently suppressing stickiness, specifically, an emulsion of a synthetic resin having a glass transition point of -30 ° C or higher. It is.

The glass transition point of the synthetic resin contained in the synthetic resin emulsion forming the above-mentioned undercoat layer is particularly preferably from -20 ° C to 0 ° C, and the synthetic resin having such a glass transition point. The amount of the inorganic filler to be added when the emulsion is used is in the above range, that is, 150 to 25 per 100 parts by weight of the solid content of the synthetic resin.
0 parts by weight.

The synthetic resin emulsion or rubber latex for forming the undercoat layer may further contain, if necessary, antimony trioxide, antimony pentoxide, zinc borate, magnesium tertiary phosphate, magnesium phosphite, sulfamic acid. Non-halogen flame retardants such as guanidine, thiourea and guanidine phosphate; viscosity modifiers such as acrylate copolymers, sodium polyacrylate, carboxymethylcellulose, hydroxyethylcellulose, various polymer surfactants, and polyvinyl alcohol A printability improving agent such as an emulsified terpene; a drying retarder such as ethylene glycol, diethylene glycol and polyethylene glycol; an anti-adhesive such as stearate, silicone oil, paraffin wax; a defoaming agent such as a mineral oil system; Yes without halogen And various additives such as inorganic antibacterial and antifungal agents such as aluminosilicates; deodorants; crosslinking agents such as epoxy resins; dispersants; vulcanizing agents; coloring agents such as pigments; it can.

The synthetic resin emulsion or rubber latex to which the above-mentioned inorganic fillers and various additives are added as required is uniformly mixed and dispersed by an appropriate mixer, and then is mixed with a doctor knife coater, a roll coater, and an air mixer. It is applied to the surface of the fibrous base material by an appropriate means such as a knife coater and dried and solidified to form an intermediate layer. This undercoat layer needs to be formed at least on the front side of the fibrous base material (the side on which the printed pattern is formed), and a similar layer is formed on the back side of the fibrous base material (the side on which the backing layer is formed). It may be formed.

Since the synthetic resin emulsion or rubber latex is partially impregnated into the fibrous base material, if the coating amount is too small, the fibrous base material is exposed, and it is difficult to apply a printed pattern clearly. There is concern that it will be difficult. On the other hand, if the coating amount is too large, the thickness of the middle layer is about 0.05 to 1.0 mm because the thickness of the middle layer is too thick, and there is a concern that warpage or the like is likely to occur. It is desirable to adjust the application amount so as to be as follows.

The viscosity of the mixture / dispersion of the synthetic resin emulsion or rubber latex, the inorganic filler and the various additives is set at 2,000 to ensure the surface smoothness of the undercoat layer and to prevent the dispersion of the coating. ~ 20,000 cp
It is desirable to adjust to about s.

The printing pattern layer formed on the above-mentioned undercoating layer is printed once to several times with a suitable printing machine such as a gravure printer using a commonly used solvent-based or water-based printing ink, It may be formed, or may be formed using so-called transfer paper or the like. Of course, this print pattern layer may include so-called solid printing.

The transparent top layer formed on the printed undercoat layer, like the undercoat layer, is a layer obtained by applying a synthetic resin emulsion or rubber latex containing no halogen and drying and solidifying the emulsion.

As the synthetic resin containing no halogen,
Acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, acrylamide,
Acrylic resin such as a homopolymer or copolymer of one or more acrylic monomers selected from acrylonitrile and the like, or a copolymer with other monomers copolymerizable with the above acrylic monomers An acrylic-styrene copolymer resin; an ethylene-vinyl acetate copolymer resin; a water-soluble polyester resin; and a mixture of one or more resins selected from the group.

As the synthetic resin contained in the synthetic resin emulsion forming the transparent top layer, a resin having a glass transition point of -30 ° C to 30 ° C is desirably used. In addition, as long as the properties of the obtained floor material are not impaired, a synthetic resin having a glass transition point exceeding 30 ° C. may be mixed with a synthetic resin having a glass transition point of 30 ° C. or less.

In the non-halogen floor material of the present invention, SBR latex, MBR latex, NBR latex, IIR latex are used instead of the above synthetic resin emulsion.
A transparent top layer can also be formed from one or a mixture of two or more rubber latexes such as latex.

The synthetic resin emulsion or rubber latex forming the transparent top layer may contain a so-called matting agent in an amount of 10 to 300 parts by weight, more preferably 50 to 1 part by weight, per 100 parts by weight of the synthetic resin or rubber solids.
It is desirable to add 50 parts by weight. By adding this matting agent, it is possible to suppress the stickiness of the surface of the obtained flooring material.

It is to be noted that an inorganic filler such as calcium carbonate or aluminum hydroxide can be added to the synthetic resin emulsion or rubber latex for forming the transparent top layer to suppress stickiness. Is unfavorable because a problem of impairing the transparency occurs.

As the above-mentioned matting agent, white fine particles such as silica, silicate and alumina can be used as they are. However, such white fine particles have poor dispersibility in a synthetic resin emulsion or rubber latex. It is desirable to use a sol in which white fine particles are dispersed, such as silica sol, silicate sol, alumina sol, titanium sol, and nickel sol. As the above white fine particles,
Those having an average particle size of about 7 to 50 nm are particularly suitable.

The above-mentioned matting agent has a glass transition point of 50 to 200 ° C, more preferably 80 to 120 ° C.
The average particle size is 1 to 100 μm, more preferably 10 to
Acrylic resin granules of 80 μm can also be used. Since the acrylic resin particles are excellent in dispersibility in the above synthetic resin emulsion, they can be added as they are without forming them into a sol as in the case of the above white fine particles. There is an advantage that no concentration is added. Further, by using the acrylic resin particles as a matting agent, there is an advantage that the surface strength (abrasion resistance, scratch resistance, etc.) of the transparent top layer (that is, floor material surface) is further improved.

When the transparent top layer is formed of a synthetic resin emulsion, as in the case of the intermediate layer,
In order to ensure cold resistance, it is necessary to use an emulsion of a synthetic resin having a glass transition point of 30 ° C. or lower,
Even when such a synthetic resin emulsion is used, there is a concern that the surface is sticky and dirt easily adheres. Therefore, it is necessary to eliminate the stickiness by adding the above-mentioned matting agent. . It is more preferable that the synthetic resin in the synthetic resin emulsion forming the transparent top layer has a glass transition point of -20 ° C to 0 ° C.
When the emulsion of such a synthetic resin is used, the addition amount of the matting agent is in the range described above, that is, 50 to 150 parts by weight per 100 parts by weight of the solid content of the synthetic resin. .

To the synthetic resin emulsion or rubber latex forming the transparent top layer, the obtained transparent top layer is imparted with further antifouling property and water whitening resistance (a property of preventing whitening when moisture adheres). For this purpose, a water repellent may be added in addition to the above matting agent. The amount of the water repellent added is 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, per 100 parts by weight of the solid content of the synthetic resin or rubber.

It should be noted that even when the above-mentioned acrylic resin granules are used as a matting agent, it is possible to add a water repellent, but the acrylic resin granules are used as a matting agent. In this case, a flooring material having sufficiently excellent antifouling property and water whitening resistance can be obtained without adding a water repellent.

The synthetic resin emulsion or rubber latex for forming the transparent top layer may contain, if necessary, a non-halogen flame retardant, a viscosity modifier, a drying delay, similarly to the synthetic resin emulsion or rubber latex for forming the intermediate layer. Agents, anti-adhesives, defoamers, antibacterial and antifungal agents, deodorants,
Various additives such as a crosslinking agent, a vulcanizing agent, and a dispersing agent can be added, and a small amount of a coloring agent can be added as long as the transparency is not impaired.

The synthetic resin emulsion or rubber latex to which the above-mentioned matting agent and various additives are added as required is uniformly mixed and dispersed by an appropriate mixer.
It is applied by an appropriate means such as a doctor knife coater, a roll coater, and an air knife coater, and is dried and solidified to form a transparent top layer.

When the transparent top layer is dried and solidified, it is preferable to raise the temperature to about three stages in order to form a uniform film. And completely solidified at a temperature that promotes self-crosslinking. Needless to say, the means for drying by raising the temperature to about three stages as described above is not limited to the case of forming the transparent top layer, but can also be employed in the case of forming the above-described undercoat layer or the backing layer described later.

If the transparent top layer is too thin, the printed pattern may be worn out during use because of poor abrasion resistance. If the transparent top layer is too thick, warpage is likely to occur. The thickness of the transparent top layer is 0.0
It is desirable to set it to about 5 to 0.3 mm.

Furthermore, the viscosity of the mixed / dispersed liquid of the synthetic resin emulsion or rubber latex, the inorganic filler and the various additives is used to secure the surface smoothness of the transparent top layer and to prevent the application unevenness. , 2000-
It is desirable to adjust to about 20,000 cps.

The non-foamed non-foamed backing layer formed on the back surface of the fibrous base material is a non-foamed layer formed of a halogen-free synthetic resin, rubber, or a mixture thereof.

The halogen-free synthetic resin includes polyethylene such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; ethylene-vinyl acetate copolymer and ethylene- (meth) acrylate ester copolymer. Ethylene copolymers such as polymers; homopolypropylene which is a homopolymer of propylene, random polypropylene which is a random copolymer of propylene and ethylene, block polypropylene which is a block copolymer of propylene and ethylene, etc. Polypropylene; butene-based polymers such as polybutene and butene-α-olefin copolymer; olefin-based, polyester-based, urethane-based and styrene-based thermoplastic elastomers; and mixtures thereof. Examples of the rubber containing no halogen include SBR, MBR, NBR and IIR.
And the like, synthetic rubbers and natural rubbers, and mixtures thereof. Incidentally, as the synthetic resin or rubber forming the backing layer, ethylene copolymers, thermoplastic elastomers,
Those having a certain degree of compression elasticity when formed into sheets, such as rubber, are preferred.

One or more inorganic fillers selected from calcium carbonate, aluminum hydroxide, magnesium hydroxide and the like are synthesized with the above synthetic resin or rubber forming the backing layer in consideration of flame retardancy. 50 per 100 parts by weight of resin
It is desirable to add 〜500 parts by weight, more preferably 100-300 parts by weight. In addition to the above-mentioned inorganic fillers, various additives such as antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers such as hindered amine compounds, lubricants, antibacterial and antifungal agents, deodorants, colorants and the like. Can be added as necessary.

The thickness of the backing layer is 0.5 to 3 mm,
More preferably, it is desired to be about 1 to 2 mm. If the backing layer is too thin, there is a concern that the function that the flooring material should originally have is impaired, such as a poor walking sensation, and if the thickness of the backing layer is too large, there is a concern that warpage is likely to occur.

Means for laminating a fibrous base material (hereinafter referred to as a surface decorative layer) on which the above-mentioned intermediate layer, printed pattern and transparent top layer are formed, and the above-mentioned backing layer are conventionally ordinarily performed. Any method may be used as long as it is a means. For example, a wet lamination method (wet lamination method) in which an adhesive is applied and the two are bonded, and then dried, and the adhesive is applied and dried, Means such as a dry lamination method (dry lamination method) in which both are bonded and pressed together, and a hot melt lamination method in which the two are immediately bonded after being heated and melted and then cooled to room temperature can be employed. Also, without using an adhesive as described above, the backing layer is formed by extruding a synthetic resin or the like forming a backing layer from the T-die of an extruder on the back surface of the surface decorative layer, and rolling it with a pair of rolls or the like. You can also.

Further, on the back surface of the backing layer formed as described above, a nonwoven fabric, a cold gauze, or a fabric such as the above-mentioned fibrous base material may be laminated. When such fabrics are laminated on the back surface, there is an advantage that the adhesive used at the time of construction is not restricted as in the case where the layer made of the synthetic resin or the like is used as the backmost layer.

When the fabrics are laminated on the back surface of the backing layer as described above, as a means for laminating the surface decorative layer and the backing layer, a synthetic resin or the like forming the backing layer is extruded from a T-die of an extruder. It is desirable to adopt a method of rolling with a roll or the like. If the backing layer is to be laminated by this method, the fabrics to be laminated can be rolled by a pair of rolls or the like, so that the fabrics can be laminated without increasing the number of steps. is there.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments.

FIG. 1 is a partially enlarged sectional view showing an embodiment of the flooring material of the present invention. In the drawing, reference numeral 1 denotes the flooring material of the present invention, reference numeral 21 denotes a fibrous base material, and reference numeral 22 denotes an intermediate layer. Reference numeral 23 denotes a transparent top layer (a laminate of “fibrous base material 21 / intermediate layer 22 / transparent top layer 23” is used as surface decorative layer 2) and reference numeral 3
Indicates a backing layer.

A method of manufacturing the flooring 1 shown in FIG. 1 will be described. First, a glass-pulp mixed nonwoven fabric (containing 50% by weight of glass fiber) having a thickness of 0.2 mm was used as a fibrous base material 21, and an acrylic material having the composition shown in Table 1 obtained by mixing the surface with a mixer was used. The acid ester copolymer resin emulsion was applied using a doctor knife coater, and dried in an oven to form a 0.1 mm thick (excluding the portion impregnated in the fibrous base material) intermediate layer 22.

[0048]

[Table 1]

Next, a printing pattern 24 is formed on the surface of the intermediate coating layer 22 by using a gravure printing machine to form a printing pattern 24.
Acrylic ester copolymer resin emulsion having the composition shown in Table 2 obtained by mixing with a mixer and coated with a mixer using a doctor knife coater, and dried in an oven, A transparent top layer 23 having a thickness of 0.1 mm was formed.

[0050]

[Table 2]

In this way, after forming the subbing layer 22, the printed pattern 24, and the transparent top layer 23 on the fibrous base material 21 sequentially, the design emboss 25 is applied to the surface of the transparent top layer 23, and the surface decorative layer is formed. 2 was formed.

An ethylene-vinyl acetate copolymer resin composition having the composition shown in Table 3 and forming a backing layer 3 on the back surface of the surface decorative layer 2 obtained as described above was used.
It was extruded in a sheet form from a die, and pressed together with a polyester nonwoven fabric 4 further laminated on the back side of the backing layer 3 with a pair of pressure rolls to obtain the flooring material of the present invention shown in FIG. In the example shown in FIG. 1, the thickness of the backing layer 3 is 1.5 m
m.

[0053]

[Table 3]

FIG. 2 shows a step of laminating the backing layer 3 and the polyester nonwoven fabric 4 on the back surface of the surface decorative layer 2.
The symbol T in the figure indicates a T die of the extruder, and R indicates a pressure roll.

[0055]

The non-halogen flooring material of the present invention has no problems in workability and has various properties required as a flooring material.
The material is equivalent to or better than flooring materials made of vinyl chloride resins which have been used conventionally.

[Brief description of the drawings]

FIG. 1 is a partially enlarged sectional view showing one embodiment of the flooring material of the present invention.

FIG. 2 shows an example of a process for laminating a backing layer and a nonwoven fabric further laminated on the back surface of the surface decorative layer (fibrous base material / intermediate layer / transparent top layer) in the flooring material of the present invention. FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Flooring material 2 Surface decorative layer 21 Fibrous base material 22 Intermediate layer 23 Transparent top layer 24 Print pattern 25 Design emboss 3 Backing layer 4 Nonwoven fabric

Claims (4)

(57) [Claims] At least a fibrous base material, an intermediate layer formed by applying and drying and solidifying a halogen-free synthetic resin emulsion or rubber latex on the fibrous base material,
A transparent top layer formed by applying and drying and solidifying a halogen-free synthetic resin emulsion or rubber latex on the printed pattern applied on the intermediate coating layer and the printed intermediate coating layer, and formed on the back of the fibrous base material A halogen-free non-foamed backing layer. 2. A synthetic resin contained in a synthetic resin emulsion forming an undercoat layer has a glass transition point of -30 ° C. to 3 ° C.
The non-halogen floor material according to claim 1, wherein the temperature is 0 ° C, and the synthetic resin emulsion or rubber latex contains 50 to 300 parts by weight of an inorganic filler per 100 parts by weight of the solid content of the synthetic resin or rubber. 3. The synthetic resin contained in the synthetic resin emulsion forming the transparent layer has a glass transition point of -30 ° C. to 3 ° C.
2. A synthetic resin emulsion or rubber latex containing 0 to 300 parts by weight of a matting agent per 100 parts by weight of synthetic resin solids or rubber solids at 0 ° C.
Or the non-halogen floor material according to 2. 4. A matting agent having a glass transition point of 50 to 20.
The non-halogen floor material according to claim 3, which is an acrylic resin particle having an average particle diameter of 1 to 100 µm at 0 ° C.