JP3486964B2 - Wall covering sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is, absorbing and releasing moisture, condensation-preventing properties, excellent heat resistance, deodorizing properties, it relates to the excellent wall covering sheet to decorative on having excellent antimicrobial properties.

[0002]

2. Description of the Related Art Conventionally, in order to make the living environment comfortable,
Various functions are added to the wall covering sheet. For example, with regard to the humidity control function, a method of adding fine particles of an organic polymer such as sodium polyacrylate having a moisture absorbing / releasing property or an inorganic fine particle such as silicon dioxide having a porous surface, deodorizing property, antibacterial property, activated carbon , Zeolite,
A method of adding a quaternary ammonium salt of organic silicon, cuprous sulfate, a metal phthalocyanine compound, an extract from a natural plant, etc. has been proposed. However, the method of using these substances is that after filling the resin for wall covering,
After being formed into a sheet or a wall covering sheet, a treatment agent containing such a substance is applied to the sheet surface,
The method of filling the resin, the physical properties such as the strength of the sheet is reduced, in manufacturing the sheet, an extra step of mixing the functional substance is required, for the sheeting method, in the extrusion process, There is a limitation in the manufacturing method because the packing is clogged. In addition, in the method of applying to the surface of the sheet, there are various problems such as the loss of the original tactile sensation of the sheet, an increase in the cost of the applying step, and easy stain of the coated product.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to provide a wall covering sheet having excellent physical properties, high humidity control, deodorization, antibacterial properties, and excellent surface decoration. Ah
It

[0004]

The present invention has the following constitution in order to achieve the above object.

That is, the wall covering sheet of the present invention is a sheet composed of an ethylene / acrylic acid copolymer or an ethylene / methacrylic acid copolymer, and the carboxyl terminal group of the polymer has the following 1 to 3 Cation selected from
In Ru der which is characterized in that it is substituted. (1) Na + or K + ion (2) Zn2 +, Cu2 +, Mn2 +, Ag +, Fe2 +
At least one metal ion selected from the group (3) quaternary ammonium ion

[0006]

In the present invention, as a result of earnestly studying a wall covering sheet having excellent physical properties and decorativeness, particles or resin for adding functionality as in the conventional case is added, or it is applied to the surface of the sheet. it not, by replacing the sheet carboxyl end groups comprising ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer with a cation such as a metal ion or a quaternary ammonium ion, said <br/> physical A sheet having both physical properties and various functions can be obtained, and further, the spacing or thickness is 0.1 to 100 on the sheet surface.
By forming an extremely fine uneven pattern of μ,
It has been clarified that various functions are effectively exerted because the decorative property is excellent and the surface area of the sheet surface becomes large.

An ethylene / acrylic acid copolymer of the present invention,
The ethylene / methacrylic acid copolymer is a block or random copolymer of ethylene and acrylic acid or methacrylic acid, and those commercially available as a copolymer can generally be used and are not particularly limited. Absent. The copolymerization ratio is 100 by weight of ethylene,
Acrylic acid or methacrylic acid is 5 to 40, preferably 10 to 30. In the present invention, the copolymer is formed into a sheet, and a known method such as a calendering method or a T-die extrusion method can be adopted as a sheeting method, and the sheet has a thickness of 0.01 to It is 1 mm. It does not matter if it is joined to a fiber cloth when it is formed into a sheet.

One of the hydrogen ions of the carboxyl group of the copolymer of the present invention is one which is replaced by Na + or K + ion.

In the present invention, the content of such a carbobixyl group substituted with a predetermined metal ion is 3 × 1.
0 is intended to ^-5 gram equivalent / gram polymer above, it is possible to impart Hygroscopic performance of cotton comparable Such substitutions are those that significantly improve heat resistance, which is estimated to be due to ionic cross-linking can be imparted .

The hydrogen ion of the carboxyl group of the copolymer of the present invention includes Zn + 2, Cu + 2, Ni + and Mn.
It is substituted with at least one metal ion selected from the group consisting of +2, Ag + and Fe2 +.

In the present invention, the content of the carboxyl group substituted with the predetermined metal ion is 1 × 10.
^-5 gram equivalent / gram polymer or more,
If less than 1 × 10 ⁻⁵ gram equivalent / gram polymer,
It becomes difficult to eliminate the bad smell such as hydrogen sulfide which is the object of the present invention. In addition to the carboxyl group substituted with a predetermined metal ion of the present invention, a free acidic group is added at 2 × 10 ^−4.
It is preferable that the polymer also contains ˜1 × 10 ⁻² gram equivalent / gram polymer, because it can simultaneously deodorize basic malodor such as ammonia and alkylamine in addition to acidic malodor such as hydrogen sulfide.

[0012] Hydrogen ions of the carboxyl groups of the copolymer of the present invention, one is also intended to be replaced by quaternary ammonium ions. Examples of such a quaternary ammonium ion source include a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group, a hydrocarbon group forming a heterocyclic ring of nitrogen of the nitrogen compound, and a combination of these groups. There is no particular limitation as long as it is a quaternary nitrogen compound having a hydrogen group and has antibacterial and antifungal properties. Among them, there is a quaternary ammonium salt represented by the following general formula as a typical quaternary nitrogen compound having a total carbon number of the hydrocarbon group of 10 or more, preferably 15 or more.

[0013]

[Chemical 1] Here, R1 to R4 represent a monovalent hydrocarbon group, but in place of any two or four of these hydrocarbon groups,
It may have a structure having one or two divalent hydrocarbon groups having a bond so as to form a nitrogen-containing heterocycle. X represents a halogen ion, and a chlorine ion or a bromine ion is generally used. Specific examples thereof include lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl trimethyl ammonium chloride, cetyl pyridinium chloride and the like, and these can be used alone or as a mixture of two or more kinds.

Further, within the range that does not impair the effects of the present invention,
Various deodorants, antibacterial agents, coloring agents, flame retardants and the like may be contained.

The wall covering sheet of the present invention has an extremely fine uneven pattern formed on the surface. Such engraving may be performed before or after modifying the carboxyl terminal group.

The wall covering sheet excellent in decorativeness of the present invention has extremely fine irregularities in which the intervals and the thickness of the lines are 0.1 to 100 μm. Such an uneven pattern is also extremely fine in terms of depth, and it is possible to clearly confirm even a depth of about 1 μ.

The method for producing a sheet having a fine uneven pattern of the present invention includes, for example, a fiber sheet (including a woven fabric, a knitted fabric, a non-woven fabric, a composite cloth thereof and a laminated cloth thereof) and a sheet having a fine uneven pattern on the surface (plastic). , Wood, metal plates, sheets made of various materials such as leather), etc., and at least the surface used for engraving of the engraved sheet with engraved patterns, etc. After thermocompression bonding, cooling, and then peeling.

In the formation of the concavo-convex pattern of the present invention, the engraved pattern obtained by engraving a plurality of thin cloths can express even fine fine irregularities that exhibit moire.

As the water-repellent agent of the present invention, a fluorine-based resin, a silicon-based resin, a wax-based resin or the like can be used, but it is possible to form a clear engraved pattern and to use the engraving sheet a plurality of times. The former two are preferred.

As a method for producing the uneven pattern of the present invention, for example, the engraved sheet (for example, the texture pattern of the fibrous structure) is formed on one surface of the molten resin sheet extruded in a sheet shape from a T die. After inserting and pressing between a cooling roll and a pressure roll, a method of peeling off the engraved sheet, or when the engraved sheet is inserted into at least one surface at the time of forming into a sheet by a thermal calendar, pressed and cooled. After that, a method of peeling the fibrous structure, and a method of laminating the fibrous structure on the surface of a sheet formed by various methods and pressing it between heated rolls or flat plates can be adopted.

The fine concavo-convex pattern of the present invention not only enhances the decorative property and fashionability of the wall covering sheet, but also increases the surface area of the sheet surface. Therefore, when the carboxyl terminal group is modified after engraving. The treatment efficiency is improved, and various functions such as deodorizing property, humidity control property, antibacterial property, etc. of the modified carboxyl terminal group can be more effectively exhibited.

[0022]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

The performances shown in Examples and Comparative Examples were measured by the following methods.

(Hygroscopicity) A sheet of 1 g is dried at 100 ° C. for 24 hours.
hr Weigh after drying (W1), 20 ℃, 65%
Weight (W) after leaving for 24 hours in RH temperature and humidity atmosphere
2), the weight (W3) after standing in a humidity atmosphere at a temperature of 30 ° C. and 95% RH for 24 hours was measured, and the amount of moisture absorption was determined from the weight change.

M1 (%) = (W2-W1) / W1 × 100 M2 (%) = (W3-W1) / W1 × 100 (condensation) 200 cc of hot water at 20 ° C. in a 300 cc beaker
The sheet was put in, and the sheet was weighed in advance (a), the lid was covered, and the sheet was left in a humidity atmosphere of 5 ° C. and 60% RH for 2 hours. Then, the sheet weight (b) containing the dewed water was measured and then dewed. The weight (c) after the water was wiped off with a filter paper was measured, and the amount of dew condensation (A) and the amount of moisture absorption (B) were calculated.

A (g / m ² ) = (bc) / beaker mouth area B (g / m ² ) = (ca) / beaker mouth area (heat resistance) The lit part of the cigarette with the mark was kept in contact with it vertically, and the degree of damage when the cigarette was removed after 5 seconds was evaluated.

◯: There was no hole Δ: There was a hole of about half the diameter of the cigarette ×: There was a hole of the same size as the diameter of the cigarette (ammonia deodorization) of 0.3% in a 500 cc polyethylene resin container 80 μg of ammonia water was added dropwise, 3 g of the sheet was placed in the container and sealed, and the residual ammonia concentration after 20 minutes was measured using a gas detector tube manufactured by Gastec Co., Ltd., and the amount of ammonia in 100 cc of gas in the container was measured. did. The ammonia concentration at the start is about 150 ppm.

(Deodorization of hydrogen sulfide) Iron sulfide 300
The measurement was carried out by the same method as the ammonia deodorization except that 100 mg of 0.6% sulfuric acid and 0.6% sulfuric acid were used. The hydrogen sulfide concentration at the start is about 40 ppm.

(Antibacterial a) Staphylococcus aureus 12 on a sterilized sheet
732) broth suspension was added, and the mixture was placed in a closed container.
The viable cell count after culturing at 18 ° C. for 18 hours was measured, and the increase / decrease value with respect to the inoculum count was determined. An increase / decrease value of 1.6 or more has excellent antibacterial properties.

(Antibacterial B) Klebsiella (K
lebsiella pneumoniae ATCC
4352) was added, and the viable cell count after shaking at 150 times / min for 1 hour in a closed container was measured to determine the reduction rate of the added suspension with respect to the cell count. It has an excellent antibacterial property with a reduction rate of 26% or more.

(Tensile Strength of Sheet) JIS K 67
It measured by the method prescribed | regulated in 30, and the tenacity retention (%) was calculated.

(Deepness of color of sheet) Reflectance of sheet (L
Value) was measured by a digital colorimetric color difference meter manufactured by Suga Test Instruments Co., Ltd. The smaller the number, the darker the color.

(Evaluation of engraved pattern) The number of grooves formed per inch and the width of grooves formed of monofilaments of yarns constituting the fabric were measured by observing with a microscope.

The diameter of the single fiber in the woven fabric is 10.1 μ.

Examples 1 to 7 and Comparative Examples 1 to 4 A resin prepared by mixing an ethylene / methacrylic acid copolymer consisting of 85 parts by weight of ethylene and 15 parts by weight of methacrylic acid with a blue colorant and a weathering agent is extruded from a T die. A sheet with a thickness of 0.1 mm was formed with or without an engraved sheet, treated with the following treatment liquid at 70 ° C for 30 minutes, washed with water, dried, and then evaluated for performance. Shown in 1.

(Engraving sheet) A flat Georgette fabric dyed in black (manufactured by Toray Industries, Inc.), which is made of 75-denier 72-filament strongly twisted polyester fiber as warp and weft.
Dip warp density 93 threads / inch, weft density 72 threads / inch in Toray Silicon SH8240 (Toray Dow Corning Co., Ltd. silicon water repellent) 40 g / ■ aqueous solution,
After adjusting the squeezing amount to 80% by weight with the mangle,
It was dried at 0 ° C and heat set at 180 ° C.

A piece obtained by engraving one of the woven fabrics was designated as (A), and a piece formed by stacking two woven fabrics was designated as (B).

(Modification Treatment of Carboxyl Terminal Group) a. 1% aqueous sodium hydroxide solution b. 2% aqueous copper sulfate solution c. 2% zinc sulfate aqueous solution d. As a comparative example of a 1% aqueous solution of lauryldimethylbenzylammonium chloride, 5 and 20% by weight of a non-modified carboxyl terminal group (Comparative Example 1) and a sodium polyacrylate superabsorbent polymer (Sumikagel SP510 manufactured by Sumitomo Chemical Co., Ltd.) A mixture of 1 part by weight (Comparative Examples 2 and 3) and a mixture of 2 parts by weight of silver zeolite particles (Comparative Example 4) were similarly evaluated.

[0039]

[Table 1] It can be seen from Table 1 that the present invention does not deteriorate the physical properties of the sheet and has excellent moisture absorption / release properties, dew condensation prevention properties, heat resistance, deodorizing properties, antibacterial properties, and decorative properties.

As a result of observing the engraved pattern of Example 2 with a microscope, the number of grooves formed by the warp yarn was 92 / inch, and the width of the groove formed by the single fiber of the woven fabric was 10.1 μ. It was confirmed that the fiber structure of the woven fabric was engraved extremely clearly.

The color developability of the sheet having the pattern engraved is a deep hue.

[0042]

EFFECTS OF THE INVENTION According to the present invention, it has excellent physical properties and functions such as high moisture absorption and desorption, dew condensation prevention, heat resistance, deodorization, and antibacterial properties, and has excellent decorative properties as a wall covering material. It is possible to stably supply a wall covering sheet having an appearance.

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Claims (4)

(57) [Claims] 1. A sheet comprising an ethylene / acrylic acid copolymer or an ethylene / methacrylic acid copolymer,
Also, the carboxyl terminal group of the polymer is 1 to 3 below.
A wall covering sheet characterized by being replaced with a cation selected from the above. (1) Na + or K + ion (2) Zn2 +, Cu2 +, Mn2 +, Ag +, Fe2 +
At least one metal ion selected from the group (3) quaternary ammonium ion 2. A thickness of the sheet surface, spacing and line 0.1
A contract characterized by having an uneven pattern of -100 μm
The wall covering sheet according to claim 1 . Wherein said uneven pattern, according to claim 2 which is a moire pattern
Wall covering sheet according to. 4. A depth of the uneven pattern is, wall covering sheet according to claim 2 or 3 is at least 1 [mu].