JP2015148083A - Floor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor material that has excellent wear resistance and flexibility and is hard to become dirty.SOLUTION: A floor material 1 is provided which includes: a floor material body 2 including a resin layer 3; and a surface layer 5 provided on the floor material body 2. The surface layer 5 includes: a polyolefin resin layer; and a polyamide resin layer stacked on the polyolefin resin layer through an adhesion layer. The polyolefin resin layer includes: an olefin homopolymer resin; an olefin copolymer resin; or a mixed resin of the olefin homopolymer resin and olefin copolymer resin. The floor material body 2 further includes a shape stabilization layer 4.

Description

  The present invention relates to a flooring material that is excellent in wear resistance and flexibility and is hardly soiled.

Conventionally, various flooring materials have been widely used. Among them, the resin flooring generally has a flooring main body and an upper layer laminated on the flooring main body, and the surface of the flooring main body is covered with the upper layer. In addition, in order to prevent wear due to dirt, wear, scratches, etc., a resin of a material resistant to dirt, wear, or scratches may be laminated on the surface of the upper layer. Examples of such a resin include an ultraviolet curable resin, hard vinyl chloride, a vinyl chloride generally used for a flooring material mixed with an antiwear additive, and other resins other than vinyl chloride.
For example, Patent Document 1 discloses an olefin-based flooring in which a surface protective layer made of an ultraviolet curable resin is provided on the surface of an olefin-based sheet.
However, since the surface protective layer made of an ultraviolet curable resin is hard, if it is formed to be relatively thick, there is a risk of cracking or cracking when the flooring is deformed along the uneven surface. On the other hand, when the thickness of the surface protective layer is reduced, part of the surface protective layer is easily lost due to aging, and the surface protective function of the flooring is not achieved.
Patent Document 2 discloses a laminated tile composed of at least a surface layer made of a coextruded film of a polyamide resin and an ethylene polymer and a resin layer made of an adhesive resin containing an inorganic filler. ing. This laminated tile has excellent abrasion resistance because the surface layer contains polyamide, but has a problem that it lacks flexibility. Normally, the floor material body is relatively flexible so as to absorb the unevenness of the floor surface, but if the surface layer lacking flexibility is laminated on the surface of the floor material body, the flexibility of the entire floor material May decrease and may not follow the unevenness of the floor. Furthermore, the floor material in which the ultraviolet curable resin or the polyamide resin is laminated on the surface of the floor material body also has a problem that it is easily warped.

JP 2002-105874 A JP 2000-103022 A

The first object of the present invention is to provide a flooring material that is excellent in wear resistance and flexibility and is hardly soiled.
A second object of the present invention is to provide a flooring material that is excellent in wear resistance and flexibility, is hardly soiled, and is less likely to warp.

  The flooring of the present invention has a flooring body having a resin layer, and a surface layer provided on the flooring body, and the surface layer is bonded onto the polyolefin resin layer and the polyolefin resin layer. And the polyolefin resin layer includes an olefin homopolymer resin, an olefin copolymer resin, or a mixed resin of an olefin homopolymer resin and an olefin copolymer resin. .

In a preferred floor material of the present invention, the floor material body further has a shape stabilizing layer.
In a preferred floor material of the present invention, the resin layer has an upper resin layer and a lower resin layer, and the shape stabilizing layer is interposed between the upper resin layer and the lower resin layer.
In a preferred flooring material of the present invention, the thickness of the upper resin layer is the same as or smaller than the thickness of the lower resin layer.

In a preferred flooring material of the present invention, the polyamide-based resin is at least one of 11-nylon and 12-nylon.
A preferred flooring material of the present invention has a dimensional change rate of ± 1.1% or less when stored for 7 days in an environment of 40 ° C. and 90% relative humidity.

  ADVANTAGE OF THE INVENTION According to this invention, it is excellent in abrasion resistance and a softness | flexibility, and can provide a flooring which is hard to get dirty. Since such a flooring material absorbs unevenness of the floor surface, it has a good appearance after construction and can be used in a clean state for a long time.

The top view of the flooring which concerns on 1st Embodiment of this invention. The expanded sectional view which cut | disconnected the flooring with the II-II line | wire of FIG. The expanded sectional view of the flooring concerning a 2nd embodiment (cutting in the same portion as the II-II line of Drawing 1). The expanded sectional view of the flooring concerning a 3rd embodiment (cutting in the same portion as the II-II line of Drawing 1). The expanded sectional view of the flooring concerning a 4th embodiment (cutting in the same portion as the II-II line of Drawing 1). The expanded sectional view of the flooring concerning a 5th embodiment (cutting in the same portion as the II-II line of Drawing 1). The expanded sectional view of an example of the surface layer used for the flooring. The expanded sectional view of the other examples of the surface layer used for the flooring. The expanded sectional view of the further another example of the surface layer used for the flooring. The graph which shows the result of the dimensional stability of the surface layer of Example 10. FIG. The graph which shows the result of the dimensional stability of the surface layer of Example 10. FIG. The graph which shows the result of the dimensional stability of the surface layer of Example 10. FIG. The graph which shows the result of the dimensional stability of the surface layer of Example 12. FIG.

Hereinafter, the present invention will be described with reference to the drawings as appropriate.
In this specification, the “surface” or “upper” of a layer refers to the surface or direction far from the floor on which the flooring is laid, and the “back” or “lower” refers to the opposite side (the flooring The surface or direction on the side near the floor to be laid.
In the present specification, a numerical range represented by “to” means a numerical range including numerical values before and after “to” as a lower limit value and an upper limit value.
In addition, it should be noted that dimensions such as thickness and size in each drawing are different from actual ones.

[Basic structure of flooring]
FIG. 1 is a plan view of the flooring of the first embodiment, and FIG. 2 is a cross-sectional view of the flooring of the first embodiment.
1 and 2, a flooring 1 according to the first embodiment includes a flooring main body 2 having a resin layer 3 and a surface layer 5 provided on the flooring main body 2. The flooring body 2 preferably further includes a shape stabilizing layer 4. The resin layer 3 preferably has an upper resin layer 31 and a lower resin layer 32, and the shape stabilizing layer 4 is interposed between the upper resin layer 31 and the lower resin layer 32. A decorative layer 6 is provided on the surface of the upper resin layer 31. Therefore, the flooring 1 of the first embodiment is configured by laminating the surface layer 5, the decorative layer 6, the upper resin layer 31, the shape stabilizing layer 4, and the lower resin layer 32 in this order from the upper side to the lower side. .

As shown in FIG. 1, the flooring 1 is formed in a long band shape in plan view. The long band shape is a rectangular shape in which the length in one direction is sufficiently longer than the length in the other direction (the other direction is perpendicular to the one direction). The length in the direction is 2 times or more, preferably 4 times or more. The long belt-like flooring 1 is usually wound on a roll and stored and transported, and is cut into a desired shape and used at a construction site. But the flooring 1 of this invention is not restricted to elongate strip | belt shape, You may form in sheet form, such as a planar view square shape (not shown).
The surface of the flooring 1 (in the case of this embodiment, the surface of the surface layer 5) may be embossed as necessary. Moreover, the back surface of the flooring 1 (in this embodiment, the back surface of the lower resin layer 32) may be embossed as necessary.

3 to 6 are cross-sectional views of floor materials according to second to fifth embodiments. In addition, the plan view of the flooring material of the second to fifth embodiments is omitted because it is the same as FIG.
In FIG. 3, the flooring material 1 according to the second embodiment has a lower resin layer 32 composed of two layers. The lower resin layer 32 may be composed of three or more layers. In FIG. 4, the flooring material 1 of 3rd Embodiment is comprised by the upper resin layer 31 by two layers. The upper resin layer 31 may be composed of three or more layers. Although not particularly shown, the lower resin layer 32 may be composed of two or more layers, and the upper resin layer 31 may be composed of two or more layers. When the lower resin layer 32 and / or the lower resin layer 32 is composed of two or more layers, the resin components of the layers constituting the resin layer 3 may be the same, the same, or different.

In FIG. 5, the flooring 1 of 4th Embodiment is provided with the base material layer 7 on the back surface of the resin layer 3 (lower resin layer 32).
In FIG. 6, in the flooring 1 of the fifth embodiment, the resin layer 3 is composed only of the lower resin layer. That is, the flooring 1 of the fifth embodiment does not have a resin layer between the shape stabilizing layer 4 and the surface layer 5, and the resin layer 3 is provided on the back side of the shape stabilizing layer 4. Although not particularly illustrated, the flooring 1 may be the flooring 1 that has the resin layer 3 between the shape stabilizing layer 4 and the surface layer 5 and does not have the resin layer 3 on the back side of the shape stabilizing layer 4.
Hereinafter, the floor material body 2 and the surface layer 5 of the floor material 1 of each of the above embodiments will be described in detail.

[Floor body]
The flooring main body 2 is a main part constituting the strength and weight of the flooring 1. In the present invention, the flooring body 2 preferably has at least the resin layer 3 and the shape stabilization layer 4. The specific thickness of the preferable floor material body 2 is, for example, 0.2 mm to 6 mm, preferably 1.5 mm to 5 mm, and more preferably 1.5 mm to 4.5 mm.

  The synthetic resin component of the resin layer 3 (the lower resin layer 32 and the upper resin layer 31) is not particularly limited, and conventionally known ones can be used, and generally a thermoplastic resin is used. Further, the resin components of the upper resin layer 31 and the lower resin layer 32 may be the same, the same, or different. The same kind of resin component means that the monomers constituting the main repeating unit of the resin component are the same, and when having a copolymer monomer, the copolymer monomer is different and / or the degree of polymerization is Including different cases. That the resin component is the same means that the repeating unit (and the copolymer monomer, if any) is the same, includes the case where the polymerization degrees are different.

Examples of the thermoplastic resin include vinyl chloride resins such as vinyl chloride and vinyl chloride-vinyl acetate copolymers; polyolefin resins; vinyl acetate resins such as ethylene-vinyl acetate copolymers; acrylics such as ethylene-methacrylate resins. Polyamide resins; ester resins; various elastomers such as olefin elastomers and styrene elastomers; rubbers and the like. These can be used alone or in combination of two or more. The resin layer 3 containing a vinyl chloride resin as a main component is preferable because it has excellent flexibility and is firmly adhered to the surface layer 5. The flooring 1 having the resin layer 3 mainly composed of a vinyl chloride resin is excellent in flexibility, and thus has a good feeling of walking, and further, while being curved, the floor surface (the construction surface on which the flooring 1 is laid) ). In addition, the vinyl chloride resin is inexpensive, and when it is used, the production of the flooring 1 is simplified.
As the vinyl chloride resin, those produced by an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like can be used. A vinyl chloride resin obtained by an emulsion polymerization method or a suspension polymerization method is preferred because it is easy to process and handle. These vinyl chloride resins may be used alone or in combination of two or more.
The vinyl chloride resin obtained by the emulsion polymerization method is obtained by coating a surfactant on the surface of a fine powder having a basic particle diameter of several μm or less (preferably 1 to 3 μm) composed of a large number of fine particle aggregates, A paste is formed by blending a plasticizer or the like. As the vinyl chloride resin by the emulsion polymerization method, those having an average degree of polymerization of about 1000 to 2000 are preferably used.
The vinyl chloride resin obtained by the suspension polymerization method is preferably a fine powder of 20 to 100 μm, and is used after being processed into a sheet by a calendar molding method. The vinyl chloride resin by the suspension polymerization method preferably has an average degree of polymerization of about 700 to 1500, more preferably about 700 to 1000, from the viewpoint that roll tackiness suitable for the calendar molding method can be imparted. preferable.
Each vinyl chloride resin preferably has a K value of about 60 to 95, and more preferably has a K value of about 65 to 80.
As the vinyl chloride, a commercially available product can be used. For example, in addition to the vinyl chloride resin used in the following examples, “ZEST 70L” (K value: 60.5 to 63.63) manufactured by Shin-Daiichi PVC Co., Ltd. 1. Degree of polymerization 650 to 730), “ZEST 800Z” (K value 60.3 to 62.8, degree of polymerization 750 to 850). In addition, when using a vinyl chloride-vinyl acetate copolymer in place of or in combination with vinyl chloride, “MB1008” (K value 56.0-59.0, manufactured by Kaneka Corporation). 8 to 12%).
The resin layer 3 usually contains various additives in addition to the resin. As the additive, conventionally known ones can be used, and examples thereof include a filler, a plasticizer, a flame retardant, a stabilizer, an antioxidant, a lubricant, a colorant, a foaming agent, and an antifungal agent.

The resin layer 3 may be non-foamed or foamed. In the first embodiment, the resin layer 3 includes the upper resin layer 31 and the lower resin layer 32. For example, one of the upper resin layer 31 and the lower resin layer 32 is a foamed resin and the other is a non-foamed resin. Or both may be made of non-foamed resin or foamed resin.
The expansion ratio of the foamed resin is not particularly limited, but is preferably 1.2 times to 20 times, and more preferably 1.5 times to 4 times. If the expansion ratio is too low, the flooring 1 cannot be substantially cushioned. On the other hand, if the expansion ratio is too high, the flooring 1 becomes too soft.

The thickness of the upper resin layer 31 and the thickness of the lower resin layer 32 may be the same, or one of them may be small. Since the warpage can be effectively suppressed, the thickness of the upper resin layer 31 is preferably the same as the thickness of the lower resin layer 32 or smaller than the thickness of the lower resin layer 32, and the thickness of the upper resin layer 31 is smaller than that of the lower resin layer 32. More preferably, it is smaller than the thickness. Specifically, the thickness of the upper resin layer 31 is preferably 0.05 to 0.8 times the thickness of the lower resin layer 32, more preferably 0.1 to 0.5 times, and more preferably 0.1 to 0.3 times is particularly preferable.
The specific thickness of the upper resin layer 31 is, for example, 0.1 mm to 5 mm, preferably 0.2 mm to 3 mm, and more preferably 0.2 mm to 2 mm. The specific thickness of the lower resin layer 32 is, for example, 0.1 mm to 5 mm, preferably more than 1 mm and 4 mm or less, and more preferably 1.5 mm to 3.5 mm.

The shape stabilizing layer 4 is a layer for suppressing a dimensional change of the flooring 1 due to shrinkage and expansion over time, and further for suppressing warpage in cooperation with the surface layer 5.
As the shape stabilizing layer 4, a nonwoven fabric or a woven fabric can be used. The material of the fibers constituting the nonwoven fabric and the woven fabric is not particularly limited, and examples thereof include synthetic resin fibers such as polyester and polyolefin; inorganic fibers such as glass and carbon; natural fibers and the like. It is preferable to use a glass fiber nonwoven fabric as the shape stabilizing layer 4 because the dimensional stability of the flooring 1 can be enhanced, the dimensional variation is extremely small compared to organic fibers, and the familiarity with the resin is good.
The thickness of the shape stabilizing layer 4 is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.07 mm to 0.4 mm, and further preferably 0.07 mm to 0.35 mm. It is. If the thickness of the shape stabilizing layer 4 is too small, the effect of suppressing dimensional change and warping is small. On the other hand, if the thickness of the shape stabilizing layer 4 is too large, the feeling of use of the flooring 1 may be reduced.
Note that the nonwoven fabric made of fibers such as glass fibers, preferably has weight per unit area of ^{10g / m 2 ~100g / m 2} , ^further ones of 30g / ^{m 2} ~50g / m 2 is more preferable.

The decorative layer 6 is a layer that imparts a design to the flooring 1. The decorative layer 6 is provided as necessary. The decorative layer 6 may be provided on the surface of the flooring main body 2 or may be provided inside the flooring main body 2. The decorative layer 6 may be provided directly on the back surface of the surface layer 5, and the surface layer 5 with the decorative layer may be laminated on the surface of the flooring body 2.
The decorative layer 6 may be composed of a design printing transfer layer or a design printing layer, or may be composed of a thermoplastic resin layer. The transfer layer is formed by transferring a design-transferred transfer sheet to the front surface of the resin layer 3 or the back surface of the surface layer 5. The design printing layer can be formed by directly applying design printing or laminating a design printing sheet on the front surface of the resin layer 3 or the back surface of the surface layer 5. Examples of the thermoplastic resin layer include those exemplified in the column of the resin layer 3. Since the thermoplastic resin layer is firmly adhered to the resin layer 3 and the surface layer 5, a resin mainly composed of a vinyl chloride resin is used. preferable. A colorant may be mixed in the thermoplastic resin layer. In the thermoplastic resin layer, a colorant and a resin chip exhibiting a color other than the color of the colorant may be mixed.
Although the thickness of the said decorative layer 6 is not specifically limited, For example, they are 1 micrometer-1 mm, Preferably they are 2 micrometers-0.3 mm. In the case where the decorative layer 6 is composed of a design printing transfer layer or a design printed layer, the thickness of the decorative layer 6 may be less than 1 μm.

The said base material layer 7 is a layer located in the backmost surface of the flooring main body 2 (flooring material 1). The base material layer 7 is provided as necessary. By providing the base material layer 7, the warp of the flooring 1 can be more effectively suppressed.
Examples of the base material layer 7 include non-woven fabric (including felt), woven fabric, paper, and the like, preferably non-woven fabric or woven fabric, more preferably non-woven fabric. By using a non-woven fabric or a woven fabric, the base resin layer 3 is impregnated with the synthetic resin component of the resin layer 3, and the warp of the flooring 1 can be more effectively prevented.
Examples of the nonwoven fabric include spunbond nonwoven fabric, thermal bond nonwoven fabric, chemical bond nonwoven fabric, needle punch nonwoven fabric, and spunlace nonwoven fabric. These can be used alone or in combination of two or more. Among these, it is preferable to use a spunbond nonwoven fabric. The material of the fibers constituting the nonwoven fabric and the woven fabric is not particularly limited, and examples thereof include synthetic resin fibers such as polyester and polyolefin; inorganic fibers such as glass and carbon; natural fibers and the like.
Although the thickness of the said base material layer 7 is not specifically limited, For example, it is 0.1 mm-0.5 mm, Preferably it is 0.2 mm-0.4 mm.

[Surface]
The surface layer 5 is a layer provided to prevent dirt from adhering to the floor material surface.

As shown in FIG. 7, the surface layer 5 includes a polyolefin resin layer 53, an adhesive layer 52 laminated on the polyolefin resin layer 53, a polyamide resin layer 51 laminated on the adhesive layer 52, These are composed of laminated sheets laminated in this order. In addition, the “sheet” in this specification is generally called a film. The polyolefin resin layer 53 and the polyamide resin layer 51 are directly bonded via an adhesive layer 52. Such a surface layer 5 is excellent in wear resistance and further excellent in transparency. Since the surface layer 6 is excellent in transparency, the flooring 1 having the surface layer 5 can clearly visually recognize the design of the decorative layer provided on the back side of the surface layer 5 (when no decorative layer is provided). The coloration of the flooring main body 2 can be clearly recognized.
In addition, although the flooring main body is laminated | stacked on the back surface side (under the paper surface of FIG. 7) of the surface layer, the flooring is not illustrated in FIG. 7 (the same applies to FIGS. 8 and 9).

(Polyamide resin layer)
The polyamide resin constituting the polyamide resin layer 51 is a polymer obtained by polymerization of lactam or aminocarboxylic acid or polycondensation of diamine and dicarboxylic acid. The polyamide resin may be a homopolymer or a copolymer. Further, the polyamide-based resin may be a single type or a mixed mode of a plurality of types. By using a polyamide-based resin for the polyamide-based resin layer 51, appropriate wear resistance can be imparted to the flooring 1.

Examples of the lactam include butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
Examples of the aminocarboxylic acid include ω-aminocarboxylic acid and α, ω-amino acid, which are compounds in which the above lactam is ring-opened. The aminocarboxylic acid may be a linear or branched saturated aliphatic carboxylic acid substituted at the ω position with an amino group, such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecane. An acid etc. are mentioned. Furthermore, the aminocarboxylic acid may be an aromatic aminocarboxylic acid, and examples thereof include paraaminomethylbenzoic acid.

Examples of the diamine include aliphatic diamines and aromatic diamines.
Examples of the aliphatic diamine include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine. , And linear aliphatic diamines such as tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, And branched aliphatic diamines such as 2,4-dimethyloctamethylenediamine. Furthermore, alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine are also included.
Examples of the aromatic diamine include aromatic diamines such as metaxylylenediamine, orthoxylylenediamine, and paraxylylenediamine.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2,3-diethylglutaric acid. Acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, Examples thereof include linear or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as octadecanedioic acid, eicosanedioic acid, and diglycolic acid.
Examples of the aromatic dicarboxylic acid include unsubstituted or terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Examples thereof include aromatic dicarboxylic acids having 8 to 20 carbon atoms substituted with various substituents.

  The dicarboxylic acid includes not only the above dicarboxylic acid compound but also a compound equivalent to the above dicarboxylic acid. The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the above-mentioned dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acid. Is mentioned.

  The main monomer component (at least one of lactam, aminocarboxylic acid, or diamine and dicarboxylic acid) constituting the polyamide-based resin more preferably has an aliphatic hydrocarbon chain having 10 or more carbon atoms. The upper limit of the carbon number is not particularly limited, but is 20, for example. Alternatively, the ratio of carbon number to amide group number (carbon number / amide group number) in the polyamide-based resin is, for example, 8 or more, preferably 9 or more, more preferably 10 or more, and further preferably 11 or more. The upper limit of the ratio of carbon numbers is not particularly limited, but is 20, for example.

  By using the polyamide-based resin having a relatively long hydrocarbon chain as described above, the polyamide-based resin layer 51 can be made of a resin having a low hygroscopic property. The water absorption of the polyamide-based resin is preferably 8.0% by weight or less, more preferably 4.0% by weight or less, still more preferably 1.5% by weight or less, and further preferably 0.5% by weight or less. . Further, the polyamide resin may have a melting point of 160 ° C. to 270 ° C. This makes it easy to select versatile engineering plastic as the polyamide resin.

  More specifically, as polyamide-based resin, nylon 6, nylon 66, nylon 46, nylon 10, nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, a copolymer of metaxylylenediamine and adipic acid (Nylon MXD6), nylon 66/6 copolymer, copolymer of paraaminomethylbenzoic acid and ε-caprolactam (nylon AHBA), 2,2,4- / 2,4,4-trimethylhexamethylenediamine terephthalate Polyamides mainly composed of acid salts (nylon THDT, THDT / 6I) and the like can be used. In view of low hygroscopicity, among the above examples, nylon 10, nylon 610, nylon 612, nylon 1010, nylon 11, and nylon 12 are preferably used.

  The polyamide-based resin layer 51 may contain an additive. The additive can be appropriately determined by those skilled in the art in consideration of the manufacturing process of the surface layer 5 and / or the application to the flooring 1. Additives include, for example, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antiblocking agents (inorganic particles such as silica and aluminosilicates), fillers (calcium carbonate) Inorganic fillers such as magnesium hydroxide, aluminum hydroxide, and titanium oxide, and organic fillers such as polymer beads).

  The thickness of the polyamide-based resin layer 51 is not particularly limited. For example, the thickness of the entire surface layer is 0.1 times or more, preferably more than 0.15 times, more preferably 0.2 times or more, and the upper limit is For example, it is 0.9 times or less. If it is below the above range, it tends to be difficult to ensure the wear resistance of the surface layer 5, and if it exceeds the above range, it is difficult to ensure the flexibility of the surface layer 5.

(Adhesive layer)
As the adhesive resin constituting the adhesive layer 52, a resin that adheres the polyamide resin layer 51 and the polyolefin resin layer 53 is used.
Examples of the adhesive resin include a modified polyolefin resin modified with an unsaturated carboxylic acid or an acid derivative, and a polymer and a mixture of the modified polyolefin resin and the polyolefin resin.

  The modified polyolefin resin is a copolymer of an olefin monomer as a main component and an unsaturated carboxylic acid or acid derivative. For example, it may have a structure in which a polyolefin is the main chain and an unsaturated carboxylic acid or acid derivative is grafted.

  As said polyolefin principal chain, the polymer or copolymer of a C2-C8 alpha olefin or a propylene is mentioned, for example. In the case of a copolymer, examples of the copolymerization mode include alternating copolymerization, random copolymerization, and block copolymerization. For example, the polyolefin main chain may be a random and / or block copolymer of polyethylene resin or polypropylene resin and other α-olefin, specifically, polypropylene-ethylene copolymer, propylene-1-hexene. Examples thereof include a copolymer, a propylene-4-methyl-1-pentene copolymer, poly-4-methyl-1-pentene, and polybutene-1. These resins can be used alone or in combination of two or more.

Examples of the polyethylene resin include high density type (HDPE), medium density type (MDPE), low density type (LDPE), and linear low density type (L-LDPE) polyethylene, and ethylene-α olefin copolymer, And ethylene-vinyl acetate copolymer. These resins can be used alone or in combination of two or more.
Polypropylene resins include random and / or block copolymers of isotactic polypropylene or propylene and other small amounts of α-olefins, specifically propylene-ethylene copolymers and propylene-1-hexene copolymers. Examples thereof include polymers, poly-4-methyl-1-pentene, and polybutene-1. From the viewpoint of heat resistance, a polypropylene structure is preferable. These resins can be used alone or in combination of two or more.

Examples of the unsaturated carboxylic acid include dibasic unsaturated fatty acids and anhydrides thereof. More specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid and the like can be mentioned.
Acid derivatives include anhydrides, amides, and esters, and more specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, vinyl acetate, glycidyl. Examples include acrylate, glycidyl methacrylate, acrylamide, methacrylamide, and sodium acrylate. These acid compounds can be used alone or in combination of two or more.

  Examples of the polyolefin resin that may be further polymerized or mixed with the modified polyolefin resin include, for example, polymers of α-olefins having 2 to 8 carbon atoms.

  The Vicat softening point of the resin constituting the adhesive layer 52 is preferably 80 ° C. or higher. Below 80 ° C., the adhesive strength tends to be unstable under high temperature and high humidity conditions. The upper limit value of the Vicat softening point is not particularly limited, but is 120 ° C., for example.

  The adhesive layer 52 may be substantially free of inorganic filler. “Substantially free of inorganic filler” means that the inorganic filler is not included at all, or includes more than 0 wt% and less than 10 wt%, preferably more than 0 wt% and not more than 5 wt%. It is an acceptable meaning. Here, the inorganic filler refers to calcium carbonate, magnesium hydroxide, aluminum hydroxide, titanium oxide and other arbitrary inorganic fillers.

  Although the thickness of the contact bonding layer 52 is not specifically limited, For example, it is 0.02 to 0.2 times the thickness of the whole surface layer, Preferably it is 0.04 to 0.15 times. The adhesive layer 52 having such a thickness can make use of the properties of both the polyamide-based resin layer 51 and the polyolefin-based resin layer 53 while ensuring the adhesiveness.

  Further, the adhesive layer 52 is manufactured by a dry laminate in which the surface layer 5 is prepared by preparing the polyamide-based resin layer 51 and the polyolefin-based resin layer 53, and applying and bonding an adhesive between the two layers. In some cases, it may be constituted by the adhesive. In this case, examples of the adhesive include isocyanate-based, urethane-based, imine-based, and titanate-based adhesives.

(Polyolefin resin layer)
The polyolefin resin layer 53 is an olefin homopolymer resin, an olefin copolymer resin, or a mixture of an olefin homopolymer resin and an olefin copolymer resin. By using the resin as described above as the polyolefin-based resin layer 53, appropriate flexibility can be imparted to the flooring 1. Furthermore, when mixing and using an olefin homopolymer resin and an olefin copolymer resin, transparency can be provided, maintaining mechanical strength.

The olefin homopolymer resin is a branched polyolefin composed substantially only of olefin monomers. Examples of the olefin monomer include α-olefins having 2 to 8 carbon atoms. The olefin homopolymer resin is preferably polyethylene or polypropylene from the viewpoint of flexibility. Particularly in the case of polyethylene, from the viewpoint of transparency, the density of the ethylene homopolymer resin is preferably less than 910 kg / ^{m 3} or more 930 kg / ^{m 3.} A preferred example of such branched polyethylene is low density polyethylene (LDPE).

  The olefin copolymer resin is a resin composed of an olefin monomer and another comonomer. Examples of copolymerization modes include alternating copolymerization, random copolymerization, and block copolymerization. Preferably, a linear olefin copolymer resin having a polyolefin linear chain as a main chain and a side chain derived from a comonomer. It is. In addition, as the olefin copolymer resin, the following resins may be used alone or in a mixed manner.

  Examples of the comonomer of the olefin copolymer resin include at least one of other α-olefins, vinyl compounds, and acrylamide compounds.

  The α-olefin as the comonomer has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. More specifically, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like can be mentioned. These α-olefins may be used alone or in combination of two or more.

  More specific examples of the ethylene copolymer resin having an α-olefin as a comonomer include linear low density polyethylene (L-LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

  Examples of the vinyl compound as the comonomer include unsaturated carboxylic acids such as vinyl acetate and methyl (meth) acrylate, and unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether. These vinyl compounds may be used alone or in combination of two or more. From the viewpoint of ensuring transparency, the copolymerization ratio of the vinyl compound is, for example, 60% by weight or less, preferably 50% by weight or less.

  The acrylamide compound as the comonomer may be, for example, N-alkyl acrylamide, N, N-dialkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl methacrylamide and the like. Specifically, N-ethylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, Nn-butylacrylamide, N-isobutylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, Nn-propylmethacrylamide, Nt-butylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-methyl-N-ethyl Examples include acrylamide. These acrylamide compounds may be used alone or in combination of two or more. The copolymerization ratio of the acrylamide compound is, for example, from 0.01% by weight to 50% by weight, and preferably from 0.05% by weight to 45% by weight, from the viewpoint of ensuring transparency and ensuring mechanical strength. .

  In the mixture, the mixing ratio of the olefin copolymer resin to the olefin homopolymer resin (olefin copolymer resin / olefin homopolymer resin) is, for example, 1 to 35 on a weight basis, preferably 1 to 19, more preferably 5 to 5. 9, particularly preferably 2 to 5.5, and 4 is an example. By setting the mixing ratio within the above range, the surface layer 5 having good mechanical strength and low haze can be obtained.

  An additive may be used for the polyolefin resin. Examples of the additive include a transparency improver (for example, lithium carbonate), a light stabilizer, an ultraviolet absorber, an antioxidant, a lubricant, and an antiblocking agent (that is, AB agent).

  The thickness of the polyolefin-based resin layer 53 is not particularly limited. For example, the thickness of the entire surface layer is 0.1 times or more, preferably 0.16 times or more, more preferably 0.2 times or more, and the upper limit is For example, it is 0.9 times or less. Below the above range, it is difficult to ensure the flexibility of the surface layer 5. When it exceeds the above range, it tends to be difficult to ensure the wear resistance of the surface layer 5.

The thickness of the polyolefin resin layer 53 is 0.1 to 9 with respect to the thickness of the polyamide resin layer 51 (that is, the ratio of the thickness of the polyolefin resin layer 53 / the thickness of the polyamide resin layer 51), for example, Preferably it is 0.3-7. If it falls below the above range, the surface layer 5 tends to have a relatively small amount of flexibility, and if it exceeds the above range, the wear resistance tends to be relatively small.
Since the surface layer 5 is formed by laminating the polyamide resin layer 51 and the polyolefin resin layer 53, both the wear resistance and flexibility suitable for the flooring 1 can be imparted to the friction and bending. And become stronger. Furthermore, in the polyolefin-type resin layer 53, since the olefin homopolymer resin and olefin copolymer resin are mixed and used, it can be set as the surface layer 5 with high mechanical strength, and high transparency.

  The haze (Haze value) of the surface layer 5 of the present invention is preferably 8 or less, because it is excellent in transparency and the design of the decorative layer 6 can be visually recognized. In particular, it is more preferably 7 or less because it can be seen well. . The haze (Haze value) is determined according to JIS K7136 (2000) by using a haze meter (turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd., “NDH2000”, light source D65). It can be measured by entering light from the surface side.

  Moreover, since the surface layer 5 has a small dimensional change rate, it is excellent in the curvature suppression effect. Specifically, the surface layer 5 has a dimensional change rate of, for example, ± 1.1% or less, preferably ± 0.5% or less, more preferably ± 0.2% at 40 ° C., a relative humidity of 90% or less, and storage for 7 days. % Or less. In this case, the dimensions of the surface layer 5 hardly change even under wet conditions of about 90% relative humidity and dry conditions of about 4% relative humidity.

  The Young's modulus (JIS K7127) of the surface layer 5 is, for example, 300 MPa to 800 MPa, preferably 300 MPa to 450 MPa. The tensile strength (JIS Z1702) of the surface layer 5 is, for example, 30 MPa to 70 MPa, preferably 30 MPa to 60 MPa. Furthermore, the elongation (JIS Z1702) of the surface layer 5 is, for example, 350% to 500%, preferably 400% to 500%. The surface layer 5 satisfying at least one of these physical properties has preferable flexibility. It is sufficient that at least any one of these physical properties is satisfied, but it is preferable that all of them are satisfied. By using the surface layer 5 having preferable flexibility, it is possible to configure the flooring 1 having moderate cushioning properties and appropriate rigidity, and hardly causing undesired deformation.

  Although the specific thickness of the whole surface layer is not specifically limited, For example, it is 0.05 mm-1 mm, Preferably it is 0.1 mm-0.5 mm, More preferably, it is 0.1 mm-0.2 mm.

(Other examples of surface layer)
The surface layer 5 is not limited to the layer configuration as shown in FIG. For example, as shown in FIG. 8, the polyamide-based resin layer 51 may be composed of two layers. These two layers are composed of two different types of polyamide resins. The first polyamide resin layer 511 and the second polyamide resin layer 512 are preferably composed of resins having different hygroscopic properties and / or resins having different abrasion resistances.
For example, the first polyamide resin layer 511 constituting the outermost layer can be made of a polyamide resin having lower hygroscopicity than the second polyamide resin layer 512. That is, a polyamide resin excellent in moisture absorption resistance can be used only for the outermost layer that is in direct contact with the external environment. As a result, the polyamide-based resin layer 51 can be manufactured at a low cost while ensuring the desired moisture absorption resistance.

  In addition, the first polyamide resin layer 511 can be made of a polyamide resin having higher wear resistance than the second polyamide resin layer 512. That is, a polyamide-based resin having high wear resistance can be used only for the outermost layer that is directly subjected to external impact. Thereby, the polyamide-based resin layer 51 can be manufactured at a low cost while ensuring desired wear resistance.

  Furthermore, the first polyamide resin layer 511 and the second polyamide resin layer 512 are made of polyamide resins having different moisture absorption resistance, wear resistance, melting point, and other characteristics, respectively, so that the polyamide resin The layer 51 can be multifunctional. More specifically, for example, by forming the first polyamide resin layer 511 with a polyamide resin having a higher melting point, resistance to melting due to friction is increased.

The thickness of the first polyamide resin layer 511 is, for example, 0.1 to 0.9 times the thickness of the entire polyamide resin layer 51, and preferably 0.2 to 0.8 times.
Moreover, the said polyamide-type resin layer 51 may be comprised by 3 or more layers. In addition, the adhesive layer 52 and the polyolefin-based resin layer 53 may also be composed of two or more layers independently.

Further, the outermost surface of the surface layer 5 (the back surface of the polyolefin-based resin layer 53) may be subjected to a hydrophilic treatment. Examples of the hydrophilic treatment include corona discharge treatment, plasma treatment, flame (flame) treatment, ultraviolet irradiation treatment, and combustion chemical vapor deposition treatment. By performing the hydrophilic treatment, the adhesion between the back surface of the surface layer 5 and the surface of the flooring body 2 is improved. In particular, when a decorative layer is provided on the back surface of the surface layer 5, the decorative layer is And can be firmly bonded.
The wetting index (JIS K6768) on the outermost surface of the surface layer 5 subjected to the hydrophilic treatment is, for example, 35 dynes to 55 dynes, and preferably 35 dynes to 45 dynes.

  For example, as shown in FIG. 9, the primer layer 8 may be provided on the back surface of the surface layer 5. The surface layer 5 in FIG. 9 includes a polyamide-based resin layer 51, an adhesive layer 52, a polyolefin-based resin layer 52, a decorative layer 61, and a primer layer 8 in order from the top. If the decorative layer 61 is provided on the back surface of the surface layer 5, the adhesion between the surface layer 5 and the floor material body 2 may be reduced. However, by providing the primer layer 8, the surface layer 5 can be firmly bonded to the floor material body 2. . Resins used for the primer layer include ester resins, urethane resins, acrylic resins, polycarbonate resins, polyvinyl chloride resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, etc. Can be mentioned. These resins can be used alone or in combination. The primer layer can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

The surface layer 5 can be formed by a general method as a method for forming a laminated film, for example, a coextrusion method, a thermal bonding method, an extrusion lamination method, a dry lamination method, an extrusion dry lamination method, a vacuum deposition method, or the like. However, a coextrusion method is preferably used. The coextrusion method is preferable when the surface layer 5 is formed as a thin layer having an overall thickness of 25 μm or less because it can be formed with uniform adhesive strength and less defects such as wrinkles.
For example, the surface layer 5 can be manufactured by a coextrusion method in which a polyolefin resin, an adhesive resin, and a polyamide resin are melted and formed at a time. Examples of the coextrusion method include a coextrusion method using a T die and a coextrusion method using inflation. For example, when forming the surface layer 5 in which one polyamide-based resin layer 51 is assumed to be relatively thick, the co-extrusion method using a T die is preferable from the viewpoint of film formation. In addition, the surface layer 5 may be manufactured by a dry laminating method in which each layer is sequentially laminated.

[Method for producing flooring of the present invention]
The flooring 1 of the present invention can be manufactured, for example, as follows.
For example, the floor material body 2 may be a paste sol gel method or a calender molding method using known equipment such as a roll or calender molding machine, an extruder, an injection molding machine, a blow molding machine, a laminating apparatus, or a casting molding apparatus. It can be formed by a melt extrusion method, a solvent casting method, an inflation method, or the like. Among these, the calender molding method is preferable because the floor material body 2 having high strength and high water resistance can be formed. For example, the case where the flooring 1 having the flooring main body 2 shown in FIG.
(1) First, a vinyl chloride resin, a plasticizer, a stabilizer and a filler are kneaded, and the mixture is formed into a sheet by a calendering machine. Thereby, the lower resin layer 32 is obtained.
(2) Next, the shape stabilizing layer 4 is placed on the lower resin layer 32, and this is rolled between calendar rolls. Thereby, the shape stabilizing layer 4 is integrated with the lower resin layer 32.
(3) Next, a vinyl chloride resin, a plasticizer, a stabilizer and a filler are kneaded, and the mixture is formed into a sheet by a calendering machine. Thereby, the upper resin layer 31 is obtained. The upper resin layer 31, the shape stabilizing layer 4 and the lower resin layer 32 are integrated with each other by superimposing the upper resin layer 31 on the shape stabilizing layer 4 and rolling and bonding the upper resin layer 31 between calendar rolls. The floor material body 2 is obtained.
(4) The back surface of the polyolefin-based resin layer 53 of the surface layer 5 is placed on the upper resin layer 31, and the floor material body 2 and the surface layer 5 are integrated by rolling and joining again between the calender rolls. It is possible to obtain a floor material 1 that has been turned into a floor.

  In addition, when the flooring body 2 is formed by a paste sol gel method, a resin material composed of additives such as a vinyl chloride resin and a plasticizer is applied to a development surface such as a development film, A shape stabilizing layer 4 such as a glass nonwoven fabric is placed, and a vinyl chloride paste is applied thereon to form a laminate of the upper resin layer 31, the shape stabilizing layer 4 and the lower resin layer 32. Pregelled at 140 ° C to 150 ° C. When the decorative layer 6 is provided, the design is printed or transferred from the transfer sheet. Thus, the flooring main body 2 before gelation can be obtained.

The back surface of the polyolefin resin layer 53 of the surface layer 5 is placed on the surface of the upper resin layer 31 of the floor material body 2 before gelation, and the whole is heated. The heating temperature is preferably 160 ° C to 200 ° C. The heating time is preferably 2 to 10 minutes. By heating, the vinyl chloride resin is gelled, and the flooring 1 in which the flooring main body 2 and the surface layer 5 are integrated can be obtained.
In addition, in order to improve the adhesiveness of the surface layer 5 and the flooring main body 2, you may adhere | attach both, after embossing to at least one surface of the back surface of the surface layer 5, and the surface of the flooring main body 2. FIG.

  Although the surface of the flooring material is worn or soiled by the shoe sole or the like, the flooring material 1 of the present invention is provided with the surface layer 5 as described above on the surface of the flooring material body 2, so that it has high wear resistance. Excellent and hard to get dirty. Moreover, since the surface layer 5 is excellent in flexibility, the floor material body 2 is not hindered, and when the floor material 1 of the present invention is constructed, the floor surface is uneven. 1 is difficult to reflect, and the construction appearance of the flooring is also good. Further, the flooring 1 of the present invention having the shape stabilizing layer 4 is less likely to warp, and in particular, the floor of the upper resin layer 31 is the same as the thickness of the lower resin layer 32 or smaller than the thickness of the lower resin layer 32. The flooring 1 having the material body 2 can effectively suppress warping over time.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

[Example 1]
Nylon 6 (6Ny) (“Ube Nylon 1022B” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF308” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (manufactured by Prime Polymer) A mixed resin of “Neozex 2540R”) and branched low density polyethylene (LDPE) (“Ube Polyethylene F522” manufactured by Ube Maruzen Polyethylene) is melt-cast by a co-extrusion method using a T-die, and 6Ny / AD / LLDPE + LDPE A surface layer having a total thickness of 150 μm laminated in order was obtained. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 97/3 (weight basis).
The thickness of the 6Ny layer after film formation was 52.5 μm, the thickness of the AD layer was 15 μm, and the thickness of the mixed resin layer of LLDPE and LDPE was 82.5 μm.

[Example 2]
The surface layer was formed in the same manner as in Example 1 except that the mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 80/20 (weight basis) and the thickness of each layer after film formation was changed as follows. Produced. The thickness of the 6Ny layer was 37.5 μm, the thickness of the AD layer was 15 μm, and the thickness of the mixed resin layer of LLDPE and LDPE was 97.5 μm.

[Example 3]
Nylon 12 (12Ny) (“Ube Nylon 3030U” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical) A mixed resin of “Sumikasen L211”) and branched low density polyethylene (LDPE) (“Ube Polyethylene F522” manufactured by Ube Maruzen Polyethylene) was melt-formed by co-extrusion using a T-die, and 12Ny / AD / LLDPE + LDPE A surface layer having a total thickness of 150 μm laminated in order was obtained. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 80/20 (weight basis).
The thickness of the 12Ny layer after film formation was 120 μm, the thickness of the AD layer was 7.5 μm, and the thickness of the mixed resin layer of LLDPE and LDPE was 22.5 μm.

[Example 4]
A surface layer was produced in the same manner as in Example 1 except that the thickness of each layer after film formation was changed as follows. The thickness of the 12Ny layer after film formation was 45 μm, the thickness of the AD layer was 7.5 μm, and the thickness of the mixed resin layer of LLDPE and LDPE was 97.5 μm.

[Evaluation of mechanical properties]
For Examples 1 to 4, the following physical properties relating to mechanical properties were measured. The measurement results are shown in Table 1.
(Flexibility)
The tensile strength was measured based on a test method based on JIS Z1702.
The elongation percentage was measured based on a test method based on JIS Z1702.
The Young's modulus was measured based on a test method based on JIS K7127.
(Abrasion resistance)
A wear test was performed based on a test method based on JIS A1453. A sample which was subjected to 2000 rotations and was resistant was evaluated as “good”.

[Example 5]
Nylon 12 (12Ny) (“UBESTA 3030U” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (“Sumitomo Chemical” Sumikacene L211 ") and branched low-density polyethylene (LDPE) (" F522 "made by Ube Maruzen Polyethylene) are melted into a film by co-extrusion using a T-die and laminated in the order of 12Ny / AD / LLDPE + LDPE The obtained surface layer was obtained. The thickness of the 12Ny layer after film formation was 50 μm, the thickness of the AD layer was 10 μm, and the thickness of the mixed resin layer of LLDPE and LDPE was 90 μm.
In Example 5, the ratio of LLDPE to LDPE (LLDPE / LDPE) was 90/10. The ratio is based on weight.
About the surface layer formed into a film, the haze was measured by the method based on JISK7136.

[Example 6]
A surface layer was obtained in the same manner as in Example 5 except that the ratio of LLDPE to LDPE (LLDPE / LDPE) was 80/20, and the haze was measured.
[Example 7]
A surface layer was obtained in the same manner as in Example 5 except that the ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40, and the haze was measured.
[Example 8]
A surface layer was obtained in the same manner as in Example 5 except that LDPE was not used, and the haze was measured.
[Example 9]
A surface layer was obtained in the same manner as in Example 5 except that LLDPE was not used, and its haze was measured.

[Evaluation of haze]
Table 2 shows the measured haze values for Examples 5 to 9. As shown in Table 2, in all Examples, a surface layer having a low haze was obtained. Therefore, the surface layer excellent in transparency was obtained by Example 5 thru | or Example 9.
In particular, in Examples 5 to 7 using a mixture of LLDPE and LDPE, a surface layer having a lower haze was obtained. Therefore, in Examples 5 to 7, a surface layer particularly excellent in transparency was obtained.

[Example 10]
The following four samples T021, T022, T023, and T024 were prepared.
(Sample T021)
Nylon 6 (6Ny) (“Ube Nylon 1022B” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical) A mixed resin (PE) of "Sumikasen L211") and branched low-density polyethylene (LDPE) ("Ube Polyethylene F522" manufactured by Ube Maruzen Polyethylene) was melt-cast by a co-extrusion method using a T-die, and 6Ny / AD A surface layer sample T021 laminated in the order of / PE was obtained. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The 6Ny layer had a thickness of 105 μm, the AD layer had a thickness of 22 μm, and the PE layer had a thickness of 32 μm.

(Sample T022)
Nylon 6-based resin (modified 6Ny) (“1022FDX99” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical) (Sumikasen L211)) and a branched low-density polyethylene (LDPE) ("Ube polyethylene F522" from Ube Maruzen polyethylene) are melt-cast into a film by a co-extrusion method using a T-die, and modified 6Ny / A surface layer sample T022 laminated in the order of AD / PE was obtained. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The modified 6Ny layer had a thickness of 100 μm, the AD layer had a thickness of 20 μm, and the PE layer had a thickness of 29 μm.

(Sample T023)
Nylon 12 (12Ny) (“UBESTA 3030U” manufactured by Ube Industries), maleic acid modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and linear low density polyethylene (LLDPE) (“Sumitomo Chemical” A mixed resin (PE) of Sumikasen L211 ") and branched low density polyethylene (LDPE) (" Ube Polyethylene F522 "manufactured by Ube Maruzen Polyethylene) was melt-formed by co-extrusion using a T-die, and 12 Ny / AD / A surface layer sample T023 laminated in the order of PE was obtained. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The 12Ny layer had a thickness of 101 μm, the AD layer had a thickness of 20 μm, and the PE layer had a thickness of 30 μm.

(Sample T024)
Nylon 6 (6Ny) (“Ube Nylon 1022B” manufactured by Ube Industries), acid-modified LLLDPE (modified AD) (“Admer NF587” manufactured by Mitsui Chemicals, Vicat softening point 65 ° C.), and linear low density polyethylene (LLDPE) ) (Sumitomo Chemical "Sumikasen L211") and branched low density polyethylene (LDPE) (Ube Maruzen Polyethylene "Ube Polyethylene F522") mixed resin (PE) melted by co-extrusion with T-die A surface layer sample T024 was obtained, which was laminated in the order of 6Ny / modified AD / PE. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The thickness of the 6Ny layer was 99 μm, the thickness of the modified AD layer was 20 μm, and the thickness of the PE layer was 31 μm.

[Evaluation of dimensional change rate]
Samples T021, T022, T023, and T024 were stored in an aluminum bag in a moisture-proof state (5 days) immediately after film formation, and then each sample was cut into three sample pieces and the dimensions were measured to obtain reference dimensions. Further, the sample pieces for which the reference dimensions were determined were (i) 40 ° C., 4% relative humidity, 7 days, (ii) 40 ° C., 60% relative humidity, 7 days, and (iii) 40 ° C., 90% relative humidity. And stored for 7 days. Then, the dimension and the moisture content (A & D Co., Ltd. heat drying type moisture meter MS-70 120 degreeC) were measured. Furthermore, the expansion / contraction rate (%) was obtained from the actually measured dimensions based on the reference dimensions. The shrinkage rate was represented by + when the measured dimension was expanded from the reference dimension, and by-when the measured dimension was contracted from the reference dimension.

  The moisture content (horizontal axis) and shrinkage rate (vertical axis) when stored under the above conditions (i) 40 ° C., relative humidity 4%, 7 days are shown in FIG. 10, and (ii) 40 ° C. The moisture content (horizontal axis) and shrinkage rate (vertical axis) when stored under conditions of 60% relative humidity and 7 days are shown in FIG. 11, (iii) 40 ° C., 90% relative humidity, 7 days. FIG. 12 shows the moisture content (horizontal axis) and the shrinkage rate (vertical axis) when stored under the above conditions.

  As shown in FIGS. 10 to 12, all the sample pieces had an expansion / contraction rate of ± 1.1% (length standard) or less, and good dimensional stability was shown. In particular, in the case of sample T023 using nylon 12, the expansion / contraction rate is only + 0.2%, and it was proved that the dimensions hardly change. Nylon 12 exhibited excellent dimensional stability not only under high humidity conditions as in condition (iii) but also under dry conditions as in condition (i).

[Example 11]
Nylon 6 (6Ny) (“Ube Nylon 1022B” manufactured by Ube Industries), maleic acid-modified LLDPE (AD) (“Admer NF518” manufactured by Mitsui Chemicals), and ethylene-methacrylic acid copolymer (EMAA) (Mitsui / DuPont) “Nucleel AN4213C”) was melt-formed by a co-extrusion method using a T-die to obtain a surface layer laminated in the order of 6 Ny / AD / EMAA. The Vicat softening point of AD was 85 ° C., the thickness of the 6Ny layer was 110 μm, the thickness of the AD layer was 20 μm, and the thickness of the EMAA layer was 30 μm.
The formed surface layer was laminated to a stainless steel plate. Lamination conditions were a temperature of 120 ° C., a pressure of 0.5 MPa, and a speed of 20 mm / second. After lamination, the laminate was stored under conditions of 60 ° C., 90% relative humidity and 1 day. In Example 11, it was shown that the AD layer maintained a stable adhesive force without peeling even after storage under the conditions.

[Example 12]
The following two types of samples T025 and T026 were prepared.
(Sample T025)
Nylon 12 (12Ny) ("UBESTA 3030U" manufactured by Ube Industries), nylon 6 (6Ny) ("Ube nylon 1022B" manufactured by Ube Industries), maleic acid-modified LLDPE (AD) ("Admer NF518" manufactured by Mitsui Chemicals) , And a mixed resin (PE) of linear low density polyethylene (LLDPE) (“Sumikasen L211” manufactured by Sumitomo Chemical) and branched low density polyethylene (LDPE) (“Ube polyethylene F522” of Ube Maruzen polyethylene), A melt film was formed by a co-extrusion method using a T die to obtain a surface layer sample T025 laminated in the order of 12Ny / 6Ny / AD / PE. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The thickness of the 12Ny layer was 30 μm, the thickness of the 6Ny layer was 80 μm, and the total thickness of the AD layer and the PE layer was 40 μm.

(Sample T026)
Nylon 12 (12Ny) ("UBESTA 3030U" manufactured by Ube Industries), nylon 6 (6Ny) ("Ube nylon 1022B" manufactured by Ube Industries), maleic acid-modified LLDPE (AD) ("Admer NF518" manufactured by Mitsui Chemicals) A mixed resin (PE) of linear low density polyethylene (LLDPE) (“SUMICACEN L211” manufactured by Sumitomo Chemical) and branched low density polyethylene (LDPE) (“UBE polyethylene F522” manufactured by Ube Maruzen Polyethylene), A melt film was formed by a co-extrusion method using a T-die to obtain a surface layer sample T026 laminated in the order of 12Ny / 6Ny / AD / PE. The mixing ratio of LLDPE to LDPE (LLDPE / LDPE) was 60/40 (weight basis). The thickness of the 12Ny layer was 50 μm, the thickness of the 6Ny layer was 60 μm, and the total thickness of the AD layer and the PE layer was 40 μm.

[Evaluation of dimensional change 1]
Samples T025 and T026 were stored in an aluminum bag in a moisture-proof state (5 days) immediately after film formation, and then the dimensions were measured to obtain reference dimensions. Furthermore, the sample for which the reference dimensions were obtained was stored under conditions of 40 ° C., relative humidity 90%, and 10 days. Then, the dimension and the moisture content (A & D Co., Ltd. heat drying type moisture meter MS-70 120 degreeC) were measured. Furthermore, the expansion / contraction rate (%) was obtained from the actually measured dimensions based on the reference dimensions. The shrinkage rate was represented by + when the measured dimension was expanded from the reference dimension, and by-when the measured dimension was contracted from the reference dimension.

The moisture content (horizontal axis) and shrinkage rate (vertical axis) when stored under the above conditions are shown in FIG.
In spite of stricter conditions than in Example 10, as shown in FIG. 13, all the sample pieces have an expansion / contraction rate of ± 1.1% or less, and good dimensional stability is shown. It was. Samples T025 and T026, which include a 6Ny layer in the polyamide resin layer, are laminated with a thickness of 12Ny layer, so that better dimensional stability is obtained than sample T021 in which the polyamide resin layer includes only the 6Ny layer. It was. Furthermore, the tendency that favorable dimensional stability was acquired was seen, so that the thickness of 12Ny layer with respect to the whole polyamide-type resin layer was large.

[Evaluation of dimensional change 2]
Samples T025 and T026 were stored under conditions of 40 ° C. and 90% relative humidity for 10 days as described above, then released from the conditions, and allowed to stand in an environment of 23 ° C. and 50% RH for 4 hours. In samples T025 and T026 after being left, neither warpage nor dimensional change occurred.

[Materials used for flooring]
(1) Resin (A): 21% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 9% by weight of DOP, A mixture of 6 wt% stabilizer, 0.4 wt% pigment, and 69 wt% calcium carbonate.
(2) Resin (B): 57% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 21% by weight of DOP, 0. A mixture of 9% by weight stabilizer, 1.1% by weight pigment, and 20% by weight calcium carbonate.
(3) Resin (C): 34% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 11% by weight of DOP, 0. A mixture of 9% by weight stabilizer, 1.1% by weight pigment, and 53% by weight calcium carbonate.
(4) Resin (D): 25% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 8% by weight of DOP, 0. A mixture of 6 wt% stabilizer, 0.4 wt% pigment, and 66 wt% calcium carbonate.
(5) Resin (E): 74% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 23% by weight of DOP, and 3 Mixture of weight percent stabilizer.
(6) Resin (F): 33.5% by weight of vinyl chloride resin (“ZEST 1000Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 64.5-68.1), 11% by weight of DOP, A mixture of 0.9 wt% stabilizer, 0.5 wt% pigment, and 54.1 wt% calcium carbonate.
(7) Resin (G): 74.6% by weight of vinyl chloride resin (“ZEST 800Z” manufactured by Shin Daiichi Vinyl Co., Ltd., K value 60.3-62.8), 19.3% by weight of DOP 6.1% by weight of a mixture of stabilizers.

(8) Fiber sheet (a): A glass fiber nonwoven fabric having a basis weight of 30 g / cm ² and a thickness of about 0.1 mm.
(9) Fiber sheet (b): Glass fiber fabric having a thickness of about 0.1 mm.
(10) Fiber sheet (c): Thickness 0 in which a glass fiber nonwoven fabric having a basis weight of 30 g / cm ² and a thickness of about 0.1 mm is impregnated with a vinyl chloride resin paste at a rate of 300 g / m ² and gelled by heat. .35 mm resin impregnated fiber sheet.
(11) Film (d): A film printed directly on a 0.07 mm thick vinyl chloride resin film.

(12) Ultraviolet curable resin (1): Urethane acrylic ultraviolet curable resin paint (“114L4” manufactured by China Paint Co., Ltd.).
(13) Ultraviolet curable resin (2): Urethane acrylic ultraviolet curable resin paint (“TLI-B07” manufactured by Dainichi Seika Kogyo Co., Ltd.).
(14) Ny-PO sheet: A sheet on which the decorative printing is applied directly to the back surface of the sheet prepared in Example 4 (the back surface of the mixed resin layer of LLDPE and LDPE).

[Example 13]
Resin (A) was calendered to produce a sheet having a thickness of 1.3 mm. Also, the resin (B) was calendered to produce a 0.5 mm thick sheet and a 1.2 mm thick sheet, respectively. The sheet of 1.3 mm thickness is placed on the sheet of 1.2 mm thickness, the fiber sheet (a) is placed thereon, the sheet of 0.5 mm thickness is placed thereon, and The back surface (printing surface) of the Ny-PO sheet was placed to prepare a laminate. The laminate was pressurized while being heated to about 200 ° C., whereby the vinyl chloride resin was completely gelled. Thus, the flooring of Example 13 having a thickness of 3 mm was produced. In addition, since it heat-pressed when integrating each layer, the thickness of a flooring is smaller than the total thickness of each layer. The surface of the flooring (the surface of the Ny-PO sheet) was embossed with a relatively rough satin pattern.

[Examples 14 to 20, Comparative Examples 1 to 3]
A flooring was produced in the same manner as in Example 13 except that the layer configuration as shown in Table 3 and Table 4 was changed and the embossing was changed.
However, for Comparative Example 1, after preparing the flooring by heating and pressing, by applying and curing the ultraviolet curable resin (1) and the ultraviolet curable resin (2) on the outermost surface and the outermost surface, respectively, A surface protective layer and a back surface protective layer having a thickness of 0.03 mm were formed. For Comparative Example 2, a flooring was prepared by heating and pressing, and then a UV-curable resin (1) was applied to the outermost surface and cured to form a surface protective layer having a thickness of 0.03 mm.

[Warp test]
In accordance with JIS A1454, the flooring produced in each of the above Examples and Comparative Examples was cut into 300 mm × 300 mm in length and breadth to prepare a test piece, which was cured at 23 ° C. and 60% humidity for 24 hours. The warp value at the end of the test piece was measured and evaluated in the following three stages. In addition, the plus of the warp value indicates a value in which the end portion warps upward (upward warp value), and the minus indicates a value in which the end portion warps downward (down warp value). The results are shown in Tables 3 and 4.
3: The warp value was -2 mm to +6 mm.
2: The warp value was −4 mm to −2 mm.
1: The warp value was +6 or more or -4 mm or less.

[Dirt test]
The flooring produced in each of the above Examples and Comparative Examples was cut into 230 mm × 230 mm vertically and horizontally to produce a test piece. The back surface of the test piece (the back surface of the flooring material) was attached to the inner wall surface of a hollow six-cubic cylinder rotary tester. Six cubic rubber lumps (material: NBR90) each having a side of 5 cm were placed inside the tester, the lid of the rotary tester was closed, and forward rotation for 15 minutes and reverse rotation for 15 minutes were performed. Then, while removing the test piece and observing the rubber | gum trace adhering to a test piece visually, the removability from a test piece was evaluated in the following four steps. The results are shown in Tables 3 and 4.
4: The amount of black heel marks (rubber marks) attached was very small, and the marks could be removed with a cloth.
3: The adhesion amount of the black heel mark was relatively small, and the mark could be removed with a cloth.
2: Although the amount of black heel mark attached was slightly conspicuous, the mark could be removed with a cloth.
1: The amount of black heel mark attached was relatively large and could not be removed with a cloth.

[Scratch test]
After removing the dirt (black heel mark) adhering to the surface of the test piece after carrying out the dirt test as much as possible, the surface of the specimen is visually observed, and the presence or absence of a scuff mark (scratch) is as follows: It was evaluated in three stages. The results are shown in Tables 3 and 4.
3: A scuff mark was not recognized.
2: A slight scuff mark was confirmed.
1: Many scuff marks were generated.

[An endurance test]
The flooring prepared in each of the above examples and comparative examples was cut into a circular shape having a diameter of 105 mm to prepare a test piece. In accordance with JIS A1453, the test piece was affixed to a wear test device, and the test device was set to 1,000 at a speed of 60 ± 2 rpm with S-42 wear paper in contact with the test piece on the surface of the test piece. Rotated. Then, the number of revolutions from the wear amount of 1000 revolutions to the limit effective wear was calculated and evaluated in the following three stages. The results are shown in Tables 3 and 4. Note that Comparative Example 3 was so brittle that the wear test could not be performed, and could not be calculated.
3: The calculation result exceeded 2000 rotations.
2: The calculation result was 600 to 2000 rotations.
1: The calculation result was less than 600 revolutions.

The flooring material of each Example was excellent in durability to the same degree or more as Comparative Examples 1 and 2 provided with a surface protective layer of an ultraviolet curable resin.
Moreover, each Example using a Ny-PO sheet as the surface layer was less susceptible to contamination than Comparative Examples 1 and 2 in which an ultraviolet curable resin layer was provided as the surface protective layer. Furthermore, although each Example using a Ny-PO sheet as a surface layer is slightly worse than Comparative Examples 1 and 2 in which an ultraviolet curable resin layer is provided as a surface protective layer in terms of scratching properties, There was no particular problem. In addition, it turns out that a scratch property is also improved by providing a rough finish as embossing like Examples 13 thru | or 15. Of the examples using the Ny-PO sheet as the surface layer, the examples 13 to 16 and 18 to 20 that are embossed are scratched more than the example 17 that is not embossed. It turns out to be difficult.
In addition, in the flooring material of each Example, although the sheet | seat produced in Example 4 was used as a Ny-PO sheet, the same effect is acquired even if it uses the sheet | seat produced in Examples 1 thru | or 3 and 5 thru | or 12. It is done.
Furthermore, it can be seen that the flooring materials of Examples 13 to 19 provided with the shape stabilizing layer are less likely to warp than the flooring material of Example 20. Further, the floor material provided with the upper resin layer and the lower resin layer with the shape stabilizing layer interposed therebetween more effectively suppresses the warp than the floor material of Example 15 in which the resin layer is provided only on one side. I understand that I can do it. Furthermore, among the flooring materials in which the upper resin layer and the lower resin layer are provided with the shape stabilizing layer interposed therebetween, the flooring material in which the thickness of the upper resin layer is smaller than the thickness of the lower resin layer (Example 13 to Example) It can be seen that 17) can more effectively suppress warpage than a flooring (Example 19) in which the thickness of the upper resin layer is larger than the thickness of the lower resin layer.

DESCRIPTION OF SYMBOLS 1 Floor material 2 Floor material main body 3 Resin layer 31 Upper resin layer 32 Lower resin layer 4 Shape stabilization layer 5 Surface layer 51 Polyamide-type resin layer 52 Adhesive layer 53 Polyolefin-type resin layer

Claims (6)

A flooring body having a resin layer, and a surface layer provided on the flooring body,
The surface layer has a polyolefin resin layer and a polyamide resin layer laminated on the polyolefin resin layer via an adhesive layer, and the polyolefin resin layer comprises an olefin homopolymer resin, an olefin copolymer resin, Or the flooring containing the mixed resin of an olefin homopolymer resin and an olefin copolymer resin.   The flooring according to claim 1, wherein the flooring main body further has a shape stabilizing layer.   The flooring according to claim 2, wherein the resin layer has an upper resin layer and a lower resin layer, and the shape stabilizing layer is interposed between the upper resin layer and the lower resin layer.   The flooring according to claim 3, wherein a thickness of the upper resin layer is equal to or smaller than a thickness of the lower resin layer.   The flooring according to any one of claims 1 to 4, wherein the polyamide-based resin is at least one of 11-nylon and 12-nylon.   The flooring according to any one of claims 1 to 5, wherein the surface layer has a dimensional change rate of ± 1.1% or less when stored for 7 days in an environment of 40 ° C and 90% relative humidity.

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