JP6426978B2 - Interior sheet for bathroom and floor sheet for bathroom - Google Patents

Description

  The present invention relates to an interior sheet and the like constructed on a floor surface or a wall surface in a bathroom.

Generally, hard materials such as porcelain tile, FRP and hard rubber are used as floor materials and wall materials of a bathroom. Moreover, the floor of a bathroom generally adopts a structure having small projections and irregularities on its surface in order to impart anti-slip properties and enhance drainage performance. However, in the case of adopting a structure having small protrusions and irregularities on the surface of the floor material made of the hard material, the bare skin of the bather may come in contact with the hard unevenness and the bather may feel pain. In particular, when the bather knees on the floor of the bathroom, he often feels pain because his weight is concentrated.
The present inventor has proposed an interior sheet having desired unevenness for the purpose of reducing the pain and the like (Patent Document 1). In particular, a vinyl chloride resin is suitable as a floor sheet for a bathroom because it is easy to manufacture and has an appropriate flexibility, and is excellent in a pain reducing effect.
In addition, the design layer is protected by the surface layer by using a transparent vinyl chloride resin as the surface layer (uppermost layer) of the interior sheet and further providing a design layer subjected to printing or coloring on the lower side of the surface layer. It is possible to form a finished bathroom interior sheet. Furthermore, in this case, since the printing and coloring of the design layer appear more three-dimensional due to the small projections and irregularities provided on the surface layer surface, the interior sheet exhibits excellent designability.
Thus, the vinyl chloride resin is very useful as a forming material of an interior sheet having a pain reducing effect and an excellent design property.

However, although a vinyl chloride resin is treated at high temperature (for example, 160 ° C. to 200 ° C.) when formed into a bathroom interior sheet, the vinyl chloride resin may be discolored or hardened at a high temperature. If the vinyl chloride resin is discolored or hardened, it is difficult to form it into an interior sheet. Therefore, it is required to improve the productivity of the bathroom interior sheet by using a vinyl chloride resin excellent in thermal stability at high temperature.
In addition, when a vinyl chloride resin is used as a bathroom interior sheet on a bathroom wall or ceiling, the surface of the interior sheet becomes white due to absorption of water or the like during use, causing so-called water absorption whitening. There is. Water absorption and whitening on the surface of a bathroom interior sheet is undesirable for design, and therefore its improvement is required.

JP, 2012-158914, A

An object of the present invention is to provide a vinyl chloride resin-made bathroom interior sheet that is resistant to discoloration and curing during production, is excellent in productivity and flexibility, and suppresses whitening to exhibit a good appearance .

The interior sheet for a bathroom of the present invention has a sheet body and a surface layer provided on the surface of the sheet body, and the surface layer contains a vinyl chloride resin, a plasticizer, and a heat stabilizer. The heat stabilizer contains a liquid heat stabilizer and a solid heat stabilizer, and the content of the liquid heat stabilizer is 1.5 parts by mass to 8.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. part der is, the content of the solid thermal stabilizer, Ru 1 parts by mass to 5 parts by mass der respect to the vinyl chloride resin 100 parts by mass.

Preferably, in the bathroom interior sheet of the present invention, the content of the plasticizer is 26.0 parts by mass to 38.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
Preferably, the vinyl chloride resin contains a vinyl chloride-vinyl acetate copolymer, and the content of the vinyl chloride-vinyl acetate copolymer is 25.0 with respect to 100 parts by mass of the vinyl chloride resin. It is below a mass part.
In addition, preferably, the vinyl chloride resin is substantially free of a vinyl chloride-vinyl acetate copolymer.
In addition, preferably, the thickness of the surface layer is 0.05 mm to 0.45 mm.

  According to another aspect of the present invention, there is provided a bathroom floor sheet comprising the above-described bathroom interior sheet of the present invention.

The interior sheet for a bathroom of the present invention is excellent in productivity because it is excellent in thermal stability at the time of production.
The interior sheet for a bathroom of the present invention is difficult to whiten even if water or hot water is applied to the bathroom. By using the interior sheet of the present invention, a bathroom capable of suppressing whitening for a long time can be constructed.

The top view of the interior sheet for bathrooms of this invention. The expanded sectional view cut | disconnected by the II-II line of FIG. The principal part expansion perspective view seen from the arrow III direction of FIG.

Hereinafter, the present invention will be described with reference to the drawings as appropriate.
In the present specification, the description “AAA to BBB” means “AAA or more and BBB or less”. Further, in the present specification, a bathroom interior sheet may be simply referred to as an "interior sheet". Further, in the present specification, when referring to the content of each component contained in the surface layer, the case where the total content of the vinyl chloride resin is 100 parts by mass is used as a standard.
Further, the interior sheet of the present invention is used on the inner surface of at least one bathroom selected from the floor surface of the bathroom, the wall surface of the bathroom, and the ceiling surface of the bathroom. In particular, since the interior sheet of the present invention is excellent in the whitening suppression effect, it can be suitably used on the floor of a bathroom to which water is likely to adhere. In the present specification, for convenience, an interior sheet used for a floor of a bathroom may be referred to as a floor sheet for convenience.

[Overview of Interior Sheet for Bathroom]
FIG. 1 is a plan view showing one embodiment of a bathroom interior sheet of the present invention, and FIG. 2 is an enlarged cross-sectional view thereof.
As shown in FIG. 2, the interior sheet 1 of the present invention has a sheet body 2 and a surface layer 3 provided on the surface of the sheet body 2. In addition, if the interior sheet of this invention has the sheet | seat main body 2 and the surface layer 3, the shape will not be limited and the use will not be specifically limited, either. In the present embodiment, an example in which an interior sheet is used as a floor sheet will be described.
The seat body 2 is a layer that is a basic skeleton of a bathroom interior sheet. The sheet body 2 may be a single layer or a multilayer having two or more layers. In FIG. 2, the sheet body 2 is, for example, a multilayer body having a lower layer 21, a reinforcing layer 22, an upper layer 23, and a design layer 24 in order from the bottom.
The surface layer 3 is provided, for example, for the purpose of damage due to mechanical impact of the sheet main body 2 or infiltration of water into the sheet main body 2. The surface layer 3 can function as a protective layer of the sheet body 2.
The surface layer 3 is provided on the surface of the sheet body 2, and in FIG. 2, the surface layer 3 is provided on the surface of the design layer 24 which is the uppermost layer of the sheet body 2. The surface layer 3 is a layer provided on the top of the interior sheet 1 and is a layer exposed to the air.
Hereinafter, each layer of the interior sheet according to the embodiment of the present invention shown in FIGS. 1 and 2 will be described.

[Shape of interior sheet for bathroom]
The shape of the interior sheet of the present invention is not particularly limited, but when the interior sheet is used for a floor of a bathroom, it is preferable that an uneven portion for anti-slip is formed on the surface.
For example, the interior sheet 1 (floor sheet) shown in FIGS. 1 to 3 has a concavo-convex pattern area 4 including a plurality of convex portions 31 and concave portions 32 on the surface thereof. The plurality of protrusions 31 are arranged vertically and horizontally adjacent to each other, and the plurality of recesses 32 are formed between the adjacent protrusions 31. In the present embodiment, the concavo-convex pattern area 4 including the plurality of convex portions 31 and the concave portions 32 is taken as one unit, and a plurality of unit units are arranged in the longitudinal and lateral directions of the sheet main body 2. In addition, in the example of illustration, although the shape of the convex part 31 is planar view substantially square shape, this shape can be suitably changed into arbitrary shapes. Further, in the illustrated example, the plurality of convex portions 31 are formed in the same shape and size, but convex portions 31 having different shapes and sizes may be mixed.

As shown in FIGS. 2 and 3, the convex portion 31 has a substantially flat surface at the projecting end, and the substantially flat surface is the top surface of the convex portion 31. The top surface is an inclined surface. Therefore, the water adhering to the top surface of the convex part 31 can be flowed in one direction according to the inclination of the top surface, and the drainage property is improved.
In addition, as shown in FIG. 3, in one uneven pattern region 4, at least two convex portions 31 having different inclination directions of the top surface are provided.
The inclination angle of the top surface of each convex portion 31 can be set appropriately, but if it is too small, it becomes difficult for water attached to the top surface to flow toward the recess 32, and when it is too large, the feeling of unevenness on the sole increases. It may cause the bather to feel uncomfortable. From such a viewpoint, the inclination angle of each top surface is preferably in the range of tan ⁻¹ (1/100) degree to tan ⁻¹ (10/100) degree, and tan ⁻¹ (2/100) degree to tan ⁻ The range of ¹ (8/100) degree is more preferable, and the range of tan ^-1 (3/100) degree to tan ^-1 (7/100) degree is more preferable. In addition, the inclination | tilt angle of a top surface says the angle which a horizontal surface and a top surface comprise in the state which mounted the back surface of the interior sheet 1 for bathrooms on the horizontal surface.
In addition, innumerable fine projections may be formed on the surface of the convex portion 31. In FIG. 3, the innumerable dots attached to the top surface of the convex portion 3 indicate the fine projections.
As described above, in the interior sheet 1, the uneven portion on the surface not only functions as a non-slip member, but also improves drainage. In this way, it is possible to prevent moisture from coming into contact with the surface of the convex portion 31 for a long time, and to suppress the whitening of the surface layer 3.
Hereinafter, each layer of the interior sheet 1 according to the embodiment of the present invention shown in FIG. 2 will be described.

[Sheet body]
The sheet body 2 is preferably formed of a flexible sheet. Thereby, the interior sheet 1 can be given flexibility. The flexible interior sheet 1 can be easily stored and transported, and can be easily carried into the bathroom at the time of construction.
In addition, having flexibility means that, for example, the sheet main body 2 and the interior sheet 1 can be wound around a cylindrical core having a diameter of 10 cm.
The sheet body 2 may be composed of only non-foam, but preferably contains foam. The interior sheet 1 having the sheet body 2 containing foam is excellent in cushioning properties, and can relieve pain when kneeling on the floor of a bathroom, etc., and also reduces heat shock in the bathroom and enhances warmth It can also be done. Also, in general, the sound in the bathroom is likely to resonate, but the inclusion of the foam can suppress the impact noise even when the basin or the like is dropped to the floor surface. In particular, in the case where the sheet main body 2 is a sheet containing a foam, the flexibility on the surface thereof also becomes high, so that the effect of alleviating the pain and the effect of suppressing the impact sound also become good.
Although the thickness of the sheet | seat main body 2 is not specifically limited, For example, they are 1.5 mm-10 mm, Preferably, they are 1.8 mm-7 mm.

The upper layer 23 and the lower layer 21 are layers that mainly constitute the sheet main body 2.
The material for forming the upper layer 23 and the lower layer 21 is not particularly limited, and soft synthetic resin, semi-rigid synthetic resin, hard synthetic resin, rubber, FRP, etc. may be mentioned. The soft, semi-rigid and hard are as described in JIS-K6900 (1994) plastic-terms. Preferably, the upper layer 23 and the lower layer 21 are formed of a soft synthetic resin, a semi-rigid synthetic resin, rubber or the like in order to constitute the interior sheet 1 having flexibility.
The upper layer 23 and the lower layer 21 may be either foam or non-foam, but it is preferable that at least one is made of foam.
The upper layer 23 and the lower layer 21 may be formed of the same material, or may be formed of different materials. For example, the upper layer 23 and the lower layer 21 are formed of a layer containing a synthetic resin. The resin for forming the upper layer 23 and the lower layer 21 is a vinyl chloride resin; a polyolefin resin; a vinyl acetate resin such as ethylene-vinyl acetate copolymer; an acrylic resin such as ethylene-methacrylate resin; an amide resin; Thermoplastic resins such as olefin resins and various elastomers such as styrene elastomer are used. A vinyl chloride resin is preferable as a main resin component of the upper layer 23 and the lower layer 21 because it has excellent flexibility and excellent adhesion with the surface layer 3.
In the present specification, the main resin component of a certain layer is 60% by mass or more, preferably 80% by mass, based on 100% by mass of the entire resin component contained in the layer (when the entire resin component is 100% by mass). The above means, more preferably, a resin that occupies 90% by mass or more.

The reinforcing layer 22 is a layer for enhancing the rigidity of the sheet body 2 and for providing the sheet body 2 with dimensional stability.
The arrangement of the reinforcing layer 22 in the sheet main body 2 is not particularly limited, but as shown in FIG. 2, the reinforcing layer 22 is preferably embedded between the upper layer 23 and the lower layer 21. Although not shown, the reinforcing layer 22 may be provided on the back surface of the lower layer 21. Further, although not shown, a plurality of reinforcing layers 22 may be provided. For example, the reinforcing layers 22 may be provided between the upper layer 23 and the lower layer 21 and on the back surface of the lower layer 21.
The reinforcing layer 22 is not particularly limited as long as it contains fibers, but, for example, glass mat, glass net, resin mat, resin net, non-woven fabric or felt made of inorganic fiber or organic fiber, woven fabric, etc. It can be mentioned.
The fibers used for the reinforcing layer 22 preferably have high adhesion to the upper layer 23 and the lower layer 21, and examples thereof include glass fibers, vinylon fibers, polyester fibers, polyamide fibers, and polyimide fibers. In particular, glass fibers are preferred because they are excellent in strength and small in dimensional change. When using a glass ^fiber, more preferably a glass fiber woven or nonwoven fabric of ^{10g / m 2 ~100g / m 2} . Also, for example, with regard to the fabric weight of a woven or non-woven fabric using other fibers such as polyester, a fabric weight of the same level as that of glass fiber is preferable.
The thickness of the reinforcing layer 22 is not particularly limited, but is usually about 0.1 mm to 0.4 mm.

The design layer 24 has a function to expose the handle on the surface of the interior sheet 1. The design layer designs the surface itself of the sheet main body 2 by, for example, printing or transferring a design, laminating a colored resin sheet, or including a coloring agent in the sheet main body 2 (upper layer 23) It can form by methods, such as.
When the design layer 24 is formed of a resin such as printing, transfer, or a resin sheet, preferably, the design layer 24 is formed of a thermoplastic resin as exemplified in the sections of the upper layer 23 and the lower layer 21. As a main resin component of the design layer 24, a vinyl chloride resin is preferable.
The thickness of the design layer 24 is not particularly limited, but is preferably 0.05 mm to 0.3 mm.

  In addition, the sheet | seat main body 2 is not limited to the layer structure shown by FIG. 2, For example, the design layer 24 and the reinforcement layer 22 do not need to be provided (not shown), Furthermore, it is a span on the back surface Other reinforcing layers of bonds may be provided (not shown).

[Surface]
The surface layer 3 is a layer provided on the uppermost (outmost) side of the interior sheet 1. Since the surface of the surface layer 3 is exposed to air, it is exposed to water and hot water in the bathroom. The surface layer 3 may or may not have transparency, but preferably has transparency. If the surface layer 3 has transparency, the design layer 24 can be viewed through the surface layer 3 from the outside of the interior sheet 1 by providing the above-mentioned design layer 24 on the lower side.
In the present invention, the surface layer 3 contains a vinyl chloride resin, a plasticizer and a heat stabilizer. Hereinafter, these components contained in the surface layer 3 will be described.

(Vinyl chloride resin)
The vinyl chloride-based resin is suitable as a forming material of the surface layer of the interior sheet, since it is easy to manufacture, has appropriate flexibility, and is excellent in cost.
The vinyl chloride resin is a polymer formed by polymerizing at least a vinyl chloride monomer (chloroethylene). For vinyl chloride resins, not only polymers (homopolymers) obtained by homopolymerization of chloroethylene, but also copolymers (copolymers) of homopolymers of chloroethylene and chlorethylene with homopolymers, homopolymers And mixtures of copolymers, as well as mixtures of two or more copolymers. In addition, a mixture means the polymer with which the homopolymer and the copolymer were knead | mixed, or the copolymers did not substantially superpose | polymerize.
Specifically as a vinyl chloride resin, a vinyl chloride polymer (homopolymer); partially crosslinked vinyl chloride; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer , Vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Copolymers containing vinyl chloride such as coalescence (copolymers); mixtures of homopolymers and one or more copolymers, mixtures of two or more copolymers; and the like.

As the vinyl chloride polymer (homopolymer), 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. The vinyl chloride resin obtained by the suspension polymerization method is preferable because it is easy to process, handle and whitening is difficult.
The vinyl chloride resin obtained by the suspension polymerization method is preferably a fine powder of 20 to 100 μm. The vinyl chloride resin produced by the suspension polymerization method preferably has an average degree of polymerization of about 700 to 1,500, and more preferably about 700 to 1,000. The vinyl chloride polymer (homopolymer) may be a suspension type polymer or a paste type polymer.
The copolymer containing chloroethylene, such as the vinyl chloride-vinyl acetate copolymer, may be in the form of block or random polymerization. The average degree of polymerization of the copolymer is preferably about 700 to 1000, and more preferably about 700 to 800.

The surface layer contains a vinyl chloride resin, but preferably, the surface layer contains substantially no vinyl chloride-vinyl acetate copolymer. Here, not substantially containing vinyl chloride-vinyl acetate copolymer means not only the case where vinyl chloride-vinyl acetate copolymer is not completely contained in the surface layer, but also a trace amount (for example, 1 part by mass or less) And the vinyl chloride-vinyl acetate copolymer are included.
When the surface layer contains a vinyl chloride-vinyl acetate copolymer, the content thereof is preferably 25.0 parts by mass or less, and more preferably, with respect to the total amount (100 parts by mass) of the vinyl chloride resin. Is 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, and particularly preferably 8.0 parts by mass or less.
As the blending amount of the vinyl chloride-vinyl acetate copolymer is smaller, the whitening of the surface layer can be more effectively suppressed while maintaining the thermal stability at the time of production. Although the reason for this is not clear, the structure of the vinyl chloride-vinyl acetate copolymer tends to retain water internally, and the less the content of the vinyl chloride-vinyl acetate copolymer, the less the whitening of the interior sheet can be suppressed. The present inventor estimates that.

(Plasticizer)
The plasticizer is an additive added mainly for the purpose of improving the flexibility of the vinyl chloride resin contained in the surface layer. Since the vinyl chloride resin is a main component of the surface layer, the flexibility of the surface layer is also improved if the flexibility of the vinyl chloride resin is improved. In addition, having the surface layer flexible means, for example, that the surface layer can be wound around a cylindrical core having a diameter of 10 cm.
Examples of the plasticizer include polyester plasticizers, glycerin plasticizers, polyvalent carboxylic acid ester plasticizers, and polyalkylene glycol plasticizers.

Examples of polyester plasticizers include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4- Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone.
Examples of the glycerin-based plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate and glycerin monoacetomonomontanate.
As polyvalent carboxylic acid plasticizers, for example, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, tributyl trimellitate , Trimellitic acid esters such as trioctyl trimellitate, trihexyl trimellitate, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, benzyl adipate Adipates such as butyl diglycol, citric acid esters such as triethyl acetyl citrate and tributyl acetyl citrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacine Dibutyl, and like di-2-ethylhexyl sebacate and the like.
Examples of polyalkylene glycol plasticizers include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymers of bisphenols, bisphenols Examples thereof include propylene oxide addition polymers and polyalkylene glycols such as tetrahydrofuran addition polymers of bisphenols.
As the plasticizer, a polybasic carboxylic acid plasticizer is preferably used, more preferably a phthalic acid ester is used, and particularly preferably dioctyl phthalate is used. Polyvalent carboxylic acid plasticizers have high plasticization efficiency to vinyl chloride resins. Therefore, the manufacturing cost of the interior sheet can be further suppressed by using a polyvalent carboxylic acid plasticizer.

The lower limit value of the content of the plasticizer contained in the surface layer is not particularly limited, but is preferably 24.0 parts by mass, more preferably 26.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. More preferably, it is 32.0 parts by mass, and particularly preferably 33.0 parts by mass. Further, the upper limit value of the content of the plasticizer contained in the surface layer is not particularly limited, but is preferably 41.0 parts by mass, more preferably 38.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Particularly preferably, it is 35.0 parts by mass.
By setting the content of the plasticizer in the above range, it is possible to obtain an interior sheet that is hard to whitening and excellent in heat stability. In particular, when the content of the plasticizer is 26.0 parts by mass to 38.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, an interior sheet having further excellent flexibility can be obtained.

(Heat stabilizer)
The heat stabilizer is an additive that is added mainly to prevent changes in the surface layer, such as discoloration and hardening, from being caused by heat at the time of producing the inner sheet. In the interior sheet of the present invention, a liquid heat stabilizer and a solid heat stabilizer are used as the heat stabilizer. By using a liquid heat stabilizer and a solid heat stabilizer in combination, the whitening of the interior sheet can be effectively suppressed.
The liquid heat stabilizer is a stabilizer that is liquid (including sol) and has fluidity at normal temperature and pressure (atmospheric pressure of 25 ° C.). The liquid heat stabilizer flows and is used in a fluid state. A solid heat stabilizer is a stabilizer which does not have fluidity at normal temperature and pressure. The solid heat stabilizer flows and is used without flowability.

The liquid heat stabilizer preferably contains at least one selected from an epoxy heat stabilizer and a metal heat stabilizer.
Examples of liquid epoxy heat stabilizers include epoxidized vegetable oils and epoxidized fatty acid alkyl esters.
Examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil and the like. Moreover, as the epoxidized fatty acid alkyl ester, for example, methyl epoxystearate, butyl epoxystearate, 2-ethylhexyl epoxystearate and the like can be mentioned.
As the liquid epoxy heat stabilizer, preferably, epoxidized vegetable oil is used, and more preferably, epoxidized soybean and / or epoxidized linseed oil is used.
The liquid epoxy-based heat stabilizer can not only function as a heat stabilizer but also impart flexibility to the surface layer. Therefore, the content of the plasticizer can be reduced by using a liquid epoxy heat stabilizer.

The liquid metal-based heat stabilizer is a liquid heat stabilizer containing an organometallic compound having a metal atom in the molecule.
The liquid metal-based heat stabilizer contains an organometallic compound having one metal atom, and preferably contains an organometallic compound having only one metal atom. Note that an organometallic compound having only one type of metal atom includes an organometallic compound in which one or more types of metal atoms are contained in the molecule.
Here, the metal-based heat stabilizers are generally classified according to the type of metal atom contained in the organometallic compound. For example, a thermal stabilizer containing a barium atom is referred to as a barium-based thermal stabilizer, and a thermal stabilizer containing a barium atom and a zinc atom is referred to as a barium-zinc-based thermal stabilizer. In this case, the barium-based heat stabilizer contains an organometallic compound having one metal atom, and the barium-zinc-based heat stabilizer contains an organometallic compound having two metal atoms.

The liquid metal-based heat stabilizer is not particularly limited, but preferably, a barium-based heat stabilizer, a zinc-based heat stabilizer, a calcium-based heat stabilizer, a tin-based heat stabilizer, a sodium-based heat stabilizer, a lead-based heat Thermal stabilizers are used which comprise organometallic compounds having only one metal atom, such as stabilizers.
The barium-based heat stabilizers include, for example, barium stearate, barium laurate, barium ricinoleate, barium naphthenate, barium 2-ethylhexoate and the like. Zinc-based heat stabilizers include, for example, zinc stearate, zinc octylate and the like. Calcium heat stabilizers include, for example, calcium stearate, calcium laurate and the like. Tin-based heat stabilizers include, for example, butyl tin laurate, butyl tin malate and the like. Sodium heat stabilizers include, for example, sodium oleate, sodium valmitate, sodium stearate and the like. Lead-based heat stabilizers include, for example, basic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, tribasic lead maleate and the like.
A barium-based heat stabilizer is preferably used as the liquid metal-based heat stabilizer. Since the barium-based heat stabilizer has a low odor, it can effectively prevent the unpleasant odor caused by the heat stabilizer from filling the bathroom.

The lower limit value of the content of the liquid heat stabilizer is 1.5 parts by mass, preferably 2.5 parts by mass, particularly preferably 3.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. is there. The upper limit of the content of the liquid heat stabilizer is 8.5 parts by mass, preferably 6.5 parts by mass, and more preferably 5.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Part, more preferably 5.0 parts by mass, particularly preferably 4.5 parts by mass.
The liquid heat stabilizer preferably comprises a liquid epoxy heat stabilizer and a liquid metal heat stabilizer. By using both heat stabilizers in combination, the thermal stability of the vinyl chloride resin can be improved, and an interior sheet excellent in productivity can be formed.
In particular, if the content of the liquid heat stabilizer is 1.5 parts by mass to 6.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, not only the thermal stability of the vinyl chloride resin can be improved, Furthermore, the whitening of the vinyl chloride resin can be prevented to improve its transparency.
When both heat stabilizers are used in combination, the mass ratio of the liquid epoxy heat stabilizer to the liquid metal heat stabilizer (epoxy heat stabilizer: metal heat stabilizer) is not particularly limited, but is preferably 2 : 3 to 3: 2, more preferably 4: 5 to 5: 4, and particularly preferably about 1: 1.

The solid heat stabilizer is preferably a powdered heat stabilizer. The powdery heat stabilizer is a heat stabilizer whose form is powdery among solid heat stabilizers. Here, that the heat stabilizer is powdery means that the solid heat stabilizer having an average particle diameter of less than 0.5 mm occupies 90% by mass or more of the whole solid heat stabilizer. The average particle diameter in the present specification means the average value of the maximum width of 200 particles (solid heat stabilizer) arbitrarily selected from images obtained by observing the particles with a transmission electron microscope (TEM). . If the solid heat stabilizer is powdery, it can be uniformly dispersed in the entire surface layer.
The solid heat stabilizer is preferably a metal heat stabilizer having two or more metal atoms. Thermal stabilizers having two or more metal atoms are generally referred to as composite thermal stabilizers. Complex heat stabilizers are classified according to the type of metal atom contained in the molecule. For example, thermal stabilizers comprising barium and zinc atoms are referred to as barium-zinc based thermal stabilizers.
Examples of solid complex heat stabilizers include calcium-zinc heat stabilizers, barium-zinc heat stabilizers, zinc-sodium heat stabilizers, and the like. The solid composite heat stabilizer can be formed by combining two or more of the organic metal compounds listed above.
The solid heat stabilizer is preferably a powdery composite heat stabilizer, more preferably a powdery barium-zinc heat stabilizer.

  The lower limit of the content of the solid heat stabilizer is not particularly limited, but is, for example, 1.0 part by mass, preferably 2.0 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin. Preferably, it is 2.5 parts by mass. The upper limit of the content of the solid heat stabilizer is not particularly limited, but is, for example, 5.0 parts by mass, preferably 4.0 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin. And particularly preferably 3.5 parts by mass.

The inventors of the present invention have found that the water absorption and whitening of the interior sheet is caused by the fact that light entering from the outside of the interior sheet causes diffuse reflection due to the moisture entering the fine voids present in the vinyl chloride resin. It has also been found that the use of a liquid stabilizer is one factor that promotes the absorption and whitening of the interior sheet.
However, liquid heat stabilizers can impart excellent heat resistance to vinyl chloride resins. Therefore, as the content of the liquid heat stabilizer is reduced to prevent whitening, the heat resistance of the vinyl chloride resin is lowered. Therefore, it becomes difficult to form a vinyl chloride resin into an interior sheet, and the productivity of the interior sheet is significantly reduced.
On the other hand, the inventor of the present invention can suppress the whitening of the interior sheet and can impart sufficient heat resistance to the vinyl chloride resin by using the liquid heat stabilizer and the solid heat stabilizer in combination at the above content. I found it.

  The total amount of the heat stabilizer including the liquid heat stabilizer and the solid heat stabilizer is not particularly limited, but the lower limit thereof is, for example, 2.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and preferably Is 4.5 parts by mass, more preferably 5.5 parts by mass, and particularly preferably 6.0 parts by mass. The upper limit of the total amount of the heat stabilizer is, for example, 13.5 parts by mass, preferably 10.5 parts by mass, and more preferably 9.0 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin. Part, particularly preferably 8.0 parts by mass.

  Thus, although the surface layer of the interior sheet of the present invention contains a vinyl chloride resin, a plasticizer, and a heat stabilizer, it may contain other optional additives. Such optional additives include, for example, pigments, flame retardants, antioxidants, lubricants, foaming agents, mildew proofing agents, antibacterial agents, inorganic particles and the like. The content of each additive is not particularly limited, and is appropriately added as necessary.

The surface layer of the interior sheet of the present invention preferably has a thickness of 0.05 mm to 0.45 mm, more preferably 0.05 mm to 0.35 mm, still more preferably 0.1 mm to 0.35 mm. And particularly preferably 0.2 mm to 0.3 mm.
If the thickness of the surface layer is smaller than 0.05 mm, the sheet body may not be sufficiently protected. If the thickness of the surface layer is larger than 0.45 mm, the whitening of the surface layer may be superimposed and noticeable. .

It is preferable that the surface layer used for the interior sheet of this invention is transparent.
The haze (haze value) of the surface layer is preferably 8.0% or less, and particularly preferably 7.0% or less. If the haze value is 8.0% or less, the surface of a layer (for example, a design layer) disposed below the surface layer can be visually recognized. The haze value (%) is determined using a turbidimeter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH 2000" D 65 light source) according to JIS K 7136 (Plastic-How to find haze of transparent materials). It is a value measured by entering light from the surface side of the surface layer.

  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.

[Material used]
(1) Suspension type vinyl chloride resin: trade name "800Y" manufactured by Kaneka Corporation. Degree of polymerization 800.
(2) Crosslinked vinyl chloride resin: trade name "GR1300S" manufactured by Shin-Etsu Chemical Co., Ltd. Partially cross-linked suspension type vinyl chloride resin. K value 68.
(3) Vinyl chloride-vinyl acetate copolymer: trade name "MB1008" manufactured by Kaneka Corporation. Vinyl acetate content: 10 mol%. K value 58.
(4) Plasticizer: Dioctyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., trade name "San-sizer DOP").
(5) First liquid heat stabilizer: liquid epoxidized soybean oil (manufactured by Sanwa Synthetic Chemical Co., Ltd., trade name "T-4000").
(6) Second liquid heat stabilizer: liquid barium heat stabilizer (manufactured by ADEKA Co., Ltd., trade name "AC 704").
(7) Solid heat stabilizer: powdery barium-zinc heat stabilizer (manufactured by ADEKA Co., Ltd., trade name "AP-623G").
(8) Other additives: lubricants, ethylene vinyl acetate, and fungicides.

[Examples 1 to 6 and Comparative Example 1]
The materials used above were blended in the proportions shown in Table 1 and thoroughly mixed, and then they were kneaded at 175 ° C. for 5 minutes with a twin-roll mill to produce sheets of 0.2 mm thickness. Thus, a test surface layer (100 mm long × 100 mm wide) having a thickness of 0.2 mm was formed.
In Examples and Comparative Examples in which the purpose is to confirm the presence or absence of whitening on the surface of the surface layer, the sheet main body is omitted because it is not necessary to provide a sheet main body as shown in FIG. 2 below the surface layer. Moreover, since it is not necessary to form the surface of surface layer in uneven | corrugated shape under this objective, the surface of surface layer was formed in flat form.
The whitening of the produced test surface layer and the thermal stability of the mixture of the materials used for each test surface layer were evaluated according to the following evaluation method. The results are shown in Table 1.
In addition, in Table 1, the numerical value of each used material (composition) is a mass part display. Moreover, in Table 1, in order to make an experimental result intelligible, the Example and the comparative example are arranged in order with the small amount of a liquid heat stabilizer.

(Evaluation of thermal stability)
Thermal stability is measured at a temperature (160 ° C. to 200 ° C.) assuming processing of the actual machine, by measuring the time required for forming a sheet of the mixture of the above materials into heat degradation (discoloring or curing) It evaluated. Specifically, the mixture of the above materials was put into an oven at 200 ° C., and samples were kept for 60 minutes every 5 minutes after the put-in, and the thermal deterioration of the collected samples was evaluated. In each table, "x" means that the heat stability was bad (deteriorated by 20 minutes after oven charging), "、" had sufficient heat stability (30 minutes after oven charging) Means "deterioration", "o" means having excellent thermal stability (deterioration after 40 minutes after oven charging).

(Evaluation of bleaching)
A surface layer for test is immersed in warm water at 40 ° C. for 24 hours based on JIS Z 8722 (color measurement method-reflection and transmission object color), and color difference (degree of whitening) before and after immersion is measured by a color difference meter (Nippon Denshoku Kogyo It measured using the Co., Ltd. product name and product name "Color Mater ZE2000."
Specifically, the difference between the color of the surface layer before immersion and the color of the surface layer after immersion in the CIE-L * a * b * color system corresponds to a color difference. In addition, the color difference was measured after superposing the surface layer for a test on a black base material. The larger the value, the more pronounced the whitening.
In each table, "x" means that the color difference exceeds 4.0 and significant whitening occurs before and after immersion, and "Δ" means that the color difference is more than 3.0 and 4.0 or less before and after immersion Means that the whitening occurred but was within the allowable range, “o” means that the color difference was more than 2.0 and 3.0 or less before and after immersion, and whitening was hardly seen “◎” means that the color difference was 2.0 or less before and after immersion, and almost no whitening was observed.

[Examples 7 to 12]
The materials used above were compounded in the proportions shown in Table 2 to form a test surface layer having a thickness of 0.2 mm as in Example 1, color differences were measured, and their softness was evaluated. Also, the thermal stability of the mixture of materials used was evaluated. In Table 2, in order to make an experimental result intelligible, the Example is arranged in order with the small amount of a plasticizer. The surface layer for test of Example 9 is the same as the surface layer for test of Example 3.
The flexibility of the test surface was evaluated by bending it by hand. "X" means that it was difficult to bend by hand, "△" means that it was sufficiently foldable by hand, and "o" was that it was easily foldable by hand means.

[Examples 13 to 18]
The materials used above were blended in the proportions shown in Table 3, and a surface layer for test having a thickness of 0.2 mm was formed in the same manner as in Example 1, and the color difference was measured. Also, the thermal stability of the mixture of materials used was evaluated. In Table 3, in order to make an experimental result intelligible, the Example is arranged in order with the small quantity of a vinyl chloride-vinyl acetate copolymer. The test surface layer of Example 13 is the same as the test surface layer of Example 3.

[Examples 19 to 21]
The materials used above were blended in the proportions shown in Table 4, and the surface layer for test was formed in the same manner as Example 1, and the color difference was measured. However, the surface layer for test of Example 20 had a thickness of 0.3 mm, and the surface layer for test of Example 21 had a thickness of 0.4 mm. Also, the thermal stability of the mixture of materials used was evaluated. The test surface layer of Example 19 is the same as the test surface layer of Example 3.

[Evaluation]
It can be seen from Table 1 that the smaller the content of the liquid heat stabilizer (epoxidized soybean oil and barium-based heat stabilizer), the lower the heat stability. In addition, it is understood that whitening tends to occur if the liquid heat stabilizer is too much. From Table 1, when the content of the liquid heat stabilizer is 1.5 parts by mass or more based on 100 parts by mass of the vinyl chloride resin, the thermal stability can be satisfied, and 1.5 parts by mass to 6.5 parts by mass If it is a part, it can be said that both suppression of whitening and thermal stability can be satisfied.
It can be seen from Table 2 that the less the plasticizer content, the less the coloration and the less the flexibility. From Table 2, when the content of the plasticizer in the surface layer for test is 26.0 parts by mass to 38.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, both suppression of whitening and flexibility can be satisfied. It can be said.
It is understood from Table 3 that as the content of the vinyl chloride-vinyl acetate copolymer is smaller, the whitening is less likely to occur. From Table 3, it can be said that both suppression of whitening and thermal stability can be satisfied if the content of the vinyl chloride-vinyl acetate copolymer is 25.0 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin .
It is understood from Table 4 that as the thickness of the surface layer is thinner, whitening is less likely to occur. From Table 4, it can be said that both suppression of whitening and thermal stability can be satisfied when the thickness of the surface layer is 0.45 mm or less.

  The interior sheet for a bathroom of the present invention can be used as a covering material of a general house, a bathing facility such as a public bath or a hotel, or a floor surface, wall surface or ceiling surface of various bathrooms such as a nursing care facility.

  DESCRIPTION OF SYMBOLS 1 ... Interior sheet for a bathroom, 2 ... Sheet | seat main body, 21 ... Lower layer, 22 ... Reinforcement layer, 23 ... Upper layer, 24 ... Design layer, 3 ... Surface layer

Claims (6)

A sheet body, and a surface layer provided on the surface of the sheet body,
The surface layer contains a vinyl chloride resin, a plasticizer, and a heat stabilizer,
The heat stabilizer comprises a liquid heat stabilizer and a solid heat stabilizer,
The content of the liquid heat stabilizers, Ri 1.5 parts by 8.5 parts by mass der respect to the vinyl chloride resin 100 parts by weight,
The solid heat content of stabilizer, bathroom interior sheet according to claim 1 parts by mass to 5 parts by mass der Rukoto relative to the vinyl chloride resin 100 parts by mass.   The bathroom interior sheet according to claim 1, wherein a content of the plasticizer is 26.0 parts by mass to 38.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin contains a vinyl chloride-vinyl acetate copolymer,
The bathroom interior sheet according to claim 1 or 2, wherein a content of the vinyl chloride-vinyl acetate copolymer is 25.0 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin.   The bathroom interior sheet according to claim 1 or 2, wherein the vinyl chloride-based resin substantially does not contain a vinyl chloride-vinyl acetate copolymer.   The thickness of the said surface layer is 0.05 mm-0.45 mm, The bathroom interior sheet as described in any one of Claims 1-4.   A bathroom floor sheet comprising the bathroom interior sheet according to any one of claims 1 to 5.

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