KR100877785B1 - Floor-cover with anionic polymer - Google Patents

Abstract

The present invention relates to a longboard having a functional layer containing an anionic polymer resin and a method for producing the same.

The present invention relates to a longboard and excellent method for producing a functional paper prepared by adding functional additives such as germanium-containing wood clay, charcoal to anionic polymer resin that does not absorb far infrared rays.

Flooring, flooring, wood clay, germanium, far infrared rays, anion.

Description

Longboard containing anionic polymer resin {Floor-cover with anionic polymer}

1 is a layer configuration diagram of a conventional longboard,

2 is a layer configuration diagram of the longboard of the present invention.

<Description of the symbols for the main parts of the drawings>

1. Surface layer 2. Hard coating layer 3. PVC functional layer

4. Back layer 5. Functional layer

The present invention relates to a longboard and excellent method for manufacturing the same, and particularly to the functional cardboard produced by adding a functional additive, such as wood clay, charcoal containing germanium to anionic polymer resin that does not absorb far infrared rays and its preparation It is about a method.

It is reported that the floorboard, which is a conventional finishing material for interior construction, is a PVC floorboard, which releases formaldehyde (HCHO) to cause atopic dermatitis, headache, and the like. In addition, these substances are the causative agent of sick house syndrome, and it has been reported that it takes several years or longer for the causative agent of sick house syndrome to be removed. To solve these problems, harmful substances such as formaldehyde are used. Attempts have been made to develop functional eco-friendly paperboards containing functional additives that emit far-infrared and negative ions such as ocher, tourmaline, germanium, elvan, natural jade, charcoal and silver, which are not natural materials.

As is widely known, far-infrared rays have been scientifically confirmed to be effective, and in the past, products that apply far-infrared radiation substances that existed mainly in the natural environment to daily use have been developed and released in various ways. Far-infrared rays are absorbed by human body with 30 ~ 1000 micron hot wire which has longer wavelength than visible light, and it is reported to have health promoting effect of promoting blood circulation and waste discharge, and representative materials include ocher, germanium, elvan, natural jade, etc. .

In addition, as is well known, anions are known to have a function of neutralizing cations emitted from pollutants and oxides to adsorb and neutralize cations harmful to humans in the atmosphere. , Germanium, tourmaline, natural jade, elvan, loess and silver. Various products have been developed and released. Therefore, the backing layer, the PVC resin layer, the hard coating layer, and the printing layer are laminated in order to add a functional material that has antibacterial and deodorizing functions such as ocher, germanium, and charcoal, and emits anion and far infrared rays, which are beneficial to health. Functional floorboards have been developed recently. For example, Korean Patent Laid-Open Publication No. 1998-673030 discloses a longboard having a far-infrared radiation functional layer containing a material that emits far infrared rays in PVC resin, and Korean Patent Laid-Open Publication No. 1991-18633 discloses PVC, PP, Paperboard having a functional layer in which ceramic raw materials, clay, kaolin, feldspar, copper powder, and charcoal is added to PE resin is disclosed, and Korean Laid-Open Patent Publication No. 2003-47078 has a sheet of paper having a functional layer containing clay in a synthetic resin. Is disclosed.

However, in the case of the conventional longboard containing a functional additive that emits far infrared rays and anions, even if a large amount of functional powder is added to the PVC resin, most of the anion and far infrared rays emitted from the functional additive pass through the constituent layers of the longboard and are actually lost. The problem that the amount of anion and far-infrared radiation emitted through the cardboard is very small has been raised continuously. Also, the cardboard produced by dispersing functional additives such as ocher, germanium and charcoal in PVC resin has a weak layer binding force. It was difficult to commercialize due to poor durability such as tearing or imprinting. In addition, PVC resins have been designated as environmentally regulated substances because they generate toxic gases in case of fire and release acidic substances including chlorine during waste treatment.

As a result of repeated studies and experiments to solve the above problems, the present inventors used anionic polymer resin having a functional group that absorbs far infrared rays in its molecular structure as a matrix material of a longboard functional layer. The present invention was completed by discovering that it is possible not to use PVC resin, which is the target of environmental regulation, as well as to produce a longboard which is excellent in durability and maximizes anion and far-infrared radiation.

The present invention is a functional group having a functional layer prepared by adding functional powders such as germanium-containing wood clay and charcoal to emit far infrared rays and anions to a polymer resin having a functional group absorbing far infrared rays in a molecular structure in a certain range. The purpose is to provide excellent eco-friendly wallpaper.

The configuration of the present invention for achieving the above object is attached to Figures 1 and 2, it will be described in detail the configuration, the effect of the present invention.

The present invention is a longboard having excellent functionality having a functional layer in which functional powders such as germanium-containing wood clay and charcoal are added to the anionic polymer resin.

Referring to the functional layer of the longboard of the present invention in more detail, the component of the functional layer is composed of 100 parts by weight of anionic polymer resin, germanium-containing wood clay, charcoal in which a functional group absorbing far infrared rays in the molecular structure is in a certain range. 15 to 30 parts by weight of the functional additives formed, and further comprises a dispersant or a thermal stabilizer or light stabilizer for stability over time depending on the processing needs.

Hereinafter, the components of the present invention paperboard will be described in detail.

The present invention is a longboard having a functional layer in which germanium-containing wood clay, charcoal, etc. are added to an anionic polymer resin matrix having a functional group absorbing far-infrared rays in a molecular structure, thereby preventing attenuation of far infrared rays and anions. The present invention relates to a wallpaper having improved durability problems such as tearing or bleeding, and will be described in detail from an anionic polymer resin used in the present invention.

<Anionic Polymer Resin>

In the case of conventional longboards that emit far infrared rays and anions, even if a large amount of far infrared rays or anion radioactive materials such as ocher, germanium, elvan, natural jade, and charcoal are added to the PVC resin, the far infrared rays and anions emitted from these functional materials function as the longboard. It is known that the amount of far-infrared rays and negative ions emitted from the floorboards to the room is extremely small since they are absorbed and blocked by the resin in the course of passing through the layer. In the present invention, -OH, -NH, -SH, -OR (where R = methyl group, ethyl group, propyl group) absorbing far infrared rays in the molecular structure of the polymer resin in order to minimize the reduction of far infrared rays generated in the process of passing through the functional layer Functional group content such as) to 0.01 to 0.05 mol per 1 mol of monomer, and in order to allow the anion to easily pass through the cardboard layer -COONa, -COOCa, -COOMg, -SO ₃ Na Anionic polymer resin having a number average molecular weight of 100,000 to 250,000 containing 0.1 to 0.2 mol of anionic groups, such as -SO ₃ Ca and -SO ₃ Mg, per 1 mol of monomer is used as a matrix of the functional layer. When the content of functional groups, such as -OH, -NH, -SH, or -OR, which absorbs far infrared rays, is less than 0.01 mol / monomer 1 mol, the bond between the polymer resin and the functional additive is worsened. The functional group absorbs far infrared rays, and the radiation amount of far infrared rays radiated from the cardboard to the room is drastically reduced. In the case of anionic group, the permeability of the anion does not improve when less than 0.1 mol / monomer of 1 mol. In case of more than 0.2 mol / monomer of 1 mol, the permeability of the anion increases, but the flexibility of the functional layer deteriorates due to excessive metal content. In addition, the durability is poor, such as severe changes in heat and light over time. Examples of the anionic polymer resin include metal salts of polyvinylacetate having a number average molecular weight of 100,000 to 250,000, metal salts of polybutylene-vinylacetate copolymer, metal salts of polymethyl methacrylate, and polybutylene-methyl methacrylate copolymers. And metal salts thereof. As the metal salt, monovalent and divalent metal salts such as Na, Ca, and Mg can be used. If the number average molecular weight is less than 100,000, the binding property with the functional additive is good, but the durability becomes weak. If the number average molecular weight is more than 250,000, the flexibility of the cardboard is worse, and the usability with the functional additive is sharply poor. The anionic oligomer resin aqueous solution uses a 3% aqueous solution, and the addition amount ratio of the functional additive to the anionic polymer resin is preferably 100: 15 to 30.

<Functional additive>

As an additive for emitting infrared rays and anions, 15 to 30 parts by weight of germanium-containing wood clay / charcoal = 6/4 was added to 100 parts by weight of the polymer resin. When the added amount exceeds 30 parts by weight, the radiation rate of far infrared rays and anions is increased, but the flexibility and durability of the cardboard is worsened. When the addition amount is less than 15 parts by weight, the flexibility and durability of the cardboard is improved, but the radiation amount of the far infrared rays and anions is rapidly decreased. Far-infrared rays and anions are emitted even when ocher, elvan, and natural jade are added, but in the case of ocher, the durability of the functional layer is poor even when a small amount is added due to weak bonding strength with the functional layer polymer resin, and powdered in the case of gannet and natural jade It is difficult to do this, and the dispersibility with a polymer resin matrix is weak. Germanium-containing wood clay and charcoal are dried for a long time at 200 ° C. or higher to remove moisture, and then heat treated at 500 to 600 ° C., which is below the temperature at which they are decomposed or melted, and then pulverized until the sieve rate of the 400 mesh sieve reaches 80% or more Pulverize. The functional additives are mixed at a ratio of germanium-containing wood clay / charcoal = 6/4 and added 15 to 30 parts by weight based on 100 parts by weight of the polymer resin.

<Dispersant>

When the miscibility between the polymer resin and the functional additive is insufficient, it is preferable to further include a dispersant in the dispersion process. The dispersing agent is preferably an alkyl silicate having an alkyl group having excellent compatibility with the polymer resin at one end of the chain, and Si having inorganic particles at the other end of the chain. The addition amount of the dispersant is 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the polymer resin, the improvement of dispersibility is insignificant when the addition amount is less than 0.5 parts by weight, and when the addition amount is more than 1.5 parts by weight due to excessive addition of the dispersant Over time, the dispersant migrates to the functional layer interface, causing separation of the layers.

Stabilizer

Unlike conventional PVC sheetboard, the sheetboard of the present invention uses polyvinylacetate metal salts or metal salts of polyethylene-polyvinylacetate copolymers as functional layer matrices, so there is no need for thermal stabilizers or light stabilizers. Therefore, the conventional thermal stabilizer or light stabilizer may be added 0.05 to 0.1 parts by weight based on 100 parts by weight of the polymer resin. When the amount of the stabilizer is less than 0.05 parts by weight, the effect of the stabilizer is insignificant. When the amount of the stabilizer is more than 0.1 part by weight, the stabilizer moves to the functional layer interface due to the long-term change over time, as in the case of the dispersant, to separate the layers. Cause.

<Other functional additives>

In addition to the additives described above, zeolite, charcoal, silver, etc. may be added to impart new functions to the functional layer of the cardboard. In the case of zeolite exhibits a deodorizing effect, in the case of silver exhibits an antibacterial effect, the addition amount of other functional additives is preferably 1 to 5 parts by weight relative to 100 parts by weight of the anionic polymer resin. When the addition amount of other functional additives exceeds 5 weight part, the durability of a functional layer will worsen.

Hereinafter, the manufacturing method of the longboard of the present invention will be described in detail for each manufacturing step.

First step (production of back layer)

The back layer that acts as the base film of the cardboard and blocks moisture or odor from the concrete surface uses PVC, PET (polyethylene terephthalate), which has been used in the past. Cellulose films and PEN (polyethylene naphthalate) films, which have better performance than PVC or PET, are also available, but cellulose films are vulnerable to changes over time, and PEN films are expensive. The back layer may further include a plasticizer, a dispersant, a deodorant, an antimicrobial agent, etc. in consideration of waterproofing, insect repellent, antimicrobial properties, or the like by adding flexibility according to the characteristics of the building finishing material.

Second Step (Preparation of Functional Layer Composition)

On the back layer prepared in the first step, 100 parts by weight of anionic polymer resin having a far infrared ray absorbing functional group of 0.01 to 0.05 mol / monomer 1 mol, anionic group of 0.1 to 0.2 mol / monomer 1 mol and a number average molecular weight of 100,000 to 250,000 15 to 30 parts by weight of a functional additive having a germanium-containing wood clay / charcoal ratio of 6/4 is mixed and kneaded with 1000 rpm dynomil for 1 to 2 hours at a temperature between Tg and Tm of the polymer resin to prepare a tungsten layer composition. You may add 0.5-1.5 weight part of dispersing agents and 0.05-0.1 weight part of stabilizers with respect to 100 weight part of polymer resins to a functional layer composition.

Third Step (Extrusion and Compression Lamination of Functional Layer Composition)

The back layer continuous film is supplied from a roller for supplying the back layer prepared in the first step, and after extrusion coating the functional layer composition prepared in the second step on the back layer film by a certain amount, the back layer is compressed with a high-pressure press roller. The functional layer composition is laminated on the top.

Fourth Step (Hard Coating Layer, Surface Layer Lamination)

The hard coating composition is applied on the back layer / functional layer film prepared in the third step to impart durability and protection. In the hard coating composition, a hard coating composition including a curing agent and a light stabilizer is applied to an acrylate resin on a functional layer, and then drying and curing are simultaneously performed in a process of passing the high temperature drying chamber. Thereafter, the sheet may be passed through an embossing roll to impart a three-dimensional embossing effect to give an aesthetic appearance to the cardboard surface, or through a printing roll to print a beautiful pattern. When the printed layer is placed on the functional layer, the printing may be performed on the hard coating layer. However, when the embossing effect is imparted, the embossing may be removed after additionally stacking an easy embossing layer on the hard coating layer.

5th step (drying, calendering, slitting)

The cardboard produced in the first to fourth steps was further dried at 80-100 ° C. for at least 1 hour to remove volatiles and complete curing of the layer. Thereafter, the cardboard is cut to a certain width through a calendering process and a slittering process, and then the cardboard is manufactured to be wound by rewinding to a certain length.

Hereinafter, examples and comparative examples of the present invention paperboard will be described in detail.

<Example 1>

The composition of the functional layer of the cardboard was made into the following structure, and the functional layer of the cardboard was laminated on the back layer by the above-described method. The functional layer comprises 100 parts by weight of polyvinylacetate sodium salt (0.01 mol of hydroxyl group / 1 mol of monomer, 0.15 mol of monomer / 1 mol of sodium, number average molecular weight 150,000), 20 parts by weight of germanium-containing wood clay / charcoal = 6/4 , The average dry thickness of the functional layer is 1.5 mm. The back layer was prepared by extruding and calendering a composition in which 3 parts by weight and 1 part by weight of a plasticizer and a dispersant were added to the PVC resin (number average molecular weight 75,000) and 2.5 parts by weight of zeolite, respectively, and the average thickness was 1 mm. .

<Example 2>

Example 1 was carried out except that the magnesium salt of the polybutylene-vinylacetate copolymer (number average molecular weight 200,000, hydroxyl group 0.025 mol / monomer 1 mol, magnesium 0.12 mol / monomer 1 mol) was used instead of the polyvinyl acetate sodium salt. Same as Example 1.

Example 3

In Example 1, it was the same as in Example 1 except that 1 part by weight of the decyl silicate to 100 parts by weight of the anionic polymer resin as a dispersant.

<Example 4>

In Example 1, benzyl peroxide as an optical stabilizer is the same as in Example 1 except that 0.08 parts by weight relative to 100 parts by weight of the anionic polymer resin.

Example 5

In Example 1, except that the calcium salt of the polybutylene-methylmethacrylate copolymer (number average molecular weight 230,000, hydroxyl group 0.045 mol / monomer 1 mol, calcium 0.17 mol / monomer 1mol) was added instead of the polyvinylacetate sodium salt. And the same as in Example 1.

Comparative Example 1

In Example 1, it is the same as Example 1 except having added PVC (number average molecular weight 143,000) instead of the polyvinylacetate sodium salt.

Comparative Example 2

In Example 1, it was the same as Example 1 except using the polyvinylacetate sodium salt whose number average molecular weight is 50,000.

Comparative Example 3

In Example 1, it is the same as Example 1 except the hydroxyl group content of anionic polymer resin is 0.2 mol / monomer 1 mol.

<Comparative Example 4>

In Example 1, it is the same as Example 1 except that the sodium content of the anionic polymer resin is 0.5 mol / monomer 1mol.

Table 1 shows the components of the Examples and Comparative Examples, and the evaluation results of the far-infrared absorption strength, the electrical resistance, and the tensile strength are shown in Table 2. Far-infrared absorption intensity was measured by IR measurement equipment, and tensile strength was measured by Instron. The measurement sample used the above sample laminated | stacked to the functional layer of 1.5 mm thickness on the PVC back layer of 1 mm thickness. In the measurement of IR, the absorption intensity of the wavelength absorbed in the IR region was measured by scanning IR perpendicularly to the functional layer of the sheet paper. Table 2 shows the relative absorption ratios when the absorption intensity of Comparative Example 1 was 100. In the case of electrical resistance indirectly measuring the fluidity of the anion, the resistance is measured by measuring the voltage drop generated when passing a current of 1 A after preparing a width * length = 1 * 1 mm specimen prepared in Examples and Comparative Examples. In addition, the electrical resistance shows the relative electrical resistance when the resistance of Comparative Example 1 is 100. Tensile strength was measured as the tensile strength when the wallpaper was made into rectangular specimens of width * length = 0.5 * 3cm and pulled to 10 cm / min and 10 N with Instron, and the tensile strength of Comparative Example 1 was 100. The relative value of is shown.

[Table 1] Components of Examples and Comparative Examples (unit: parts by weight)

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Sodium salt of polyvinylacetate 100 0 100 100 0 0 100 * 100 ** 100 *** Magnesium Salt of Polybutylene-Vinyl Acetate Copolymer 0 100 0 0 0 0 0 15 * 15 ** Calcium Salts of Polybutylene-Methylmethacrylate 0 0 0 0 100 0 0 0 0 PVC 0 0 0 0 0 100 0 0 0 Germanium-containing wood clay 12 12 12 12 12 12 12 12 12 charcoal 8 8 8 8 8 8 8 8 8 Dispersant (decylsilicate) 0 0 One 0 0 0 0 0 0 Light stabilizer (benzyl peroxide) 0 0 0 0.08 0 0 0 0 0

* Number average molecular weight of anionic polymer resin 50,000

** Content of hydroxyl group of anionic polymer resin (0.2 mol / monomer 1mol)

*** Sodium content of anionic polymer resin (0.5 mol / monomer 1mol)

TABLE 2 Characteristics of the Examples and Comparative Examples (Relative Evaluation when Comparative Example 1 is 100)

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Relative Ratio of Far Infrared Absorption Intensity 97 96 95 95 96 100 97 54 96 Relative ratio of electrical resistance 25 33 28 22 30 100 25 20 15 Relative ratio of tensile strength 145 140 140 143 142 100 92 150 115

In the far-infrared absorption intensity of Table 2, in the case of Comparative Example 2 having a high content of the far-infrared absorbing functional group in the polymer resin, since the absorption of far-infrared rays occurs strongly inside the functional layer, the radiation amount of the far-infrared rays transmitted through the cardboard layer to the room is insignificant. It can be expected that the electrical resistance, Comparative Example 1 in which the polymer resin does not contain a metal salt is indirectly confirmed that the electrical resistance is very high, it will be very difficult for the anion released from the functional additives to pass through the sheetboard layer. Looking at the tensile strength it can be confirmed that in Comparative Example 2 having a low molecular weight of the polymer resin and Comparative Example 4 having a high content of metal salts in the polymer resin, the tensile strength is sharply decreased and durability is weak. As can be seen from the evaluation results of the above Examples and Comparative Examples, in the present invention, the metal salt of polyvinylacetate, the metal salt of polybutylene-vinylacetate copolymer, the metal salt of polymethyl methacrylate, By using the metal salt of polybutylene-methyl methacrylate copolymer, the emissivity of far infrared rays and anions can be maximized, and durability can be provided. It can be seen.

As described above, when the anionic polymer resin metal salt having a functional group absorbing far infrared rays in the molecular structure is used as the matrix resin of the functional layer instead of the PVC resin functional layer of the conventional longboard, the emissivity of the far infrared rays and the anions is It can be seen that it is possible to manufacture eco-friendly cardboard that has excellent durability and excellent durability while maximizing durability and not using PVC, which is a target material for environmental regulation.

Claims (9)

In a sheet of paper comprising a backing layer, a functional layer, a hard coating layer, and a surface layer, the functional layer composition has an anionic content of 0.01 to 0.05 mol / monomer, 1 mol of metal salt, and 0.1 to 0.2 mol / monomer 1 mol of functional groups that absorb far infrared rays. A longboard having excellent functionality and durability, comprising 100 parts by weight of polymer resin and 20 parts by weight of germanium-containing wood clay / charcoal = 6/4 functional additives. The method of claim 1, wherein the anionic polymer resin is a metal salt of polyvinylacetate having a number average molecular weight in the range of 100,000 to 250,000, a metal salt of polybutylene-vinylacetate copolymer, a metal salt of polymethyl methacrylate, polybutylene-methyl Longboard excellent in durability and functionality, characterized in that at least one selected from the metal salt of the methacrylate copolymer. The method of claim 2, wherein the anionic polymer resin contains at least one functional group selected from -OH, -NH, -SH, -OR (R = methyl group, ethyl group, propyl group) group, -COONa, -COOCa, -COOMg A longboard excellent in durability and functionality, characterized in that it contains at least one anion selected from -SO ₃ Na, -SO ₃ Ca, -SO ₃ Mg. The sheet of paper according to claim 3, wherein the content of the functional group in the anionic polymer resin is 0.01 to 0.05 mol / monomer 1 mol, and the content of anion is 0.1 to 0.2 mol / monomer 1 mol. 5. The longboard as claimed in claim 4, wherein the anionic polymer resin is sodium salt of polyvinylacetate having a hydroxyl group of 0.015 mol / monomer 1 mol, sodium 0.15 mol / monomer 1 mol, and a number average molecular weight of 150,000. 5. The durability and functionality of claim 4, wherein the anionic polymer resin is a magnesium salt of a polybutylene-vinylacetate copolymer having a hydroxyl group of 0.025 mol / monomer 1 mol, magnesium 0.12 mol / monomer 1 mol, and a number average molecular weight of 200,000. This excellent cardboard. 5. The durability according to claim 4, wherein the anionic polymer resin is a calcium salt of a polybutylene-methacrylate copolymer having a hydroxyl group of 0.045 mol / monomer 1 mol, calcium 0.17 mol / monomer 1 mol, and a number average molecular weight of 230,000. Longboard with excellent functionality. 8. The durability and functionality as claimed in any one of claims 5 to 7, further comprising 1.0 part by weight of decyl silicate and 0.08 part by weight of a light stabilizer as a dispersant based on 100 parts by weight of the anionic polymer resin. Cardboard. In the manufacturing method of the sheet of cardboard consisting of a back layer, a functional layer, a hard coating layer, a surface layer, i) on the PVC or PET base film backing layer, ii) 100 parts by weight of anionic polymer resin containing 0.01 to 0.05 mol / monomer 1 mol, metal salt of 0.1 to 0.2 mol / monomer 1 mol and a number average molecular weight of 100.000 to 250,000, and germanium-containing wood clay The functional layer composition consisting of 20 parts by weight of a functional additive of charcoal = 6/4 was mixed and dispersed at 1000 rpm dynomil for 1 to 2 hours at a temperature of Tg ~ Tm of the polymer resin, followed by extrusion coating and compression lamination on the back layer, iii) applying, curing and laminating a hard coating composition comprising a polyacrylate and a curing agent on the functional layer, iv) A method of producing a longboard having excellent functionality and durability, which is prepared by laminating a surface layer of any one of a printing layer and an embossing layer on a hard coating layer.

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