KR20100048442A - Natural wallpaper without organic solvent and the method of manufacturing the same - Google Patents

Abstract

PURPOSE: Natural wallpaper and a manufacturing method thereof are provided to offer flameproof function and environmentally-friendly function to the wallpaper by printing patterns on the wallpaper with a high temperature and high pressure transfer method. CONSTITUTION: Natural wallpaper includes the following: a base sheet(104) consisting of natural materials; a phosphorus compound flame retardant(106) coated on one side of the sheet; and a transfer-printed layer(108) transferred to the compound flame retardant without using an organic solvent. The sheet is made of natural fiber or paper. The natural wallpaper further includes a water-soluble adhesion layer(102). An imprint printing layer is formed on the transfer-printed layer.

Description

Natural wallpaper without organic solvent and the method of manufacturing the same

The present invention relates to a wallpaper and a method of manufacturing the same. More specifically, the base-sheet of a wallpaper made of natural materials such as natural fibers or paper is first surface-treated with a solution containing a flame retardant, and the organic solvent thereon The present invention relates to a wallpaper and a method of manufacturing the same, which are provided with a flame retardant function and environmental friendliness by printing by a high temperature and a high pressure transfer method without using a.

Recently, a lot of high-quality wallpaper with a material or pattern is used as a fabric wallpaper with a laminated fabric, and these fabric wallpapers are mainly imported from Europe, and domestic production is only weak.

Sheets, which are fabrics used in the conventional fabric wallpaper, are mostly made of synthetic resin such as PVC and PS, which may cause a large amount of toxic gases in case of fire, which may cause fatal damage to the human body. In addition, the sheet of the fabric wallpaper is flame retardant with a flame retardant, halogen-based flame retardant such as bromine-based flame retardant used in the prior art may cause environmental problems due to the generation of dioxin. In order to solve these environmental problems, it is a trend to replace with a flame retardant, but since phosphorite is not produced in Korea, the total amount depends on imports.

On the other hand, even if the sheet is made of natural fibers or paper, the wallpaper is printed to show color or pattern. However, in the conventional case, so-called birdhouse syndrome may be caused by using a volatile organic solvent in the printing process. That is, the use of volatile organic solvents becomes a problem and it is preferable not to use them.

New House Syndrome is an issue with the recent well-being fever, and it can cause symptoms such as headache, irritation of the eye and nasal mucosa, cough, itching of the skin, dizziness, fatigue, decreased concentration, and prolonged exposure to organic solvents, It has been reported to cause diseases such as heart disease and cancer. In particular, the high frequency of various atopic symptoms in children is known to be related to the use of volatile organic solvents.

Therefore, the technical problem to be achieved by the present invention is to provide an eco-friendly wallpaper that does not discharge pollutants such as dioxin and gives a flame retardant function and printing without using an organic solvent. In addition, another technical problem to be achieved by the present invention is to propose a method for manufacturing the eco-friendly wallpaper.

       Solvent-friendly wallpaper of the present invention for achieving the above technical problem comprises a sheet made of a natural material, a phosphorus compound flame retardant coated on at least one surface of the sheet and a transfer printing layer transferred without containing an organic solvent on the phosphorus flame retardant. Characterized in that.

       In a preferred embodiment of the present invention, the sheet may be characterized in that made of natural fibers or paper. In addition, the flame retardant may be characterized in that it comprises a monomer having a structure of formula (1).

Here, X, W is a reaction functional group, Y, Z may be an element or a flame retardant functional group, such as carbon, phosphorus, silicon, boron. In addition, R1, R2, and R3 are aromatic functional groups, respectively.

The flame retardant may be characterized in that the monomers are bonded in a chain by a functional group to form an end functionalized structure that is a condensed structure. In another embodiment, the monomer may be bonded in a chain by a functional group to form a functional group pendant structure.

In addition, the monomer may be partially bonded in a chain form by a functional group to form an oligomer, and the oligomer may be cross-linked by an aromatic functional group to have a network structure.

It may be characterized in that it comprises a modified phosphorus-based compound comprising a nitrogen compound of the following formula (2) in the X, Z position of the monomer constituting the flame retardant.

In addition, it may be characterized in that it comprises a modified phosphorus-based compound comprising a sulfur compound of Formula 3,

       It may be characterized by including a modified phosphorus-based compound comprising a silicon compound of the formula (4).

       Here, Ph is a phosphate functional group.

       Method for preparing a solvent-free environmentally friendly wallpaper according to an embodiment of the present invention comprises the steps of preparing a sheet of natural material, forming a flame retardant layer by coating a phosphorus compound containing the monomer of Formula 1 on at least one surface of the sheet and the Characterized in that it comprises the step of forming a transfer printing layer on the flame retardant layer without containing an organic solvent.

       The flame retardant layer may be formed by surface treatment at 0.01wt% to 0.5wt% to form a residual flame time of 3 seconds or less, a residual time of 5 seconds or less, a carbon screen area of 30 cm 2 or less, and a carbonization length of 20 cm or less. In addition, the transfer printing layer may be characterized in that the transfer at a pressure of 8 kgf / cm 2 to 10 kgf / cm 2 at a temperature of 200 ℃ to 230 ℃.

According to the eco-friendly wallpaper of the present invention, by using the sheet as a natural fiber or paper, it is possible to prevent the generation of toxic gas in the fire, it is possible to solve the problem of dioxin emission by using a non-halogen self-extinguishing flame retardant. Furthermore, by using high temperature and high pressure transfer printing without using an organic solvent, generation of volatile substances (VOCs) causing sick house syndrome can be prevented in advance, and in particular, water-soluble adhesives can be introduced to further improve environmentally friendly functions.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

Embodiments of the present invention will provide a wallpaper and a method of manufacturing the same having an environmentally friendly way to form a pattern by printing the sheet by flame-retardant and printing by a high temperature, high pressure transfer method. To this end, first, the eco-friendly wallpaper will be described, and then the characteristics of the elements constituting the eco-friendly wallpaper will be described in detail. Next, the manufacturing process of the eco-friendly wallpaper will be described.

1 is a cross-sectional view of an eco-friendly wallpaper according to an embodiment of the present invention.

Referring to FIG. 1, at least one surface of the sheet 104 is provided with a flame retardant layer 106 flameproofed with a flame retardant. The sheet 104 of the wallpaper is preferably natural fibers or paper, and in the case of fibers, the thickness of the fiber fabric is preferably 100 µm to 200 µm. In addition, a transfer printing layer 108 is formed on the flame retardant layer 106 on one side of the flame-retardant sheet. In addition, the release layer 100 is positioned on the flame retardant layer 106 on the other side of the flame retardant sheet 104 via the adhesive layer 102. In this case, the release layer 100 may have a thickness of about 100 μm, and in some cases, may include a separate primer layer (not shown).

Eco-friendly wallpaper sheet 104 may be used both synthetic resin or natural fibers, but it is preferable to use natural fibers or paper, such as natural silk, cotton, hemp. This is because synthetic resins such as PVC and PS, which are used in the past, are toxic gases such as carbon monoxide and hydrogen chloride, depending on the components in case of fire.

However, if the natural fiber is used as it is, even if the various toxic gases emitted from the sheet 104 in the event of a fire, smoke and soot may still occur. In addition, it is preferable to perform flame retardant treatment because it can increase the damage of buildings by the burning of wallpaper.

The wallpaper is a finishing material in the interior of the building has a large impact on the appearance, and includes a transfer printing layer 108 to give an aesthetic. The printing layer of the conventional wallpaper is made by printing a pattern or color directly on a sheet. In order to directly print the paint on the sheet, organic solvents such as benzene and toluene are used. These organic solvents are known as causative agents such as sick house syndrome and atopy.

On the other hand, even if the adhesive is used as an eco-friendly product during the construction of the wallpaper, the wallpaper including the printing layer using the organic solvent is twice as many as the toluene and benzene emitted from the wallpaper itself than the adhesive using the organic solvent. Known. In other words, even if the adhesive is used as an eco-friendly product, it is difficult to achieve an eco-friendly effect as long as it uses a printing method using an organic solvent. In addition, since the printing method is a method of dipping a paint dissolved in an organic solvent, the state of the printing layer may be poor depending on the state of the sheet surface.

Therefore, the wallpaper according to the embodiment of the present invention is characterized by including a transfer printing layer 108. The transfer printing layer 108 transfers the printed film to a sheet in a state of high temperature and high pressure, so that the printing pattern is clearer than the conventional direct printing method, and it may have environmentally friendly characteristics because it does not use an organic solvent.

The flame retardant treatment applied to the embodiment of the present invention treats the surface of the sheet 104 with a flame retardant to suppress combustion of the sheet 104. The flame retardant refers to a material having a function of preventing the contact between the substrate and oxygen by reacting below the decomposition temperature of the substrate and preventing combustion by releasing non-combustible gas. Combustion of the sheet to which the flame retardant is applied proceeds in the order of heating, softening of the compound, decomposition and ignition of the decomposed gas, and inhibits combustion of the sheet 104 with the following characteristics.

The flame retardant delays the chain reaction by free radicals, generates incombustible vapors such as water vapor, carbon dioxide, and ammonia to maintain a high flash point of the gas decomposed from the substrate, and promotes the formation of a carbonized state. Can function. It also decomposes into an endothermic reaction with the substrate, reducing the heat of combustion and suppressing the progress of the flame.

In general, flame retardants are roughly classified into additive types which blend with a polymer to impart flame retardancy and reaction types which include a flame retardant component in the polymer itself. The flame retardant used in the embodiment of the present invention is an additive type, the additive type flame retardant is divided into an organic flame retardant and an inorganic flame retardant. Organic flame retardants include halogen flame retardants and phosphorus flame retardants, and antimony oxide and aluminum hydroxide are inorganic flame retardants and are mainly used as auxiliary flame retardants.

Halogen-based flame retardants can be broadly divided into chlorine and bromine. The brominated flame retardant is TBBA (tetrabrombisphenol A), DBDPO (decabromodiphenyloxide), DBDPE (decabromodiphenylethane) and the like, the chlorine-based is TCP (chlorinated paraffin) and the like. The halogen-based flame retardant has been widely used since it has an advantage in terms of economic efficiency and flame retardant efficiency. In particular, bromine-based flame retardants are used in combination with antimony trioxide can increase the flame retardant effect. However, some countries, such as Germany, regulate the use of the halogen or antimony flame retardant by the dioxin regulation law, and even in countries without the law, the use of the environmental problem is an international issue in recent years.

Therefore, the embodiment of the present invention uses a phosphorus-based flame retardant that can satisfy both environmental problems and efficiency of flame retardancy. Phosphorus-based flame retardants are non-halogen flame retardants that have their own digestibility. Formula 1 is an example of a flame retardant monomer structural formula according to an embodiment of the present invention.

Here, X and W are reaction functional groups, and Y and Z are carbon and phosphorus functional groups. R1, R2, and R3 are aromatic and easily combine with hydrogen (H), alkyl, (phenyl) and the like to facilitate the formation of a three-dimensional network structure. Y and Z are phosphorus functional groups that impart flame retardancy and may be the same or different phosphorus functional groups.

In the case of the phosphorus flame retardant Y or Z of the monomer may include carbon (C) or phosphorus (P), in the case of halogen flame retardant Y or Z of the monomer may include silicon (Si) or boron (B). .

The monomer of Formula 1 has a polycyclic aromatic structure. The monomer decomposes during combustion to form radicals such as HPO _{2 and} PO, and the phosphorus radicals thus formed trap H radicals or OH radicals active in the vapor phase, and dehydration of the phosphorus functional groups. It forms a highly viscous glassy or dense carbon char to block oxygen from the outside. In this case, the formation of porous carbon agglomerates increases the flame retardant effect, and the pore shape of the carbon agglomerates also varies according to the characteristics of the chemical structure of the flame retardant.

Hereinafter, examples of the flame retardant formed by using the monomer of Chemical Formula 1 will be described with reference to FIGS. 2 to 9.

 2 to 5 are structural formulas showing one example of a flame retardant according to an embodiment of the present invention.

As shown in FIG. 2, the monomer 200 may be chained together by the functional group 202 to form an end functionalized structure, which is a condensed structure. At this time, the aromatic functional group bonded to the monomer 200 is combined with hydrogen (H), an alkyl group, a phenyl group and the like to form a three-dimensional network structure.

 The flame retardant of such a terminal functional structure is coated on the sheet of the present invention (104 in FIG. 1) to form a flame retardant layer 106. Flame retardants having a terminal functional structure can, when burned, form a carbon char 204 as shown in FIG. 3. The carbon agglomerate 204 serves to block the supply of oxygen, which can prevent combustion of the sheet 104.

According to FIG. 4, the flame retardant may be formed by a macro aromatic condensation phase of a functional group pendant structure in which a structure in which the monomers 200 are suspended on the carbon chain skeleton 206 is superimposed on each other. The flame retardant having the structure of the above-mentioned large aromatic condensed phase can form the carbon lump 204 as shown in FIG. 5 when combusted. The carbon agglomerate 204 serves to block the supply of oxygen, which can prevent combustion of the sheet 104.

8 and 9 show another example of the flame retardant according to the embodiment of the present invention, and FIGS. 6 and 7 show the structure of the oligomer constituting the flame retardant shown in FIGS. 8 and 9.

6 and 7, the monomers 200 are chain-linked by the functional group 202 attached to the monomers 200 to form oligomers. These oligomers are linked to each other and the porosity is determined by the binding form. In order to improve the electrostatic attraction between the oligomers, an epoxy group may be bonded at both ends. What is shown in a flag shape for every monomer which comprises the said oligomer shows the direction in which the aromatic functional group is connected.

The oligomer combined with the oligomer and the epoxy group constitutes a flame retardant having a three-dimensional network structure to be described below by cross-linking between the functional groups 202.

Referring to FIGS. 8 and 9, the flame retardant herein forms a three-dimensional network flame retardant by crosslinking of the oligomers with the functional groups 202 of the aromatic. This feature is different from the condensed-phase flame retardant shown in FIGS. 3 and 4.

At this time, as shown in Figure 9 by bonding an epoxy group to at least one chain of the oligomer, it is possible to improve the binding force of the flame retardant.

The flame retardant having a three-dimensional crosslinked functional group on the net may form a carbon lump 204 like the large condensed phase flame retardant in FIGS. 3 and 5, although not shown when combusted. The carbon agglomerate 204 serves to block the supply of oxygen, which can prevent combustion of the sheet 104.

Hereinafter, modified examples of the phosphorus-based flame retardant represented by Chemical Formula 1 are presented.

Modified phosphorus-based functional groups shown in the following formulas (2), (3) and (4) are bonded to the Y or Z position of the formula (1). Combining heterogeneous elements can improve the flame retardant effect than when used alone. The synergistic effect of the combination of phosphorus and halogen is widely known, and chlorine-containing phosphate esters are used as flame retardants such as urethane.

The flame retardant including the modified phosphorus-based functional group reduced the amount of smoke and volatiles than when using a conventional phosphorus-based flame retardant, and also makes the generation of carbon agglomerates well.

Formula 2 below is a structural formula representing a modified phosphorus compound including a nitrogen (N) compound. Nitrogen compounds serve to facilitate the formation of carbon lumps by promoting the dehydration effect. Here, Ph represents a phosphate functional group.

Formula 3 below is a structural formula representing a modified phosphorus compound including a sulfur (S) compound. The sulfur compound also serves to facilitate the formation of carbon agglomerates by promoting the dehydration effect as the nitrogen compound. Here, Ph represents a phosphate functional group.

Formula 4 below is a structural formula representing a modified phosphorus-based compound including a silicon (Si) compound. The silicone compound plays a role of stably maintaining the crosslinking, such as the action of carbon in the organic material.

       The modified phosphorus compounds are not only environmentally friendly than halogen-based, but also have a trapping force of gaseous free radicals more than twice. The trapping power is high because the outer energy of the phosphorus atom is higher than that of halogen atoms such as bromine and fluorine.

Wallpaper according to an embodiment of the present invention can form a flame retardant layer 106 with a high-temperature, high-pressure transfer printing layer 108 and a phosphorus-based flame retardant that is self-extinguishing, thereby reducing the damage caused by dioxins or volatile organic solvents. However, the pressure-sensitive adhesive used to attach the sheet to the release layer 100 generally includes an organic solvent for functional and economic reasons. Therefore, in order to prevent microscopic side effects caused by the volatile organic solvent generated in the wallpaper, the adhesive layer 102 may be formed as a water-soluble adhesive.

A method of manufacturing a solvent-free environment-friendly wallpaper according to an embodiment of the present invention will be described with reference to FIG. 1. First, the sheet 104 of the wallpaper is selected. Although the sheet 104 may be synthetic resin, it is preferable to select natural fibers or paper such as natural silk, cotton, and hemp.

The surface of the selected sheet 104 is then treated with a flame retardant to form the flame retardant layer 106. The flame retardant is preferably a non-halogen flame retardant, in particular phosphorus-based flame retardant. At this time, the non-halogen flame retardant surface treatment of 0.01wt% to 0.5wt% is more preferably to have a flame retardancy of 3 seconds or less after residual time, 5 seconds or less after residual time, 30 cm 2 or less carbonization length, 20cm or less.

Next, the patterns and colors required for the transfer paper are separately printed. The pattern primarily printed on the transfer paper is transferred to the flame retardant sheet 104 under high temperature and high pressure. At this time, the temperature is 200 ℃ to 230 ℃, the pressure is preferably 8kgf / ㎠ to 10kgf / ㎠. When the transfer printing layer 108 is formed by the above method, no harmful substances such as azo dyes, formaldehyde, toluene, heavy metals, etc. are detected.

When it is necessary to give gloss according to the use of the wallpaper, metal, such as gold, silver, and chromium, is deposited at a high temperature to form a metal thin film separately, and then a high temperature, High pressure transfer is performed to form a metal layer (not shown). Finally, the adhesive layer 102 is coated on the release layer 100 and the wallpaper is adhered thereto to manufacture an eco-friendly wallpaper.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but many variations and modifications may be made without departing from the scope of the present invention. It is possible. For example, in the embodiment of the present invention, but limited to a sheet made of a natural material, a sheet made of synthetic resin can also be applied to the sheet of the present invention if the flame retardant treatment is sufficient.

1 is a cross-sectional view showing an eco-friendly wallpaper according to the present invention.

2 to 5 structurally illustrate one example of the flame retardant according to the present invention.

6 and 7 show the structure of the oligomer constituting the flame retardant according to the present invention.

8 and 9 structurally show another example of the flame retardant according to the present invention.

* Description of Major Symbols in Drawings *

100: release layer 102: adhesive layer

104: sheet 106: flame retardant layer

108: transfer printed layer 200: monomer

202: Carbon Lump 204: Carbon Lump

206: carbon chain skeleton 210: epoxy group

220: aromatic functional group

Claims (13)

Sheets made of natural materials; A phosphorous compound flame retardant coated on at least one side of the sheet; And Solvent free eco-friendly wallpaper comprising a transfer printing layer transferred to the phosphorus-based flame retardant does not contain an organic solvent. The solvent-free eco-friendly wallpaper according to claim 1, wherein the sheet is made of natural fibers or paper. The solvent-free wallpaper of claim 1, wherein the flame retardant comprises a monomer having a structure of Formula 1 below.

Here, X and W are reaction functional groups, and Y and Z are elements such as carbon, phosphorus, silicon, and boron or flame retardant phosphorus-based functional groups. In addition, R1, R2, and R3 are aromatic functional groups, respectively. The solvent-free wallpaper of claim 3, wherein the flame retardant forms an end functionalized structure in which the monomer is chained together by a functional group to form a condensed structure.       According to claim 3, The flame retardant is a solvent-free eco-friendly wallpaper, characterized in that the monomer is bonded in a chain by a functional group to form a functional group pendant structure (functional group pendant structure). According to claim 3, The flame retardant is a solvent-free environmentally friendly wallpaper, characterized in that the monomer is partially bonded in a chain form by a functional group to form an oligomer, the oligomer cross-linked by an aromatic functional group has a mesh structure. . According to claim 3, The flame retardant is a solvent-free environment-friendly wallpaper, characterized in that it comprises a modified phosphorus-based compound comprising a nitrogen compound of the following formula (2) in the Y, Z position of the formula (1).

Ph is a phosphate functional group. The environmentally friendly wallpaper of claim 3, wherein the flame retardant comprises a modified phosphorus-based compound including a sulfur compound represented by Formula 3 at Y and Z positions of Formula 1.

Ph is a phosphate functional group. The environmentally friendly wallpaper of claim 3, wherein the flame retardant further comprises a modified phosphorus-based compound including a silicon compound represented by Formula 4 below at the Y and Z positions.

The solvent-free eco-friendly wallpaper according to claim 1, further comprising a water-soluble adhesive layer on the sheet facing the transfer printing layer with respect to the sheet. Preparing a sheet made of natural materials; Forming a flame retardant layer by surface treatment with a phosphorus compound including the monomer of Formula 1 on at least one surface of the sheet; And A method of manufacturing a solvent-free environment-friendly wallpaper comprising the step of forming a transfer printing layer on the flame retardant layer without containing an organic solvent. 12. The method of claim 11, wherein the flame retardant layer is surface-treated at 0.01wt% to 0.5wt% to form a residual flame time of 3 seconds or less, a residual time of 5 seconds or less, a carbon screen area of 30 cm or less, and a carbonization length of 20 cm or less. Manufacturing method of solvent-free eco-friendly wallpaper. The method of claim 11, wherein the transfer printing layer is transferred at a pressure of 8 kgf / cm 2 to 10 kgf / cm 2 at a temperature of 200 ° C. to 230 ° C. 13.

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