KR100533109B1 - Flame Retardant for Paper, Method for Preparing Flame Retardant Coated Paper Using the Same and The Flame Retardant Coated Paper Thereof - Google Patents

Abstract

The present invention relates to a flame-retardant coating solution, a method for producing a flame-retardant coated paper using the same, and a flame-retardant coated paper prepared therefrom, per 100 parts total dry weight of calcium carbonate and clay mixture (A), 5-20 parts of latex (B) and guanidine A flame retardant coating liquid comprising 5-40 parts of at least one flame retardant (C) selected from the group consisting of sulfamate, antimony oxide, and aluminum hydroxide and having a concentration of 65-70% and a viscosity of 1500-3000 cps is provided.

The flame retardant coating liquid is applied to the flame-retardant base surface by flame retardant treatment by internal addition method or impregnation method using at least one flame retardant selected from the group consisting of guanidine sulfamate, antimony oxide, and aluminum hydroxide. Provided are a flame-retardant coated paper production method and a flame-retardant coated paper produced therefrom, which are coated on both sides such that a dry weight is 30-60 g / m 2.

Flame retardant coated paper according to the present invention has the effect of minimizing damage to life and property due to fire when used in public transportation and indoor and outdoor advertising.

Description

Flame Retardant for Paper, Method for Preparing Flame Retardant Coated Paper Using the Same and The Flame Retardant Coated Paper Thereof}

The present invention relates to a flame-retardant coating solution and a method for producing a flame-retardant coated paper, and more particularly to a flame-retardant coating solution containing a latex and a specific flame retardant in a calcium carbonate and clay mixture, a method for producing a flame-retardant coated paper using the same and flame retardant It is about coating place.

Paper has become an indispensable material in our lives today because of its many excellent strengths, but it also has its shortcomings, which is why it is easy to burn. Accordingly, in recent years, a flame retardant processing method has been developed to develop a flame retardant paper that has been improved to be non-flammable without losing the excellent properties of paper.

The characteristics of the advertising paper using flame-retardant coated paper are not only excellent flame retardancy but also high printability and no color discoloration at the high ink drying temperature of the printing machine when printing, and excellent daylight fastness when used as advertising material in indoor, outdoor or public transportation. Should be.

As a related art related to the development of flame retardant paper, there is Korean Patent Publication No. 91-3889, which adds 50-% aluminum hydroxide 80-95% and 0.5-3% water resistant agent, binder, flocculant, retention enhancer, etc. After manufacturing the paper, it describes a method for producing a non-combustible inorganic paper by applying a non-flammable coating solution such as aluminum hydroxide 60-80%, a binder, a sizing agent on the surface of the paper 5-15g / ㎡, The non-combustible inorganic paper produced has a problem in that it cannot print a high resolution photograph due to poor printability because the coating amount of the coating liquid is small.

Therefore, in order to solve the physical defects that may occur in the above-described conventional flame-retardant paper, it is possible to produce a flame-retardant coated paper having excellent flame retardancy and printability, especially when used as advertising paper, without discoloration at high temperatures during ink drying, and excellent daylight fastness Flame retardant technology is required.

Accordingly, the present inventors have developed a flame-retardant coated paper capable of printing high resolution such as photographs because of excellent flame retardancy and printability.

Accordingly, an object of the present invention is to provide a flame-retardant coating solution that can provide excellent flame retardancy and printability to coated paper, have no discoloration at high temperatures during ink drying, and can provide excellent daylight fastness.

Another object of the present invention to provide a method for producing a flame-retardant coated paper using the flame-retardant coating solution.

Still another object of the present invention is to provide a flame retardant coated paper having excellent flame retardancy and printability prepared using the flame retardant coating liquid.

According to one aspect of the invention, at least one selected from the group consisting of 5-20 parts of latex (B) and guanidine sulfamate, antimony oxide, and aluminum hydroxide per 100 parts total dry weight of calcium carbonate and clay mixture (A) A flame retardant coating liquid comprising 5 to 40 parts of flame retardant (C) is provided.

According to another aspect of the present invention, after flame-retarding the base paper by the addition method or impregnation method using at least one flame retardant selected from the group consisting of guanidine sulfamate, antimony oxide, and aluminum hydroxide, and then to the flame-retarded base paper Provided is a method for producing a flame-retardant coated paper comprising coating both sides of a flame-retardant coating liquid according to the present invention so that a dry weight is 30-60 g / m 2 on a surface of a base paper.

According to still another aspect of the present invention, there is provided a flame-retardant coated paper having an effect of flame retardant class 2 or higher produced by the above method.

Hereinafter, the present invention will be described in detail.

The calcium carbonate and clay mixture (A), which is an inorganic mineral used in the flame retardant coating liquid composition of the present invention, is added to improve the printability of paper, and the calcium carbonate improves the printability and whiteness of the paper, and the clay is the gloss of the paper surface. And it is added to improve the smoothness, printability. Preferably, the calcium carbonate and clay mixture (A) consists of 40-70% by weight calcium carbonate and 30-60% by weight clay. If calcium carbonate and clay are out of the above range, optical properties such as whiteness, glossiness, and smoothness of paper and printability may be degraded.

In addition, the latex (B) used in the present invention serves as a binder for adhering the calcium carbonate and clay particles, and adhering them to the flame retardant paper, and the total dry weight of the calcium carbonate and clay mixture (A) 100 Includes 5-20 copies per minute. If the amount of latex is less than 5 parts, the separation occurs due to the decrease in adhesion between the base paper and the coating layer or the calcium carbonate and clay in the coating layer, and if the amount exceeds 20 parts, the problem of flame retardancy may occur. As a latex which can be used for this invention, a styrene-butadiene monomer etc. are mentioned, for example.

In addition, at least one flame retardant selected from the group consisting of guanidine sulfamate, antimony oxide, and aluminum hydroxide is used as flame retardant (C). This flame retardant is included at 5-40 parts per 100 parts total dry weight of the calcium carbonate and clay mixture (A). The present inventors have experimentally confirmed that a flame retardant coated paper exhibiting excellent flame retardancy can be obtained when the flame retardant uses a flame retardant coating liquid contained in such a range (see Example 3). Preferably the flame retardant is included at 20-40 parts per 100 parts total weight of the calcium carbonate and clay mixture (A). In this case, guanidine sulfamate, antimony oxide and aluminum hydroxide used as a flame retardant may be added alone or mixed with each other. More preferably the flame retardant is added in 100 parts by weight of total calcium carbonate and clay mixture, 5-20 parts of guanidine sulfamate, 5-20 parts of antimony oxide and / or 5-30 parts of aluminum hydroxide.

In particular, aluminum hydroxide is preferable for the present invention because smoke generation is controlled without generating toxic gases and is physically and chemically stable. The aluminum hydroxide is preferably added at 20-30 parts per 100 parts of the total dry weight of the calcium carbonate and clay mixture (A) when added alone.

Furthermore, various auxiliary additives may be added in the flame retardant coating liquid. Useful additives useful in the present invention include, for example, water repellents, lubricants, dispersants, rheology modifiers, pH adjusters, and the like, preferably, added at 0.5-2 parts per 100 parts of the total dry weight of calcium carbonate and clay. Can be.

The flame-retardant coating solution configured as described above has a viscosity of 65-70% and a viscosity of 1500-3000 cps because the viscosity changes according to the change in concentration. If the concentration and viscosity of this range is out of the control of the coating amount required for the flame-retardant coated paper, it becomes a factor of lowering flame retardancy and quality.

A flame-retardant coated paper is produced by coating the flame-retardant coating solution of the present invention thus formed on a base paper. Application of the flame retardant coating solution of the present invention can be made as follows.

First, a flame-retardant base paper is prepared before the flame-retardant coating solution made as described above is coated onto the base paper. The flame retardant used at this time may be the same flame retardant used to prepare the flame retardant coating solution. That is, the base paper can be flame-retarded by internal addition or impregnation using at least one flame retardant selected from the group consisting of guanidine sulfamate, antimony oxide, and aluminum hydroxide as the flame retardant.

When the flame retardant treatment of the base paper is performed by the internal addition method, it is preferable to use aluminum hydroxide having an average particle size of 1.5 to 15 탆 in order to improve the paper bonding and optical properties. If the average particle size of aluminum hydroxide is less than 1.5 μm, process workability and retention rate may be lowered, and if it exceeds 15 μm, the paper bonding and optical properties may be reduced. The flame retardancy of the base paper by the internalization method is, for example, 12-15% of cellulose kraft pulp in papermaking process, 75-85% aluminum hydroxide of average particle size 1.5-15 μm of flame retardant inorganic compound, PVA as organic fiber A flame-retardant base paper is prepared by preparing a suspension and papermaking with 1-4% of fibers, 1-3% of PET fibers, and 1-3% of inorganic fibers of the SiO ₂ component.

In addition, the paper flame retardant by the impregnation method, for example, may be made by impregnating the paper-based paper with a water-soluble flame retardant guanidine sulfamate, antimony oxide, or a mixture thereof and then drying. It is preferable that guanidine sulfamate is used as the water-soluble flame retardant, and impregnated so that the dry content of the flame retardant per 5 parts by weight of the base can be obtained by flame-retarded base paper. If the dry content of the flame retardant is out of this range, that is, if the content is less than, there is a possibility that the flame retardancy is reduced, on the contrary, if the flame retardant is exceeded, the flame retardancy is very good, but the strength of the paper and unnecessary cost increase occurs. Impregnation of the water-soluble flame retardant by the impregnation method may be carried out by a method of size press known in the art of papermaking.

After flame retardant treatment of the base paper by the internalization method and impregnation method, the flame-retardant coating solution is coated on both sides of the flame-retardant base paper so as to have a dry weight of 30-60 g / m 2 to obtain a flame-retardant coated paper. If the drying content of the coating liquid is out of this range, that is, if the dry weight of the double-sided coating layer is 30g / m 2 or less, a portion that is not coated is generated, which may result in poor printability. When the dry weight is 60 g / m 2 or more, a printing process trouble occurs due to the decrease in strength and stiffness of the paper. Coating of the flame-retardant coating solution can be carried out by any method known in the art of paper making, for example, by coating on both sides of the base paper using a blister coater, a load coater, an air knife coater or a roll coater.

The flame retardant coated paper according to the present invention exhibits the efficacy of flame retardant first grade produced by the internalization method according to the original paper production method, and may exhibit the efficacy of flame retardant second grade or higher when prepared by the impregnation method.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

<Example>

Example 1 (Step for producing flame retardant base paper by internalization method)

This Example 1 shows the process of flame retarding the base paper by the internalization method. A suspension was prepared by mixing 14% by weight of cellulose kraft pulp, 80% by weight of aluminum hydroxide as a flame retardant inorganic compound, 2% by weight of PVA fiber and 2% by weight PET fiber, and 2% by weight of inorganic fiber of SiO ₂ component. The flame-retardant base paper was prepared using the above, wherein the aluminum hydroxide was used having an average particle size of various ranges of the average particle size 1.5-15㎛.

Various paper properties such as flame retardancy, whiteness, opacity, tensile strength, tear strength, thermochromic properties and photochromic properties of the flame retarded paper thus prepared were evaluated at a basis weight of 125 g / m 2, and the results are shown in Table 1 below. Indicated.

TABLE 1

Aluminum hydroxide Kinds Average particle size of aluminum hydroxide, μm 1.5 3.0 8.0 13.0 15.0   Flame retardant ^*One , Mm 37 40 37 36 37   Opacity ^*2 ,% 97.6 93.9 93.1 90.8 89.3   The tensile strength ^{* 3} , Kgf / 15mm 1.45 1.09 1.29 1.47 1.29   Tear strength ^*4 , gf 22.2 18.6 21.7 23.7 22.7   Whiteness ^{* 5} ,% 90.7 89.5 87.9 87.3 86.0   Thermochromic ^{* 6} , ΔE 0.21 0.23 0.24 0.26 0.23   Photochromic ^{* 7} , ΔE 2.21 2.25 2.26 2.24 2.25

  * 2: Measured according to KS M 7038 * 3: Measured according to KS M 7014

  * 4: Measured according to KS M 7016 * 5: Measured according to KS M 7026

  * 1: Flame retardancy, carbonization length measurement based on JIS Z 2150

  * 6: Thermochromic property, discoloration degree after treatment at 200 ℃ for 30 seconds (measure color before and after discoloration using colorimeter)

  * 7: Photochromic, UV discoloration after 2 hours treatment (color measurement before and after discoloration using colorimeter)

As can be seen from Table 1, when the average particle size of the aluminum hydroxide included as a flame retardant is in the range of 1.5-15 ㎛ exhibited excellent paper properties, in particular, the smaller the average particle size, the more flame retardant, thermochromic and light Whiteness and opacity increased while discoloration was maintained.

Example 2 (Step of producing flame retardant paper by impregnation method)

This Example 2 is an example of flame retardant second-class flame retardant process by impregnation method, so that various water-soluble flame retardants shown in Table 2 below are dissolved in water so that the dry content of the flame retardant is 15 parts per 100 parts by weight of paper. The wetland impregnated and treated using was dried in a cylinder dryer (100-105 ° C.) and evaluated for its properties and performance.

TABLE 2

Flame Retardant Type Impregnation amount ^*One (part) Flame retardant ^*2 (Mm) Thermochromic ^{* 3} (ΔE) Photochromic ^*4 (ΔE)  Guanidine sulfamate 14.9 85 0.5 4.1  Ammonium Phosphate 14.3 65 13.4 4.7  Phosphoric Acid Compound 15.1 55 3.3 4.2  Phosphoric Acid + Guanidine 14.8 60 3.6 4.6

* 1: Impregnation rate, dry impregnation rate of flame retardant to paper weight

* 2: Flame retardancy, carbonization length measurement based on JIS Z 2150

* 3: Heat discoloration, discoloration degree after 200 ℃ 30sec treatment

* 4: Photochromic property, discoloration degree after UV Lamp 2hr treatment

As can be seen in Table 2, the flame retardancy was the best phosphoric acid compound, but the color change was poor. In particular, thermochromic properties were found to change the color of the paper to dark brown. In comparison, a flame retardant comprising guanidine sulfamate as a component has relatively low flame retardancy, but shows very good results in discoloration. Other flame retardants, such as ammonium phosphate and phosphoric acid + guanidine compounds, have excellent flame retardancy, but the color of the paper turned pale yellow due to the slight heat discoloration. Therefore, it can be seen that when the impregnation amount is adjusted upward by using a flame retardant composed of guanidine sulfamate, it is possible to prepare a base paper having excellent flame retardancy and discoloration property.

Example 3-8 (The flame-retardant coating liquid process of this invention on flame-retardant base paper)

This Example 3-8 is a flame-retardant process of the coating solution composition is coated on both sides of the coating paper prepared by the impregnation method of Example 2 so that the drying content of the coating composition to 25 parts to 100 parts by weight of the base paper and treated The coated paper was dried in a hot air dryer at 100-105 ° C. and then evaluated for its properties and performance.

At this time, the production of the base paper by the impregnation method was used as a flame retardant guanidine sulfamate, and the impregnated amount of the flame retardant was dried to 100 parts of paper weight less than the conventional paper flame retardant process to evaluate the accurate flame retardancy of the coating solution composition The wetland was impregnated using a size press so that the content was 10 parts and the treated wetland was manufactured by drying in a cylinder dryer at 100-105 ° C., and then a flame retardant coating solution was prepared as follows to dry weight on the surface of the original paper. Both-side coating was performed so that it might be set to 50 g / m <2>.

On the other hand, the flame-retardant coating solution composition is 60 parts by weight of calcium carbonate, 40 parts by weight of clay per 100 parts total dry weight, 12 parts of latex of styrene-butadiene monomer, 10-20 parts of flame retardant, at this time 20 parts of aluminum hydroxide (Example 3), 10 parts of guanidine sulfamate (Example 4), 10 parts of antimony oxide (Example 5), 10 parts of aluminum hydroxide + 5 parts of guanidine sulfamate (Example 6), aluminum hydroxide 10 Partially + 5 parts of antimony oxide (Example 7), 9 parts of aluminum hydroxide + 3 parts of guanidine sulfamate + 3 parts of antimony oxide (Example 8), respectively, 0.15 parts of water-resistant agent, 0.5 part of lubricant, dispersant as other coadditives. 0.03 parts, 0.15 parts of fluidity improver, and 0.1 parts of pH adjuster were uniformly mixed to prepare a solid content concentration of 67 to 68% of the final flame retardant coating solution and to coat.

   TABLE 3

Flame Retardant Type Amount ^*One (part) Flame retardant ^*2 (Mm) Thermochromic ^{* 3} (ΔE) Photochromic ^*4 (ΔE) Example 3 (Aluminum hydroxide) 20 75 0.19 2.45 Example 4 (Guanidine sulfamate) 10 68 0.23 2.72 Example 5 (Antimony oxide) 10 57 0.21 2.68 Example 6 (Aluminum Hydroxide + Guanidine Sulfamate) 15 72 0.22 2.66 Example 7 (Aluminum Hydroxide + Antimony Oxide) 15 67 0.23 2.62 Example 8 (Aluminum Hydroxide + Guanidine Sulfamate + Antimony Oxide) 15 70 0.23 2.65

  * 1: Addition amount, flame retardant addition amount to the weight of inorganic minerals (calcium carbonate, clay) in the coating composition

  * 2: Flame retardancy, carbonization length measurement based on JIS Z 2150

  * 3: Color change after heat discoloration, 200 ℃, 30 seconds

  * 4: Photochromic, UV discoloration after 2 hours treatment

As can be seen in Table 3, the flame retardant added to the coating solution composition was able to prepare coated paper having excellent flame retardancy and discoloration property when using guanidine sulfamate, antimony oxide, aluminum hydroxide or a mixture thereof. On the other hand, the flame-retardant coated paper prepared by the above process showed the printability similar in quality to the general coated paper.

As can be seen in the above experiments, the coated paper coated with inorganic mineral material on the paper can be treated with the above flame retardant on the paper and the coating layer to satisfy the requirements of flame retardant coated paper having excellent flame retardancy, discoloration, and printability. .

The flame retardant coating solution according to the present invention imparts flame retardancy to the base paper and the coating layer used as a substrate for coating, and the flame retardant coating paper prepared by using the same is used for public transportation and indoor / outdoor advertisements, resulting in fire and damage to property. There is an effect that can be minimized.

Claims (9)

At least one flame retardant (C) selected from the group consisting of 5-20 parts of styrene-butadiene latex (B) and guanidine sulfamate, antimony oxide, and aluminum hydroxide, per 100 parts total dry weight of calcium carbonate and clay mixture (A) 5 A flame retardant coating solution comprising -40 parts and having a concentration of 65-70% and a viscosity of 1500-3000 cps. The flame retardant (C) according to claim 1, wherein the flame retardant (C) is contained in at least one of 5-20 parts of guanidine sulfamate, 5-20 parts of antimony oxide and 5-30 parts of aluminum hydroxide per 100 parts of total weight of the calcium carbonate and clay mixture (A). Flame retardant coating solution characterized in that. The flame-retardant coating solution according to claim 1, wherein the average particle size of the aluminum hydroxide is 1.5-15 µm. The flame retardant coating liquid according to claim 1, wherein the calcium carbonate and clay mixture (A) is composed of 40-70 wt% of calcium carbonate and 30-60 wt% of clay. The at least one auxiliary additive according to any one of claims 1 to 4, selected from the group consisting of a water-resistant agent, a lubricant, a dispersant, a fluidity improver, and a pH adjuster per 100 parts of the total dry weight of the calcium carbonate and clay mixture (A). Flame-retardant coating solution, characterized in that it comprises 0.5-2 parts. After flame retarding the raw paper by internal additive method or impregnation using at least one flame retardant selected from the group consisting of guanidine sulfamate, antimony oxide, and aluminum hydroxide, the flame-retardant coating liquid of claim 1 A method for producing a flame-retardant coated paper consisting of two-side coating so that the dry weight is 30-60g / ㎡ on the surface. The flame retardant treatment of the base paper according to claim 6, 12-15% by weight kraft pulp, 75-85% by weight aluminum hydroxide of average particle size 1.5-15㎛, organic fiber PVA fiber 1-4 weight % And 1-3% by weight of PET fibers, 1-3% by weight of inorganic fibers of the SiO ₂ component. The flame-retardant coating paper according to claim 6, wherein when the flame retardant treatment of the base paper is carried out by the impregnation method, the water-soluble flame retardant is impregnated with guanidine sulfamate to impregnate 5-20 parts of the dry content of the flame retardant per 100 parts by weight of the base paper. Manufacturing method. Flame retardant coated paper produced by the method of any one of claims 6 to 8 having a second or more efficacy.