KR102453470B1 - Hydrophobic Paper by Hot Pressed Gas Grafting of Fatty Acids and Method of Producing The Same - Google Patents

Abstract

The hydrophobic paper manufacturing method using the compressed heated gas grafting hydrophobic treatment facility of the present invention uses the compressed heated gas grafting hydrophobic treatment facility equipped with a non-breathable dryer belt, so that the dissipation of hydrochloric acid generated during the reaction of the chlorinated fatty acid and the paper hydroxyl group is reduced. It has the characteristic of using hydrochloric acid as a catalyst to cause an esterification reaction between fatty acids and species hydroxyl groups. Therefore, the hydrophobic paper manufacturing method of the present invention uses a mixed hydrophobic agent in which some of the expensive chlorinated fatty acids are replaced with inexpensive general fatty acids. It has the advantage of being able to manufacture at a lower manufacturing cost.
In addition, the hydrophobic paper manufacturing method using the compression heated gas grafting hydrophobic treatment facility of the present invention recycles strong acids such as hydrochloric acid generated during the reaction compared to the conventional method for producing hydrophobic paper using a chlorinated fatty acid and gas grafting hydrophobic treatment facility Therefore, there is an effect of reducing the treatment cost of strong acid.

Description

Hydrophobic Paper by Hot Pressed Gas Grafting of Fatty Acids and Method of Producing The Same

The present invention relates to hydrophobic paper subjected to compression heating gas phase grafting using fatty acids that could not be used in the conventional gas phase grafting reaction and a method for producing the same, and more particularly, using a hydrophobic hydrophobic treatment facility using chlorinated fatty acid and compression heating gas grafting. Hydrophobization paper that uses the acid generated in the hydrophobicization process of paper as a catalyst to convert fatty acids and hydroxyl groups on the surface of the paper into fatty acid esters to make them hydrophobic, replacing expensive chlorinated fatty acids with inexpensive fatty acids and reducing the generation of toxic hydrochloric acid gas during the process It relates to a manufacturing method of

Daniel Samain et al. of France developed a new technology and equipment for hydrophobizing the surface of hydrophilic cellulose using a hydrophobization treatment of cellulose using a vapor phase grafting reaction of chlorinated fatty acid (Patent Document US 6,342,268, US 8,637,119, EP 2,231,401, US 2013-0199409, US 2014-0113080, and US 2013-0236647). With this technology, also called "Chromatogenic Technology", as shown in Formula 1 below, gaseous chlorinated fatty acid reacts with a hydrophilic surface containing a hydroxyl group to form a fatty acid ester, so that the hydrophilic surface is hydrophobized.

[Formula 1]

S-OH + RCOCl ↔ S-O-CO-R + HCl (R is alkyl or alkenyl)

The conventional vapor phase grafting apparatus is designed so that the reaction heat is transferred from the drum dryer to the substrate so that the hydroxyl group of the substrate reacts effectively with the vaporized chlorinated fatty acid (see Patent Document US 2013-0236647). However, since the vapor phase grafting apparatus is in contact with the drum dryer depending only on the tension of the substrate, there is a problem in that the heat of reaction is not sufficiently transferred from the drum dryer to the substrate. If the heat of reaction is not sufficiently transferred, the efficiency of the gas phase grafting reaction is lowered, and as a result, the water resistance of the substrate is lowered. In addition, in the vapor phase grafting apparatus, as the vaporized chlorinated fatty acid is lost through the gap between the substrate and the dryer before the vapor phase grafting reaction occurs, there is a problem in that the hydrophobicization efficiency is lowered.

Accordingly, the present inventor has registered a Korean patent for a compression heating vapor phase grafting hydrophobicization device and hot water-resistant paper and oil adsorption paper manufactured using the same. A non-breathable dryer belt for compression was provided to prevent dissipation of the chlorinated fatty acid vaporized by the drying roller without reacting with the substrate, thereby improving the gas phase grafting reaction efficiency (refer to KR 10-1974895).

Therefore, by using the compression heating vapor phase grafting hydrophobicization device, the content of chlorinated fatty acid per unit area can be significantly increased. became possible

However, all conventional gas phase grafting treatment is based on a chemical mechanism in which acyl chloride, such as chlorinated fatty acid, reacts with a base hydroxyl group to form a fatty acid ester, as shown in FIG. 1, so chlorinated fatty acid, which is relatively expensive and dangerous to handle, must There was a problem that I had to use.

Therefore, if a vapor phase grafting method that can produce hydrophobic paper is developed by replacing expensive chlorinated fatty acids with inexpensive fatty acids, not only will the manufacturing cost of the hydrophobized paper be reduced, but also strong acids such as hydrochloric acid produced in the hydrophobization reaction will be reduced, resulting in acid treatment. Costs are also expected to be reduced.

The patents and references mentioned in this specification are hereby incorporated by reference to the same extent as if each publication were individually and expressly specified by reference.

Korean Patent Registration 10-0862043 US Registered Patent US 6,342,268 US registered patent US 8,637,119 European Patent EP 2,231,401. US Patent Publication US 2013-0199409 US Patent Publication US 2014-0113080 US Patent Publication No. 2013-0236647 Korean Patent Registration 10-1713416 Korean Patent Registration 10-1974895

In order to solve the above problem, the present invention uses a mixture of chlorinated fatty acid and fatty acid so that hydrophobization is achieved based on a chemical reaction mechanism in which fatty acid and hydroxyl group react to form fatty acid ester, and hot pressed gas grafting (hot pressed gas grafting) ) It aims to provide a new hydrophobization technology using hydrophobic treatment facilities.

Other objects and technical features of the present invention are set forth more specifically by the following detailed description of the invention, claims and drawings.

The present invention relates to a method for producing hydrophobic paper using a compression heating gas grafting hydrophobic treatment facility, in which a fatty acid chloride and a fatty acid are mixed in a weight ratio of 99:1 to 83:17. A first step of preparing a hydrophobizing agent; a second step of applying the mixed hydrophobic agent to a gravure roller of the compressed heated gas grafting hydrophobic treatment facility; and a third step of hydrophobizing the paper by pressing the paper to the gravure roller at a pressure of 0.1 to 2 kg/cm ² using a non-breathable dryer belt. A method for manufacturing paper is provided.

The chlorinated fatty acid (fatty acid chloride) and the fatty acid (fatty acid) are characterized in that they include a chain aliphatic compound having 6 to 22 carbon atoms, and the chlorinated fatty acid is palmitoyl chloride (C16) or stearoyl Chloride (stearoyl chloride, C18) may be used, and the fatty acid may be palmitic acid or stearic acid.

The non-breathable dryer belt promotes the fatty acid ester reaction between the fatty acid and the hydroxyl group of the paper by preventing the hydrochloric acid produced from the gas phase grafting reaction of the chlorinated fatty acid from being dissipated from the substrate.

The hydrophobic paper manufacturing method using the compressed heated gas grafting hydrophobic treatment facility of the present invention uses the compressed heated gas grafting hydrophobic treatment facility equipped with a non-breathable dryer belt, so that the dissipation of hydrochloric acid generated during the reaction of the chlorinated fatty acid and the paper hydroxyl group is reduced. It has the characteristic of using hydrochloric acid as a catalyst to cause an esterification reaction between fatty acids and species hydroxyl groups. Therefore, the hydrophobic paper manufacturing method of the present invention uses a mixed hydrophobic agent in which some of the expensive chlorinated fatty acids are replaced with inexpensive general fatty acids. It has the advantage of being able to manufacture at a lower manufacturing cost.

In addition, the hydrophobic paper manufacturing method using the compression heated gas grafting hydrophobic treatment facility of the present invention recycles strong acids such as hydrochloric acid generated during the reaction compared to the conventional method for producing hydrophobic paper using a chlorinated fatty acid and gas grafting hydrophobic treatment facility Therefore, there is an effect of reducing the treatment cost of strong acid.

1 shows the esterification process of fatty acids by acyl chloride nucleophilic addition-removal reaction in the conventional gas phase grafting process of chlorinated fatty acids. R means an alkyl group, and in the case of palmitoyl chloride, CH ₃ -(CH ₂ ) ₁₃ - means. R' means cellulose or polyvinyl alcohol.
Figure 2 shows the esterification reaction of fatty acids and alcohols by the acid catalyst of the present invention. R means an alkyl group, and in the case of palmitic acid, CH ₃ -(CH ₂ ) ₁₃ - means. R' means cellulose or polyvinyl alcohol.

The present invention relates to a method for producing hydrophobic paper using a compression heated gas grafting hydrophobic treatment facility. After applying a mixed hydrophobic agent prepared by mixing a chlorinated fatty acid and a fatty acid to the paper, compression heating gas phase grafting treatment is performed on the paper. It relates to a method for hydrophobizing a surface.

The preparation method of the present invention comprises the following steps:

A first step of preparing a mixed hydrophobic agent in which chlorinated fatty acid (fatty acid chloride) and fatty acid (fatty acid) are mixed in a weight ratio of 99:1 to 83:17;

a second step of applying the mixed hydrophobic agent to a gravure roller of the compressed heated gas grafting hydrophobic treatment facility; and

A third step of hydrophobizing the paper by pressing the paper to the gravure roller at a pressure of 0.1 to 2 kg/cm ² using a non-breathable dryer belt;

A method for producing hydrophobic paper using a compressed heated gas grafting hydrophobic treatment facility and a mixed hydrophobic agent comprising a.

Step 1: Preparing a mixed hydrophobic agent in which chlorinated fatty acid (fatty acid chloride) and fatty acid (fatty acid) are mixed in a weight ratio of 99:1 to 83:17.

The present invention uses a hydrophobizing agent to hydrophobize paper as a substrate. The hydrophobizing agent reacts with the hydroxyl group of the paper to form an ester, thereby hydrophobizing the paper.

The hydrophobic agent of the present invention can be prepared by mixing a chlorinated fatty acid (fatty acid chloride) and a fatty acid (fatty acid) as a mixed hydrophobic agent. The chlorinated fatty acid and the fatty acid may be a chlorinated fatty acid in which the hydroxyl group of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms is substituted with chlorine, or a fatty acid including a saturated fatty acid and an unsaturated fatty acid. Preferably, myristoleic acid, palmitophosphoric acid, sapienic acid, oleic acid, eladic acid, vaccenic acid, linolein linoleic acid, linoleaidic acid, α-linolenic acid, arachidonic acid, eicosapentanoic acid, erucic acid, docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, It may be a chlorinated fatty acid and a fatty acid of stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid, and more preferably the chlorinated fatty acid. The fatty acid is palmitoyl chloride or stearoyl chloride, and the fatty acid is palmitic acid or stearic acid.

The mixed hydrophobic agent of the present invention can be prepared by mixing a plurality of chlorinated fatty acid mixtures and a plurality of fatty acid mixtures.

2 shows the process of fatty acid esterification reaction in which fatty acids react with hydroxyl groups. Since the fatty acid esterification reaction is an esterification reaction in which an acid serves as a catalyst, there is a disadvantage in that the esterification efficiency is extremely low in the absence of an acid. Therefore, even under compression heating conditions in which sufficient heat is applied, if only fatty acids are introduced without acid, fatty acid esterification reaction of hydroxyl groups does not occur.

In the present invention, a mixed hydrophobic agent is prepared in which chlorinated fatty acid (fatty acid chloride) and fatty acid (fatty acid) are mixed in a weight ratio of 99:1 to 83:17. Preferably, a mixed hydrophobic agent is prepared in which a chlorinated fatty acid (fatty acid chloride) and a fatty acid (fatty acid) are mixed in a weight ratio of 90:10 to 83:17, more preferably a chlorinated fatty acid (fatty acid chloride) and a fatty acid ( A mixed hydrophobic agent is prepared in which fatty acid) is mixed in a weight ratio of 85:15.

When chlorinated fatty acid and fatty acid, which are acyl chlorides, are applied together as in the present invention, the fatty acid coexists during the process of generating hydrochloric acid gas while the chlorinated fatty acid forms a fatty acid ester by the nucleophilic addition-removal reaction, so that the esterification reaction of fatty acids The reason that essential acids are sufficiently provided is that fatty acids react with hydroxyl groups like chlorinated fatty acids to form fatty acid esters, making the surface of the substrate (paper) hydrophobic.

However, according to the embodiment of the present invention, if the content of fatty acid in the mixed hydrophobic agent exceeds 20% by weight, the acid (hydrochloric acid) is not generated sufficiently to perform the fatty acid esterification reaction, so the hydrophobization efficiency is rapidly increased. There is a problem of degradation. Therefore, the mixed hydrophobic agent of the present invention preferably has a mixing ratio of fatty acid chloride and fatty acid of less than 80:20 by weight.

Second step: applying the hydrophobic agent to the gravure roller of the compressed heated gas grafting hydrophobic treatment facility:

The prepared hydrophobic agent is applied to the gravure roller of the compressed heated gas grafting hydrophobic treatment facility. The compression heating gas grafting hydrophobic treatment facility is described in detail in Korean Patent No. 10-1974895. The compression heating gas grafting hydrophobic treatment equipment includes: an unwinder unit for continuously supplying a substrate; a drying unit for heating the surface of the substrate to which the hydroxyl groups are exposed; an application roller (gravure roller) for applying a vapor phase grafting reagent to the surface of the substrate exposed to the hydroxyl group; a drying roller for evenly distributing the applied grafting reagent to the surface of the substrate, and further comprising a touch roll for guiding the surface of the substrate to which the grafting reagent is applied toward the surface of the drying roller 40; a non-breathable dryer belt positioned on the outer surface of the substrate to which the vapor phase grafting reagent has been applied, surrounding the drying roller, and compressing the substrate (paper) coated with the vapor phase grafting reagent to the drying roller; a fan for removing hydrogen chloride generated during the gas phase grafting reaction; an air knife nozzle for removing residual vapor phase grafting reagents on the surface of the substrate; and a rewinder unit for rewinding the substrate subjected to the vapor phase grafting reaction.

The hydrophobic agent of the present invention performs a hydrophobization reaction by applying 1 to 1.6 g/m ² to the gravure roller when using a base paper for release paper having a basis weight of 70 g/m ² as a base material, and preferably 1.3 g/m to the gravure roller ² Apply.

Step 3: Using a non-breathable dryer belt, press the paper onto the gravure roller from 0.1 to 2 kg/cm ² The step of hydrophobizing by pressing under the pressure of:

The compression heated gas grafting hydrophobic treatment facility of the present invention is characterized in that the non-breathable dryer belt surrounds the drying roller. When the substrate passes through the application roller, the hydrophobizing agent is applied to the substrate. The substrate coated with the hydrophobic agent enters the drying roller, which is controlled at a high temperature of 200°C. The hydrophobicizing agent applied to the substrate is vaporized as it comes into contact with the high-temperature drying roller, and the heat of the drying roller acts as reaction heat, so that the gaseous chlorinated fatty acid and fatty acid react on the hydrophilic surface including the hydroxyl group on the substrate to form a fatty acid ester do. The vapor phase grafting reaction described above is represented by the following Chemical Formulas 1 and 2. Chemical Reaction Formula 1 shows the gas phase grafting reaction of chlorinated fatty acids, and Formula 2 shows the gas phase grafting reaction of fatty acids.

The gas phase grafting reaction of the chlorinated fatty acid described in Formula 1 proceeds at a very high speed. Since the reaction heat transferred from the drying roller promotes the reaction between the substrate and the vaporized chlorinated fatty acid, the efficiency of the chemical reaction is determined according to the degree to which the reaction heat transferred from the drying roller is transferred to the substrate. In particular, if the reaction heat of the drying roller is not transferred to the substrate, the hydrophobization rate is reduced.

In contrast, the gas phase grafting reaction of fatty acids described in Formula 2 proceeds at a rather slow rate. Hydrochloric acid (HCl), a grafting by-product of chlorinated fatty acid, has an effect of accelerating the reaction between the substrate and the vaporized fatty acid. Therefore, as in the present invention, when the gas phase grafting reaction of the chlorinated fatty acid of Formula 1 occurs at the same time as the gas phase grafting reaction of the fatty acid of Formula 2, the hydrochloric acid promotes the gas phase grafting reaction of the fatty acid to make hydrophobic by the fatty acid. will lose

In addition, the efficiency of the chemical reaction is determined according to the degree to which the heat of reaction transferred by the drying roller is transferred to the substrate. In particular, if sufficient heat of reaction of hydrochloric acid and the drying roller is not transferred to the substrate together with the fatty acid, the hydrophobization rate is reduced.

The compression heating method of the present invention has an advantage in that the degree of adhesion between the substrate and the drying roller is strong. If the degree of adhesion is weak, a gap occurs between the substrate and the drying roller, and vaporized chlorinated fatty acid, hydrochloric acid and fatty acid escape. can be

The present invention utilizes a compression heating gas phase grafting equipment equipped with a non-breathable dryer belt surrounding a drying roller so that there is no above-mentioned problem, and the non-breathable dryer belt applies the substrate to a drying roller at a pressure of 0.1 to 2 kg _f / cm ² compressed with Therefore, the hydrophobic acid and hydrophobic acid such as vaporized chlorinated fatty acid and fatty acid do not pass through the dryer belt, but stay on the surface of the drying roller and inside the substrate, so that the hydrophobic reaction of the substrate by the chlorinated fatty acid and fatty acid can be efficiently performed.

When the non-breathable dryer belt presses the substrate (paper) to the drying roller at a pressure of less than 0.1 kg _f / cm ² , the hydrophobic agent and hydrochloric acid escape and the hydrophobicization efficiency of the substrate may decrease, and the non-breathable dryer When the belt presses the substrate (paper) to the drying roller at a pressure exceeding 2 kg _f /cm ² , there is a risk that the substrate may be damaged while passing through the drying roller. Preferably, the non-breathable dryer belt presses the substrate against the drying roller at a pressure of 1.3 kg _f / cm ² .

The paper produced by the above method has hot water resistance properties. The hot water resistance property means that water is not absorbed even at a high temperature and thus has the characteristics of a hydrophobic paper.

According to an embodiment of the present invention, using the manufacturing method of the present invention, a substrate having a basis weight of 60 to 80 g/cm ² and a substrate coated with polyvinyl alcohol is hydrophobized by compression heating and gas grafting. It is possible to prepare a hot water-resistant paper that maintains hydrophobization even in hot water of 80 to 120 °C.

The hydrophobization state can be determined by measuring the Cobb size degree. If the size of the Cobb is less than 10 g/m ² , it can be used as a container for containing water and the like by sufficiently maintaining hydrophobicity. The hot water-resistant paper of the present invention is characterized in that the size of Cobb ₁₈₀₀ is 5 to 9 g/m ² in hot water having a temperature of 80 to 120 ° C. Preferably, the hot water-resistant paper of the present invention has a Cobb ₁₈₀₀ size degree of 6 to 8 g/m ² and more preferably 7.1 g/m ² in hot water having a temperature of 100° C.

The Cobb ₁₈₀₀ size diagram refers to the results of testing the degree of water absorption in water for 1800 seconds. If the size of Cobb ₁₈₀₀ is about 8 g/m ² in hot water having a temperature of 80 to 120 ° C, it can be used as a container for hot food or water by maintaining a hydrophobic state in hot water having a temperature of 80 to 120 ° C. It is not necessary to further reduce the size of the Cobb ₁₈₀₀ in hot water with a temperature of 80 to 120°C.

The hydrophobization is measured by the degree of alkylation or alkenylation formed in the hydroxyl group of the substrate by the chemical reaction, and this can be determined by measuring the content per unit area of the fatty acid ester present in the substrate after the gas phase grafting reaction. The hot water-resistant paper of the present invention is characterized in that the density of the fatty acid ester is 700 to 1300 mg/m ² . Preferably, the hot water-resistant paper of the present invention is characterized in that the density of the fatty acid ester is 1200 mg/m ² . If the density of the fatty acid ester is less than 700 mg/m ² , it is not suitable for manufacturing as a container that cannot contain hot food or water, and even if the density of the chlorinated fatty acid exceeds 1300 mg/m ² , the performance of holding hot food or water The level of improvement is negligible.

The hot water-resistant paper of the present invention has a basis weight of 60 to 80 g/cm ² and uses a substrate coated with polyvinyl alcohol. When water- and moisture-proof properties are imparted to the substrate by gas grafting of chlorinated fatty acids and fatty acids, polyvinyl alcohol (PVA) coating on the substrate can further improve hydrophobization efficiency. The PVA is a biodegradable high molecular compound having more hydroxyl groups compared to cellulose in paper.

The present invention will be described in detail through the following examples.

Example

Example 1) Preparation of PVA-coated hot water-resistant paper using a chlorinated fatty acid/fatty acid (85:15) mixed hydrophobic agent

Hydrophobic treatment facility for hot pressed gas grafting after applying 1.3 g/m ² of a hydrophobic agent blended with 85% by weight of chlorinated fatty acid and 15% by weight of fatty acid to the base paper coated with PVA with a basis weight of 70g/m ² was used to prepare PVA-coated hot water-resistant paper.

In the compression heating gas grafting facility, a dryer belt was applied to press the paper toward the dryer at a pressure of 0.5 kg _f /cm ² so that the paper to be hydrophobized adhered to the surface of the dryer.

In detail, the PVA coating was applied to the base paper of the back release paper having a basis weight of 70 g/m ² to adjust the pickup amount to 8 g/m ² . As the chlorinated fatty acid, palmitoyl chloride (C16) was used, and as the fatty acid, palmitic acid (C16) was used. The hydrophobic agent prepared by mixing the chlorinated fatty acid and the fatty acid in a weight ratio of 85:15 was applied to the PVA-coated backing paper base by an anilox roller application amount of 1.3 g/m ² .

Anilox, that is, the temperature of the gravure roller was fixed at 60 ℃, and the temperature of the drying roller was adjusted to 200 ℃. The temperature of hot air for air knife flushing was 300°C. Hydrophobization treatment was performed by fixing the operating speed of the facility to 50 m/min under the above treatment conditions.

Cobb size was measured after 1800 seconds in boiling water for the hydrophobized PVA coated paper, and the density of the reacted fatty acid ester by performing gas chromatography analysis on the hydrophobicized PVA coated paper (mg) /m ² ) was obtained.

Example 2) Preparation of PVA-coated hot water-resistant paper using a chlorinated fatty acid/fatty acid (80:20) mixed hydrophobic agent

Prepared under the same conditions as in Example 1, but 80 wt% of palmitoyl chloride, a chlorinated fatty acid, and 20 wt% of palmitic acid, a fatty acid, on a base paper coated with PVA having a basis weight of 70 g/m ² After application of 1.3 mg/m ² of the mixed hydrophobic agent prepared by mixing , PVA-coated heat-resistant water-resistant paper was prepared using a hot pressed gas grafting hydrophobicization treatment facility.

In the compression heating gas grafting facility, a dryer belt was applied to adhere the paper to the dryer at a pressure of 0.5 kg _f / cm ² in order to adhere the paper to be hydrophobized to the surface of the dryer.

In detail, the PVA coating was applied to the base paper of the back release paper having a basis weight of 70 g/m ² , and the pickup amount was adjusted to 8 g/m ² . As the chlorinated fatty acid, palmitoyl chloride (C16) was used, and as the fatty acid, palmitic acid (C16) was used. The mixed hydrophobic agent in which the chlorinated fatty acid and the fatty acid were mixed in a weight ratio of 80: 20 was applied to the PVA-coated backing paper base by an anilox roller application amount of 1.3 g/m ² . Anilox, that is, the temperature of the gravure roller was fixed at 60 ℃, and the temperature of the drying roller was adjusted to 200 ℃. The temperature of hot air for air knife flushing was 300°C. Hydrophobization treatment was performed by fixing the operating speed of the facility to 50 m/min under the above treatment conditions.

Cobb size was measured after 1800 seconds in boiling water for the hydrophobized PVA coated paper, and the density of the reacted fatty acid ester by performing gas chromatography analysis on the hydrophobicized PVA coated paper (mg) /m ² ) was obtained.

Comparative Example 1) Preparation of PVA-coated hot water-resistant paper using chlorinated fatty acid

PVA-coated hot water-resistant paper was prepared using the same hot pressed gas grafting hydrophobic treatment equipment and hydrophobic agent containing only the chlorinated fatty phase as in the above example.

In the same manner as in Example 1, PVA coating was applied to the base paper of the back release paper having a basis weight of 70 g/m ² to adjust the pickup amount to 8 g/m ² . As the hydrophobizing agent, only chlorinated fatty acid (palmitoyl chloride, plmitoyl chloride, C16) was used, and an anilox roller application amount was applied at a rate of 1.3 g/m ² once, and a total of 1.3 g/m ² was applied. Anilox (anilox), that is, the temperature of the gravure (gravure) roller was fixed to 60 ℃.

In the compression heating gas grafting facility, a dryer belt was applied to press the paper to the dryer at a pressure of 0.5 kg _f / cm ² in order for the paper to be hydrophobized to adhere to the surface of the dryer. The temperature of the drying roller was adjusted to 200 °C, and the temperature of hot air for air knife flushing was adjusted to 300 °C. Hydrophobization treatment was performed by fixing the operating speed of the facility to 50 m/min under the above treatment conditions.

The Cobb size diagram was measured after 1800 seconds in boiling water of the hydrophobized PVA-coated paper and compared with the Cobb size diagram after 1800 seconds of boiling water of the PVA-coated hot water-resistant paper prepared in Examples.

Gas chromatography analysis was performed on the hydrophobized PVA-coated paper to measure the density (mg/m 2 ) of the reacted fatty acid ester, and the reacted fatty acid ester density (mg/m ² ) of the PVA-coated hot water-resistant paper prepared through this example /m ² ).

Table 1 below shows the results of comparing the Cobb size diagram and the density of the reacted fatty acid ester of the PVA-coated hot water-resistant paper prepared in Examples 1, 2 and Comparative Example 1.

basis weight Cobb 1800s_Hot water (g/m ² ) Reacted Fatty Acid Chloride Content (g/m ² ) Comparative Example 1 70 g/m ² 7.2 1.20 Example 1 70 g/m ² 7.1 1.21 Example 2 70 g/m ² 18.2 0.52

According to Table 1, compared to Comparative Example 1, it was confirmed that the hot water Cobb size diagram of the PVA coated paper of Example 1 using a hydrophobizing agent blending 15% fatty acid with a chlorinated fatty acid of the present invention was similar. In addition, it was confirmed that the amount of fatty acid ester formation of the PVA coated paper of Example 1 using a hydrophobicizing agent containing 15% of fatty acid to chlorinated fatty acid was similar to that of Comparative Example 1 using 100% chlorinated fatty acid as a hydrophobicizing agent.

According to the present invention, despite the use of a mixed hydrophobizing agent containing 15% of fatty acids in chlorinated fatty acids, the reason for the formation of fatty acid esterosis is similar to the case of using a hydrophobizing agent containing only chlorinated fatty acids. It is judged that hydrochloric acid, a by-product generated during this process, served as a catalyst in the esterification reaction of fatty acids.

As in the present invention, when a chlorinated fatty acid, which is an acyl chloride, and a general fatty acid are applied together, the chlorinated fatty acid forms a fatty acid ester by the nucleophilic addition-removal reaction while the fatty acid coexists while generating hydrochloric acid gas, so that in the esterification reaction of fatty acids Because the essential acid is sufficiently provided, it is judged that general fatty acids react with hydroxyl groups like chlorinated fatty acids to form fatty acid esters and hydrophobize the surface of the substrate.

However, in the case of Example 2, in the case of Example 2, in which the mixing ratio of fatty acids to chlorinated fatty acids was improved to 20%, the Cob size degree increased rapidly and the amount of fatty acid ester formation rapidly decreased. This is because the amount of hydrochloric acid gas produced has decreased due to the reaction of chlorinated fatty acids acting as

In summary, the present invention is a non-breathable dryer belt that wraps the drying roller and compresses it at a pressure of 0.1 to 2 kg _f / cm ² on the surface of the drying roller by using a compression heating gas phase grafting hydrophobization device. Since phosphorus hydrochloric acid is prevented from dissipating from the substrate, if less than 20% of general fatty acids that induce the gas phase grafting reaction of fatty acids are mixed with chlorinated fatty acids, hydrochloric acid is formed as a by-product of the esterification reaction of chlorinated fatty acids. There is an advantage in that fatty acid esters are formed through the quenching reaction. Therefore, it is possible to achieve the effect of reducing the processing cost by using a mixture hydrophobizing agent prepared by replacing some of the expensive chlorinated fatty acids with inexpensive general fatty acids.

However, if the mixing ratio of general fatty acids is increased to 20% or more, the amount of hydrochloric acid (HCl), a reaction by-product of chlorinated fatty acids, is reduced, and water, a by-product generated when fatty acids and hydroxyl groups react, decomposes chlorinated fatty acids into fatty acids. It was confirmed that the ester formation efficiency was rapidly reduced.

Conventional PE laminating paper had a Cobb size of 10 g/m ² and did not get wet with moisture, so it could be used as a food container. This is the effect of the PE film, which is plastic, and shows the same effect even in boiling water, so it is used as a container for storing hot food. According to Table 1, the content of fatty acid ester is 1200 mg/m ² or more, and the Cobb size in hot water (boiling water) is also maintained at 7.1 g/m ² , so that it can be used as a container for food containing water or moisture. is expected to be possible.

Specific examples described herein are meant to represent preferred embodiments or examples of the present invention, and the scope of the present invention is not limited thereby. It will be apparent to those skilled in the art that modifications and other uses of the present invention do not depart from the scope of the invention as set forth in the claims herein.

Claims (5)

A first step of preparing a mixed hydrophobic agent in which chlorinated fatty acid (fatty acid chloride) and fatty acid (fatty acid) are mixed in a weight ratio of 99:1 to 83:17;
a second step of applying the mixed hydrophobic agent to a gravure roller of a compression heated gas grafting hydrophobic treatment facility; and
a third step of hydrophobizing the paper by pressing the paper to the gravure roller at a pressure of 0.1 to 2 kg _f / cm ² using a non-breathable dryer belt;
includes,
The chlorinated fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, eladic acid, vaccenic acid, linol linoleic acid, linoleaidic acid, α-linolenic acid, arachidonic acid, eicosapentanoic acid, erucic acid , docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid , a chlorinated fatty acid of stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid,
The fatty acids are myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, eladic acid, vaccenic acid, linolein. linoleic acid, linoleaidic acid, α-linolenic acid, arachidonic acid, eicosapentanoic acid, erucic acid, docosahexaenoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, Compression heating gas grafting hydrophobic treatment facility, characterized in that stearic acid, arachidic acid, behenic acid, lignoceric acid, or cerotic acid A method for producing hydrophobic paper using a mixed hydrophobic agent.
According to claim 1, wherein the chlorinated fatty acid (fatty acid chloride) and the fatty acid (fatty acid) is a compressed heated gas grafting hydrophobic treatment facility and mixed hydrophobic acid comprising a chain aliphatic compound having 6 to 22 carbon atoms. A method for producing hydrophobic paper using a topical agent.
[2] The hydrophobicity of claim 1, wherein the non-breathable dryer belt prevents the hydrochloric acid produced from the graft reaction of the chlorinated fatty acid from dissipating from the substrate. How to make paper.
4. The compression heating according to claim 3, wherein the fatty acid chloride produces hydrochloric acid as a by-product through a grafting reaction, and the hydrochloric acid promotes a fatty acid ester reaction between the fatty acid and the hydroxyl group of the paper. A method for producing hydrophobic paper using a gas grafting hydrophobic treatment facility and a mixed hydrophobic agent.
The method of claim 1, wherein the hydrophobic paper prepared by the method for producing the hydrophobic paper has a fatty acid ester density of 700 to 1300 mg/m ² and a Cobb size (Cobb 1800s-Hot water) of 5 to 9 g/m ² A method for producing hydrophobic paper using a pressurized heated gas grafting hydrophobic treatment facility, characterized in that.

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