KR101918042B1 - Hydrophobic Fruit Paper Bag Based On Fatty Acid Chloride Treatment And Manufacturing Thereof - Google Patents

Abstract

The present invention relates to a hydrophobic fruit bag using chlorinated fatty acid and a manufacturing method thereof. The hydrophobic fruit bag gives hydrophobicity to a fruit bag by a gaseous grafting reaction of chlorinated fatty acid instead of conventional wax or oil to have excellent waterproof and water repellent effects to maintain microclimate in the bag in a high-temperature dry state to improve a sugar content of fruit, protects a fruit tree from infiltration of harmful insects and bacteria and contamination of agricultural chemicals, and uses excellent biodegradable coating agents (PVA) and vegetable chlorinated fatty acid to give hydrophobicity to have excellent recycling properties. Also, the hydrophobic fruit bag forms a PVA coating layer that is easily discolored by hydrochloric acid produced in a hydrophobic treatment process using the gaseous grafting by using a polyvinyl alcohol coating solution for a gas grafting reaction including an alkali carbonic acid metal salt slurry to prevent discoloring of the PVA coating layer even when hydrophobicity results from a gaseous grafting reaction to maintain a unique paper color with an excellent transparent property.

Description

Technical Field [0001] The present invention relates to a hydrophobic fruit bag based on chlorinated fatty acid,

The present invention relates to a process for producing a hydrophobic bag using a chlorinated fatty acid and a method for producing the same. More specifically, the present invention relates to a method for producing a fruit bag in which fruit sap is treated with chlorinated fatty acid, which is a vegetable fatty acid, and vapor grafting to protect the fruit from pesticides and pests; Improve the sugar content of the fruit by preventing rapid changes in the microcirculation conditions inside the bag; PVA, which is a biodegradable polymer, and vegetable chlorinated fatty acid which does not form a film, so that it can be recycled, and a manufacturing method thereof.

Paper is made from natural wood fibers that can be reproduced, which is biodegradable and easy to recycle by dissolving in water. However, it has weak drawbacks such as being easily wetted and loosened in water as compared with a plastic film which is a competitive material. In order to overcome the disadvantages of such paper, a method of applying wax or oil on the surface of paper has been used. However, since the wax or oil treatment does not dissolve in water, the paper is not dissolved in water, There is a problem that recycling is difficult. Therefore, it is possible to protect resources and the environment by using water-resistant paper and water that can be regenerated by environmentally friendly methods. However, in addition to the conventional treatment using wax or oil, There was a limitation that it was impossible to recycle and it was costly. In particular, in the case of a fruit bag in which demand for agricultural materials is rapidly increasing, it is manufactured by a conventional method of coating oil, wax and other water repellent to maintain water repellency for a long time. Therefore, It is required to change the idea of further enhancing the environmental friendliness from the production process to the regeneration process. Fruit bags used from the 16th century have been used only for the prevention of pests in the past, but nowadays, they are used to control the light shielding, water repellency and specularity as well as insecticidal and insecticidal effect, Is required. An example of the application of fruit bags is "pears", of which golden pears are modified by cross breeding of twenty-century varieties in 1984, with high sugar content and soft flesh, Is one of the most promising varieties of exporting prospects in Australia and Europe. (The export volume of 10ha cultivation area is 5.8M / T in 12 years, and the cultivated area is 150ha in 2005. 200.6M / T). However, the above-mentioned golden boat has not satisfied the present demand due to the decrease of the commodity value due to pests such as dandruff and black spot. By cultivating the insecticidal insecticide treated with the insecticidal insecticide, it is possible to reduce the number of pesticide spraying, prevent pesticide contamination of the insecticide by preventing pesticides directly from the insecticide, and to prevent intrusion of pests and bacteria into the insecticide. . However, conventional fruit bags used in domestic use recycled paper such as newspaper, magazine, and kraft paper. Although the recycled paper has an advantage of low cost, the light transmittance required for fruit growth is reduced due to the color and translucency of paper. Due to the thickness of the production, there is a problem in the workability of the trajectory, the temperature control ability and the durability; There is a problem that the durability of the bag is deteriorated due to the characteristics of recycled paper. In recent years, a fruit bag has been produced in which sizing agents, oils and waxes are treated between natural pulps to enhance workability and physical properties (water repellency). Water repellency and water repellency of fruit bags have a direct effect on the sugar content of fruits. However, if water repellency is weak and sudden changes in the micro conditions in the bag due to changes in the outside air, sugar content of fruit is lowered, But also the durability of the bag is also deteriorated. Considering that the internal microcapsule in the bag is high in temperature and dryness, the water-repellency of the bag should be excellent considering that the sugar content of the fruit is high. However, as the throughput of the oil or wax is increased, the natural decomposition of the bag is difficult and recycling is impossible. Therefore, a new concept of hydrophobic reforming method that can control the water repellency of bags when manufacturing fruit bags, irrespective of water loosening or natural decomposition of paper, has been developed. If applied to the manufacture of fruit bags, the quality of fruit improves, It is expected that the recycling efficiency of paper will be improved as well as saving the foreign currency. The meteorological grafting method is a method of hydrophobizing hydrophilic paper because vegetable acid forms fatty acid ester by reacting chlorinated fatty acid with hydrophilic OH group such as paper. The paper hydrophobized by the above method is advantageous in that it can be easily recycled if it is pulverized for recycling. Daniel Samain of France developed a new technology to hydrophilize hydrophilic cellulose using the hydrophobization treatment of cellulose using a meteorological grafting reaction, patented and partly registered (US 6,342,268, US 8,637,119, EP 2,231,401, US 2013-0199409, US 2014-0113080, US 2013-0236647). This technique, also called "Chromatogenic Technology", has the principle of forming a fatty acid ester by reacting gaseous chlorinated fatty acid on a hydrophilic surface including hydroxyl groups as shown in the following chemical reaction formula.

A patent (US 2013-0236647) has also been filed for a "chromatogenic gas grafting" plant in which the surface of a pulp sheet rolled by the above chemical reaction formula 1 is hydrophobized through the vapor phase grafting reaction of a chlorinated fatty acid. Since 2010, Daniel Samain has set up BT3 Technologies based on the above-described source technology to promote the commercialization of the technology, but only to verify the feasibility of producing waterproof and moisture-proof paper using a pilot machine But has not yet been applied to the manufacture of agricultural fruit bags.

Korean Published Patent Application No. 10-2016-014920 US registered patent US 6342268 US registered patent US 8637119 European Registered Patent EP 2231401 US Published Patent US 2013-0199409 US Published Patent US 2014-0113080 US Published Patent US 2013-0236647 Japanese Laid-Open Patent JP 2001-515103 China Registered Patent CN 1186118

The present inventors have made efforts to develop an environmentally-friendly fruit bag which is excellent in waterproofing and water repellency and can be recycled at a low manufacturing cost while improving the sugar content of the fruit. As a result, when the foliar encapsulated paper is coated with PVA, and the polyvinyl alcohol coating layer and the paper are hydrophobized using the vegetable fatty acid, chlorinated fatty acid and the vapor grafting method, the waterproof and water repellency of the fruit seal is improved, The present invention has been accomplished by confirming that the hydrophobized PVA and paper are easily released into water while improving the sugar content, and that the PVA and the chlorinated fatty acid have excellent biodegradability due to recyclability.

Accordingly, an object of the present invention is to provide a base paper having a basis weight of 25-45 g / m < ² > A hydrophobic fruit containing a cover including a hydrophobicized polyvinyl alchohol (PVA) coating layer formed on the hydrophobicized raw paper and an inlay with a basis weight of 20-30 g / m ² which directly surrounds the fruit by the inside of the cover Bag.

Another object of the present invention is to provide a process for producing a hydrophobic fruit bag comprising the steps of:

a) a first step of preparing a paper for a fruit bag cover;

b) a second step of forming a polyvinyl alcohol (PVA) coating layer by using a polyvinyl alcohol coating solution for gas-grafting reaction containing an alkali metal carbonate slurry on the primer;

c) a third step of hydrophobizing the raw paper on which the PVA coating layer is formed by using a vapor phase grafting method with chlorinated fatty acid to produce a fruit envelope; And

d) a fourth step of filling the fruit-sealed bag for saponification and the inlaid bag for fruit sealing.

Other objects and technical features of the present invention will be described in more detail with reference to the following detailed description, claims and drawings.

According to one aspect of the invention there is provided a) a basis weight 25-45g / m ^2, and a hydrophobic-treated base paper (base paper); b) a cover including polyvinyl alcohol (PVA) coating layer formed on the hydrophobicized raw paper and hydrophobized, and an inlay having a basis weight of 20-30 g / m ² which directly surrounds the fruit by being located inside the cover To provide a hydrophobic fruit seal. In addition, an additional fatty acid ester layer may be additionally formed on the hydrophobized PVA coating layer.

According to an embodiment of the present invention, said substrate is a substrate comprising cellulose; The PVA coating layer is formed such that the PVA is uniformly formed at ³ to 7 g / m ² on the raw ground; The fatty acid ether layer is uniformly formed at 0.3-0.8 g / m ² on the PVA coating layer using a gas grafting method using a chlorinated fatty acid.

According to another embodiment of the present invention, the PVA coating layer is coated with a polyvinyl alcohol coating solution for a gas-grafting reaction containing an alkali metal carbonate slurry.

According to another embodiment of the present invention, the vapor phase grafting method includes a vapor grafting treatment apparatus having a stainless steel belt containing voids capable of receiving hydrogen chloride generated during a vapor phase grafting reaction on the outer circumferential surface of a drying roller, .

According to another aspect of the present invention, the present invention provides a method of making a hydrophobic fruit bag comprising the steps of:

a) a first step of preparing a paper for a fruit bag cover;

b) a second step of forming a polyvinyl alcohol (PVA) coating layer by using a polyvinyl alcohol coating solution for gas-grafting reaction containing an alkali metal carbonate slurry on the primer;

c) a third step of hydrophobizing the raw paper on which the PVA coating layer is formed by using a vapor phase grafting method with chlorinated fatty acid to produce a fruit envelope; And

d) a fourth step of filling the fruit-sealed bag for saponification and the inlaid bag for fruit sealing.

The present invention relates to a process for producing a hydrophobic bag using a chlorinated fatty acid and a method for producing the same. The hydrophobic fruit packing according to the present invention is excellent in waterproof and water repellent effect by imparting hydrophobicity to the fruit bag through the vapor phase grafting reaction of the chlorinated fatty acid instead of the conventional wax or oil and maintaining the microfibers in the bag at high temperature and dry state, (PVA) and vegetable chlorinated fatty acid, which are excellent in biodegradability, to impart hydrophobicity and thus have an excellent recyclability, as well as an effect of improving the sugar content, as well as protecting fruit trees from infestation of pests or bacteria and pesticide contamination. In addition, the hydrophobic fruit packing of the present invention is formed by using a polyvinyl alcohol coating solution for gas-grafting reaction containing a slurry of alkali metal carbonate slurry, in which the PVA coating layer, which is easily discolored by hydrochloric acid generated in the hydrophobic treatment process using the vapor grafting, Therefore, even if hydrophobicity is imparted through the vapor phase grafting reaction, discoloration of the PVA coating layer is prevented, thereby maintaining not only the inherent color of the paper but also excellent transparency.

1 shows a planar structure of a fruit bag. Panel A) shows a plan view of a fused bag consisting of a hydrophobized PVA coating layer, a hydrophobicized raw paper and an inlaid panel. Panel B) shows a fruit bag consisting of a fatty acid ester layer, a hydrophobized PVA coating layer, a hydrophobicized raw paper, It shows the floor plan.
Figure 2 illustrates the process of the meteorological grafting reaction.
Fig. 3 shows a schematic diagram of an improved vapor graft processing apparatus. The vapor grafting treatment apparatus comprises an unwinder portion 1 for continuously supplying base paper coated with PVA; A drying unit (2) for heating a surface of the raw paper on which a hydroxyl group is exposed; An application roller (3) for applying a vapor grafting reagent to a raw paper surface on which the hydroxyl group is exposed; A drying roller (4) for uniformly spreading the applied grafting reagent on the surface of the paper, further comprising a belt (6) positioned between the drying roller and the substrate and rotating around the circumference of the drying roller, A drying roller (4) further comprising a touch roll (5a, 5b) for adhering a raw paper surface coated with the grafting reagent to the surface of the belt; A ventilator (7) for removing hydrogen chloride (HCl) produced during the vapor phase grafting reaction; An air knife nozzle (8) for removing the remaining vapor grafting reagent on the substrate surface; A drying roller 4, touch rolls 5a and 5b, a belt 6, and a rewinder portion 9 for rewinding the substrate subjected to the vapor-phase grafting reaction. At least two successive "vapor grafting processing units" each consisting of an air knife nozzle 8, an air blower 7 and an air knife nozzle 8 are provided continuously between the drying section 2 and the rewinder section 9.

According to one aspect of the present invention, the present invention provides a composition comprising: a) a base paper having a basis weight of 25-45 g / m ² ; And b) a cover including a polyvinyl alchohol (PVA) coating layer formed on the hydrophobized ground and hydrophobized, and an inlay having a basis weight of 20-30 g / m ² which directly surrounds the fruit by being positioned inside the cover, And the fatty acid ester layer can be uniformly formed on the hydrophobized PVA coating layer at a density of 0.3-0.8 g / m ² . The above-mentioned fruit bag means a bag used to protect fruit from being protected from sunlight, pesticide contamination, penetration of pests or bacteria, and to keep the micro-organisms in the bag dry at high temperature to improve the sugar content of the fruit. The fruit pouch can be used as a two-ply bag composed of one ply inlay and one ply overlay. Conventional fruit bags were made of cheap paper such as newspaper, magazine, and kraft paper. The fruit bag should have waterproof, water repellency, light transmittance, speculatability, and temperature control ability for fruit growth and sugar content improvement. However, fruit bags made of cheap paper materials such as newspapers, magazines, and kraft paper have insufficient light transmittance, waterproofing, and water repellency, so that the effect of improving the sugar content of fruit is limited, and durability of bags against rain or moisture is also problematic. In particular, in order to improve the sugar content of the fruit, it is necessary to keep the microcapsules in the bag dry at a high temperature. For this purpose, conventional fruit bags are manufactured by coating paper with oil or wax on cheap paper such as newspaper, magazine, kraft paper and the like. However, due to low quality of paper, the holding performance of micro paper is low, And the recyclability is poor.

On the contrary, the present invention is characterized in that PVA, which is a biodegradable polymer dissolved in water, is coated on the raw paper, and the raw paper and the PVA coating layer are hydrophobicized using a chlorinated fatty acid which is a vegetable fatty acid and a vapor grafting method, Layer is formed, water-repellent, water-repellent, and recyclable. Thus, an eco-friendly fruit bag can be manufactured. In addition, since the hydrophobic treatment of the present invention can maintain the durability of the fruit sealant paper without treating the wet paper strength enhancer, unlike conventional fruit bags, it is advantageous in that it can be reused in water.

According to one embodiment of the present invention, the substrate of the present invention is a cellulose-based substrate having a basis weight of 25-45 g / m ² . Preferably, the substrate of the present invention is paper or paperboard and has a basis weight of 30-40 g / m ² . More preferably, the paper of the present invention is paper and has a basis weight of 35 g / m ² . When the basis weight of the raw paper is less than 25 g / m ^{2, the} effect of improving the sugar content of the fruit is deteriorated due to the dimming effect of sunshine. If the basis weight exceeds 40 g / m ² , the processability as a fruit bag wrapping the fruit after coating with the PVA coating and fatty acid ester is lowered .

According to another embodiment of the present invention, the present invention performs a PVA coating on the raw ground. The PVA is used as a base material for improving surface strength of dough, improving durability and improving gas grafting efficiency using chlorinated fatty acid. The PVA has a hydroxyl group (-OH) as a biodegradable polymer, and the hydroxyl group reacts with the chlorinated fatty acid in the vapor grafting process to generate a fatty acid ester and hydrogen chloride.

According to one embodiment of the present invention, the PVA coating layer is uniformly formed on the raw paper at a density of 1-10 g / m ² . Preferably, the PVA coating layer is uniformly formed on the raw paper at a density of 3 to 7 g / m < ^{2 &} gt ;. More preferably, the PVA coating layer is uniformly formed on the raw paper at 5 g / m < ^{2 &} gt ;. When the PVA coating layer is coated to less than 1 g / m ² , the improvement of the surface strength and durability of the raw paper are insignificant and the efficiency of hydrophobing by fatty acid in the vapor grafting process is lowered. In addition, when the PVA coating layer is more than 10 g / m ² , the rigidity of the paper increases excessively, and there is a disadvantage in that the bag as a fruit bag wrapping the fruit, that is, the paper bag is not easy.

According to an embodiment of the present invention, the raw paper and the PVA coating layer are hydrophobized by forming a fatty acid ester using chlorinated fatty acid and a vapor grafting method.

The vapor phase grafting method utilizes a method in which a fatty acid chloride, which is a vegetable fatty acid on a gas phase, is reacted with a hydroxyl group (-OH) of a hydrophilic base to form a fatty acid ester on a substrate, and hydrogen chloride (HCl) is produced as a byproduct. The chemical reaction of the vapor phase grafting is represented by the chemical reaction formula 1. When the vapor phase grafting reaction is carried out on the PVA-coated paper of the present invention, fatty acid esters are formed in the hydroxyl groups contained in the raw paper and the PVA, resulting in hydrophobicity. According to an embodiment of the present invention, the hydroxy group of the cellulose of the PVA coated cellulose and the hydroxyl group of the PVA coating layer react with the chlorinated fatty acid to be converted into the fatty acid ether, so that it is hydrophobic.

In the vapor phase grafting method of the present invention, a grafting reagent containing a chlorinated fatty acid is applied to the PVA-coated raw paper and then heated to form a fatty acid ester. The chlorinated fatty acid contained in the grafting reagent means a compound in which a hydroxyl group (-OH) of a saturated fatty acid, a monounsaturated fatty acid, or a polyunsaturated fatty acid is substituted with chlorine (Cl). Wherein the saturated fatty acid is selected from the group consisting of propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, But are not limited to, acetic acid, myristic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosic acid, behenic acid, tricosolic acid, lignoceric acid, pentacosilicic acid, But are not limited to, fumaric acid, melissic acid, henatriacontylic acid, raceoic acid, tristricoctanoic acid, tetra-triacontanoic acid, pentatriacontanoic acid or hexatriaconic acid. The monounsaturated fatty acid may be, but is not limited to, palmitooleic acid, vasicic acid, or oleic acid. The polyunsaturated fatty acids are selected from the group consisting of omega-3 fatty acids such as alpha-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid, or omega-6 fatty acids such as linolenic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, and arachidonic acid linoleic acid But is not limited thereto.

According to an embodiment of the present invention, the chlorinated fatty acid of the present invention is a saturated fatty acid in which the number of carbon chains is 12 to 22 and the hydroxyl group is replaced by chlorine, and the lauric acid, tridecylic acid, It has been found to be useful in the manufacture of pharmaceutical compositions containing myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, Arachidic acid, Heneicosylic acid, or a chlorinated fatty acid in which the hydroxyl group of Behenic acid is substituted with chlorine, or a mixture of two or more thereof. Preferably, the chlorinated fatty acid of the present invention is a chlorinated fatty acid (palmitoyl chloride) in which the hydroxyl group of palmitic acid is substituted with chlorine, and a chlorinated fatty acid (stearoyl chloride) in which the hydroxyl group of stearic acid is substituted with chlorine, ≪ / RTI > or a mixture of the two.

According to one embodiment of the present invention, when the palmitoyl chloride and stearoyl chloride are mixed and used, the chlorinated fatty acid is mixed at a weight ratio of 1: 1.

According to another embodiment of the present invention, in the vapor phase grafting method of the present invention, in order to prevent non-uniform hydrophobic reaction due to shrinkage of paper in the step of applying and heating the chlorinated fatty acid during the reaction, an improved vapor graft processing apparatus . The improved vapor graft processing apparatus is characterized in that the outer circumferential surface of the drying roller is provided with a stainless steel belt which presses the paper to minimize the deformation due to paper contraction during the vapor phase grafting reaction.

Fruit bags are low basis weights less than 50 g / m ^{2, and} when they come into contact with a hot drying roll, the paper is heated quickly and shrinks as the water content decreases. If the paper has a high basis weight and the paper temperature gradually increases and the shrinkage is slight, uneven hydrophobic reaction due to the dimensional change of the paper can be avoided. However, in the case of a low basis weight paper having a low strength so that sufficient tension can not be applied, The shrinkage phenomenon can not be avoided. Therefore, the improved vapor graft treatment apparatus is indispensable.

The improved vapor graft processing apparatus comprises an unwinder section 1 for continuously supplying a base paper coated with the PVA; A drying unit (2) for heating a surface of the raw paper on which a hydroxyl group is exposed; An application roller (3) for applying a vapor grafting reagent to a raw paper surface on which the hydroxyl group is exposed; A drying roller (4) for uniformly spreading the applied grafting reagent on the surface of the paper, further comprising a belt (6) positioned between the drying roller and the substrate and rotating around the circumference of the drying roller, A drying roller (4) further comprising a touch roll (5a, 5b) for adhering a raw paper surface coated with the grafting reagent to the surface of the belt; A ventilator (7) for removing hydrogen chloride (HCl) produced during the vapor phase grafting reaction; An air knife nozzle (8) for removing the remaining vapor grafting reagent on the substrate surface; A drying roller 4, touch rolls 5a and 5b, a belt 6, and a rewinder portion 9 for rewinding the substrate subjected to the vapor-phase grafting reaction. At least two continuous "vapor grafting processing units" constituted by the air knife nozzle 8, the fan 7, and the air knife nozzle 8 are successively provided between the drying section 2 and the rewinder section 9 3). The improved vapor graft processing apparatus is described in detail in Korean Patent Laid-Open No. 10-2016-0141920.

According to one embodiment of the present invention gas phase graft of the present invention is putting the anilox (anilox) applying roller coating amount divided by 2 circuit 0.15-0.4g / m ² was applied by a total 0.3-0.8g / m ^2, and; Anilox (gravure) roller temperature 50-70 ° C; Temperature of drying roller 180-200 DEG C; The vapor grafting reaction is carried out at an operating speed of 40-60 m / min under the conditions of a temperature of hot air for air knife flushing of 280-320 ° C .; Preferably, gas phase grafting of the present invention is the anilox (anilox) applied to the roller application amount 0.25g / m ² divided by coating twice as long as a total of 0.5g / m ^2, and; Anilox (gravure) roller temperature 60 캜; Temperature of the drying roller 190 캜; And the vapor grafting reaction is carried out at an operating speed of 50 m / min under the conditions of a hot air temperature of 300 DEG C for air knife flushing.

The PVA coating layer is easily discolored by hydrochloric acid generated in the vapor phase grafting process. Accordingly, the present invention minimizes the discoloration of the PVA coating layer (KR 2016-0141920) by adopting a method in which a belt rotating around the circumference of a drying roller is made of a stainless steel belt having a plurality of voids and the hydrogen chloride is received using the voids discoloration of the PVA coating layer had a color change only 2/5 the amount (0.04 0.8 g / m ²⁾ of the amount (0.1-2g / m ²⁾ of the fatty acid chloride is applied in common for the grafting gas (gas grafting) reaction In addition to the mechanical approach, an additional approach is used because it is a very sensitive reaction to occur.

According to one embodiment of the present invention, the PVA coating layer of the present invention is coated using a polyvinyl alcohol coating solution for a gas-grafting reaction comprising an alkali metal carbonate slurry.

According to one embodiment of the present invention, the polyvinyl alcohol coating solution for the gas-grafting reaction containing the alkali metal carbonate slurry contains 8-12 wt% of polyvinyl alcohol and 88-92 wt% of water (Polyvinyl alcohol) is added to a polyvinyl alcohol coating solution for gas-grafting reaction using a chlorinated fatty acid in an amount of 1.5 to 5 parts by weight, based on 100 parts by weight of the polyvinyl alcohol, of a 75 to 80% by weight alkali metal carbonate slurry. In a polyvinyl alcohol coating solution for a gas-grafting reaction using a chlorinated fatty acid, preferably containing 9-11% by weight of polyvinyl alcohol and 89-91% by weight of water, the polyvinyl alcohol ) Is added in an amount of 3 to 6 parts by weight based on 100 parts by weight of the alkali metal carbonate slurry. More preferably, a polyvinyl alcohol coating solution for gas-grafting reaction using a chlorinated fatty acid containing 10% by weight of polyvinyl alcohol and 90% by weight of water is prepared by mixing 100 parts by weight of polyvinyl alcohol By weight of a 77% by weight alkali metal carbonate slurry in an amount of 2.5 parts by weight. When the 77 wt% alkali metal carbonate slurry is added in an amount of less than 1.5 parts by weight based on 100 parts by weight of the polyvinyl alcohol, the effect of removing hydrogen chloride is insignificant, If the amount is more than 5 parts by weight based on 100 parts by weight of polyvinyl alcohol, the hydrophobization efficiency is lowered.

According to one embodiment of the present invention, the alkali metal carbonate slurry is any one or a mixture of two or more selected from the group of metal carbonate salts consisting of calcium carbonate (CaCO ₃ ), barium carbonate (BaCO ₃ ) and magnesium carbonate (MgCO ₃ ) . Preferably, the alkali metal carbonate slurry is calcium carbonate (CaCO ₃ ).

The process of removing hydrogen chloride when a slurry of calcium carbonate (CaCO ₃ ) is used as a slurry of alkali metal carbonate in a polyvinyl alcohol coating solution for gas-grafting reaction using the chlorinated fatty acid of the present invention is as follows.

Two hydrogen chloride (HCl) molecules and calcium carbonate (CaCO ₃ ) form H ₂ CO ₃ after the reaction. This neutralizes the hydrogen chloride, resulting in a vapor grafting reaction with minimal discoloration by hydrogen chloride. However, when the carbonate formed is decomposed into water and carbon dioxide and reacts with the chlorinated fatty acid, it is necessary to adjust the amount of calcium carbonate to be added because a chain reaction may occur where fatty acid and hydrogen chloride are produced and the reaction of hydrogen chloride and calcium carbonate occurs again. As shown in the following chemical reaction formula 2, when two chlorinated fatty acids react with each other to form an ester bond based on two hydroxyl groups, two hydrogen chlorides are generated and one calcium carbonate is required to neutralize them.

( ^* H ₂ CO ₃ ) is formed by decomposing carbonic acid ( ^* H ₂ CO ₃ ) while one of carbonic acid is formed by neutralization of two hydrogen chloride with calcium chloride. One water formed by decomposing the formed carbonic acid ( ^* H ₂ CO ₃ ) consumes one chlorinated fatty acid, Respectively. To neutralize one hydrogen chloride, it takes 1/2 of calcium carbonate, 1/2 of carbonic acid, and 1/2 of water. The 1/2 water consumes 1/2 of the chlorinated fatty acid and forms 1/2 of the hydrogen chloride repeatedly. Therefore, when enough calcium carbonate is present, the two hydroxyl groups are grafted to the chlorinated fatty acid, In order to completely neutralize, two chlorinated fatty acids and 1 + 1/2 + 1/4 + 1/8 + ... ... ... The amount of chlorinated fatty acid is consumed by the sum of the infinite isobaric series represented by Geometric progression a _n = a ₁ × r is the sum of ^n-1 S _n = a ₁ × because ^{(1-r n) / (} 1-r) 1 × (1-1 / 2 n) / (1-1 / 2), when n is infinite, S _n converges to 2. Therefore, there is a problem that a chlorinated fatty acid which is twice the number of hydroxyl groups is required to completely neutralize hydrogen chloride with calcium carbonate. That is, when calcium carbonate is basically added to neutralize hydrogen chloride, it is inevitable that the vapor phase graft efficiency is lowered. However, considering that it is not necessary to neutralize the total amount of hydrogen chloride generated to control the discoloration due to actual hydrogen chloride, it is preferable to neutralize the hydrogen chloride to such an extent that the discoloration does not occur by introducing at least calcium carbonate.

According to one embodiment of the present invention, even in the gas phase grafting conditions hydrophobic reaction (vapor phase grafting reaction), the PVA hydrophobic coating layer is further fatty acid ester layer 0.3-0.8g / m ² in the present invention through performing a . Preferably, the fatty acid ester layer can be formed uniformly at 0.4-0.7 g / m ² on the hydrophobized PVA coating layer, more preferably 0.5 g / m ² .

The vapor grafting method of the present invention has the effect of reducing the manufacturing time because the hardening time is not required compared to the conventional hydrophobic process of paper using wax and oil and since the raw paper is stored in a roll form, There is an advantage in that the user can save money.

According to one embodiment of the present invention, the hydrophobic fruit envelope of the present invention manufactured by the above method has a Cobb size of 5 to 10 g / m ² after 1800 ° C, and after dissociation for 15 minutes, The flake content is 1.5-4.5 wt%. Preferably, the surface of the hydrophobic fruit bag has a flake content of 2.9 wt% which is filtered by a screen having a Cobb size of 7.2 g / m ² after 1800 属 C and a slot width of 150 탆 after 15 minutes of dissociation . The hydrophobic fruit seal of the present invention is advantageous in water repellency due to its low cobb size and high dissociation and high recyclability after use.

The fruit bags of the present invention can be used for fruit cultivation of varieties having high sugar content, such as pears, apples, and peaches. Preferably, the fruit pouch of the present invention is used for cultivation of pears.

According to another aspect of the present invention, the present invention provides a method of producing a hydrophobic fruit bag comprising the steps of:

A first step: preparing a paper for a fruit bag front;

Step 2: forming a coating layer of polyvinyl alcohol (PVA) on the base using a polyvinyl alcohol coating solution for gas-grafting reaction containing an alkali metal carbonate slurry;

Step 3: hydrophobizing the raw paper on which the PVA coating layer is formed by using a chlorinated fatty acid and a vapor grafting method to produce a fruit envelope;

Step 4: The step of removing the fruit-sealed bag and the bag for fruit sealing, which have been subjected to hydrophobic treatment.

Step 1: Preparing a paper for fuse bag

The source of the fruit pouch is a base material on which a PVA coating is performed and can be hydrophobized by a vapor grafting reaction.

According to one embodiment of the present invention, the substrate of the present invention is a substrate comprising cellulose, preferably paper.

Since newspapers, magazines, kraft paper, etc. conventionally used are paper modified through a secondary process after paper production, the number of hydroxyl groups in cellulose may be small, which may limit the hydrophobicization due to the vapor grafting reaction, Or it is difficult to adjust the transmittance depending on the thickness of the paper. Therefore, it is preferable to use a substrate containing cellulose which has not undergone a secondary modification.

Step 2: Coating polyvinyl alcohol (PVA) on the base paper

Since the PVA has a hydroxyl group, it is capable of hydrophobing by chlorophilic acid and vapor phase grafting, as well as improving the surface strength of the raw paper and improving releasing force. Also, since PVA is a biodegradable polymer, it is environmentally advantageous.

According to one embodiment of the present invention, the PVA coating layer is uniformly formed on the raw paper at a density of 1-7 g / m ² . Preferably, the PVA coating layer is uniformly formed on the raw paper at 3 - 6 g / m ² . More preferably, the PVA coating layer is uniformly formed on the base paper at 5 g / m < ^{2 &} gt ;.

According to an embodiment of the present invention, the PVA coating layer is formed using a polyvinyl alcohol coating solution for gas-grafting reaction containing an alkali metal carbonate slurry. The alkali metal carbonate neutralizes the hydrogen chloride (hydrochloric acid) formed in the vapor phase grafting process using the chlorinated fatty acid, thereby preventing discoloration of the PVA coating layer. Since the effect and mechanism of the discoloration prevention of the alkali metal carbonate slurry are described above, they are not described in order to avoid duplication of the present specification.

Step 3: PVA  The effect of chlorinated fatty acid and vapor phase Grafting  A step of hydrophobizing using a method to prepare a bag of fruit bags

The present invention relates to a process for producing a water-based grafting agent by applying a vapor phase grafting reagent containing a chlorinated fatty acid, which is a vegetable fatty acid, to a raw paper on which a PVA coating layer is formed and heating the raw paper and the PVA coating layer by a vapor grafting method, do. The vapor grafting method is performed using an improved vapor graft processing apparatus. The description of the type of chlorinated fatty acid contained in the vapor grafting reagent and the improved vapor grafting treatment apparatus are given above, and thus are not described in order to avoid duplication of the present specification.

According to one embodiment of the present invention, the fatty acid ester layer may be uniformly formed on the PVA coating layer of the raw paper on which the hydrophobic PVA coating layer is formed, in an amount of 0.3-0.8 g / m ² . Preferably, the fatty acid ester layer is uniformly formed on the PVA coating layer at 0.4-0.7 g / m < ^{2 &} gt ;. More preferably, the fatty acid ester layer of the present invention is uniformly formed at 0.5 g / m ² on the PVA coating layer.

Step 4: The step of filling the fruit envelope with the fatty acid ester layer and the bag for fruit sealing

The outer surface of the fruit bags prepared above and the inlay for fruit sealing are manufactured to produce fruit fruit bags. According to one embodiment of the present invention, the inlay for bagging is a bag of 20-30 g / m ² in weight. Preferably a basis weight of 25 g / m < ² >.

Example

Example: Manufacture of a hydrophobic fruit bag using a chlorinated fatty acid

(CaCO ₃ ) slurry in a raw paper (bacillus ridge) to prepare a hydrophobic fruit bag (fruit sapling with chlorinated fatty acid) using chlorinated fatty acid, polyvinyl alcohol (polyvinyl alcohol, PVA) forming a coating layer to prepare a geotji (hydrophobic geotji) treated for hydrophobicity a PVA coated base paper using a chlorinated fatty gas grafting (gas phase grafting) technology and the geotji and basis weight 27 g / m ² The standard inlay was discharged. First, hydrophobic processing of the fruits of the fruit bags was carried out by using a chlorinated fatty acid vapor grafting facility (see FIG. 2) installed at T company, a production company of the release paper in Dongduchon, Gyeonggi Province. The PVA coating on the paper was a polyvinyl alcohol coating solution for gas-grafting reaction containing calcium carbonate (CaCO ₃ ) slurry. The PVA coating solution was prepared by adding 2.5 parts by weight of a 77% calcium carbonate slurry (OMYA hydrocarb 95) to 100 parts by weight of 10% polyvinyl alcohol (PVA) in the polyvinyl alcohol coating solution for the gas-grafting reaction. Performing PVA coating on fruit bag base paper having a basis weight of 35 g / m ² was adjusted by the amount of pick-up (pick up) the 5 g / m ^2. In order to confirm the PVA discoloration prevention effect of the polyvinyl alcohol coating solution for the gas-grafting reaction, a coating solution was prepared by varying the amount of the calcium carbonate slurry, and the coating solution was coated with the coating solution (see Table 1).

Composition of polyvinyl alcohol coating solution 10% polyvinyl alcohol solution 77% calcium carbonate slurry PVA coating solution 1 100 parts by weight 2.5 parts by weight PVA coating solution 2 100 parts by weight 0 parts by weight PVA coating solution 3 100 parts by weight 1 part by weight PVA coating solution 4 100 parts by weight 10 parts by weight

The chlorinated fatty acid was a mixture of palmitoyl chloride (C16) and stearoyl chloride (C18) in an amount of 5: 5. The anilox roller application amount was adjusted to 0.25 g / m 2 ^2, and applied in a total amount of 0.5 g / m ² . The temperature of the anilox (gravure) roller was fixed at 60 DEG C, the temperature of the drying roller was adjusted to 190 DEG C, and the temperature of the hot air for air knife flushing was 300 DEG C Respectively. Under the above-mentioned treatment conditions, the operation speed of the equipment was fixed at 50 m / min to perform hydrophobic treatment. The chlorinated fatty acid vapor grafting apparatus is a vapor grafting apparatus equipped with a stainless steel belt containing voids capable of accommodating hydrogen chloride generated during the vapor phase grafting reaction on the outer circumferential surface of a drying roller. Korean Patent Laid- -014920.

Comparative Example: Preparation of water-repellent coated fruit bags

To fabricate the water-repellent coated fruit bags, a water-repellent coated cover was prepared and poured into a standard inlay of a basis weight of 27 g / m ^{2 on} the cover. The water-repellent coating of the cover was prepared by using a water-repellent coating solution in a roll state with a basis weight of 35 g / m ² . The water-repellent coating solution includes toluene, paraffin wax, silicone oil, amadine oil, soybean oil, seed oil, camellia oil, preservative, antioxidant and pesticide.

Drug type toluene Paraffin wax Silicone oil Linseed oil Soybean oil Seed oil Camellia oil antiseptic Antioxidant pesticide Content (㎏) 57.4 3.67 3 6.17 0.88 0.88 0.88 0.02 0.018 0.023

Experimental Example 1: Confirmation of discoloration of PVA coating layer

The PVA coating solution 1, the PVA coating solution 2, the PVA coating solution 3, and the PVA coating solution 4 were subjected to PVA coating on the base paper and hydrophobic treatment was carried out using vapor phase grafting. Cobb size after aging was measured.

Composition of polyvinyl alcohol coating solution Whiteness
(ISO brightness,%) Cobb size (Cobb 1800s_water, g / m ² ) 10% polyvinyl alcohol solution 77% calcium carbonate slurry PVA coating solution 1 100 parts by weight 2.5 parts by weight 82.5 8.2 PVA coating solution 2 100 parts by weight 0 parts by weight 27.6 7.9 PVA coating solution 3 100 parts by weight 1 part by weight 37.6 8.0 PVA coating solution 4 100 parts by weight 10 parts by weight 85.6 25.1

According to the results shown in Table 3, the hydrophobic coverings prepared by treating the PVA coating solution 1 of the present invention had much better whiteness than the hydrophobic coverings using the PVA coating solution 2 containing no calcium carbonate slurry in the polyvinyl alcohol coating solution . Also, as a result of comparing Cobb water absorption, which is a waterproof property, it was found that hydrophobic coverings using PVA coating solution 2 containing no calcium carbonate slurry, hydrophobic treatment using PVA coating solution 3 in which 1 part by weight of calcium carbonate slurry was added to a polyvinyl alcohol coating solution M ² , 8.0 g / m ² and 8.2 g / m ² in the case of the hydrophobic coverings using the PVA coating solution 1 in which 2.5 parts by weight of calcium carbonate slurry was added to the coating solution and the polyvinyl alcohol coating solution Similar to each other. In addition, in the case of the hydrophobic cover using the PVA coating solution 4 in which 10 parts by weight of the calcium carbonate slurry was added to the polyvinyl alcohol coating solution, the Cobb size was 25.1 g / m ² , which was much higher than the other hydrophobic bases .

The results of the whiteness measurement of the hydrophobic coverings using the PVA coating solution containing calcium carbonate of the present invention show that calcium carbonate effectively suppresses the discoloration of the polyvinyl alcohol coating layer caused by the hydrogen chloride generated in the hydrophobic treatment using the chlorinated fatty acid.

As a result of the experiment, it was confirmed that the whiteness was improved by increasing the calcium carbonate content of the PVA coating solution (see Table 3). In the case of the hydrophobic cover (PVA coating solution 1) in which the content of the calcium carbonate was 2.5 parts by weight, the whiteness degree of the release paper reached 82.5%, and the hydrophobic cover (PVA coating solution 4) The whiteness is similarly maintained at 85.6%, so that the titratable amount of calcium carbonate for improving whiteness is considered to be 2.5 parts by weight or more.

The measurement results of the Cobb size for the hydrophobic coverings prepared above show the hydrophobicity of the chlorinated fatty acid by the calcium carbonate. As a result of the experiment, it was confirmed that when the calcium carbonate content of the PVA coating solution was increased, the cobb size was increased (see Table 3). The Cobb size of the hydrophobic cover (PVA Coating Solution 2) prepared without adding calcium carbonate to the PVA coating solution was measured to be 7.9 g / m ² , and it was confirmed that the outer surface of the hydrophobic cover was well hydrated. In the PVA coating solution, (PVA coating solutions 3 and 1) prepared by adding 2.5 parts by weight of water to the PVA coating solution were measured to have a Cobb size of 8 and 8.2 g / m ² , respectively. It was confirmed that the hydrophobicization was performed well similar to the cover (PVA coating solution 2). However, it was confirmed that the hydrophobic cover (PVA coating solution 4) prepared by adding 10 parts by weight of calcium carbonate to the PVA coating solution was measured to have a Cobb size of 25.1 g / m ² and the efficiency of hydrophobicization of the cover was extremely low.

Therefore, the amount of calcium carbonate added to the PVA coating solution tends to be inversely proportional to the hydrophobization efficiency by the chlorinated fatty acid. When the PVA coating solution contains 2.5 parts by weight or less of the PVA coating solution, the hydrophobicization efficiency by the chlorinated fatty acid It was confirmed to be well maintained similar to a hydrophobic cover.

In summary, the hydrophobic cover (PVA coating solution 1) prepared by adding 2.5 parts by weight of calcium carbonate to the PVA coating solution has a similar whiteness degree to the Cobb size of the release paper having different cobb sizes, Which means that the discoloration was effectively suppressed.

Experimental Example 2: Water-repellent performance of a chlorinated fatty acid hydrophobic bag

Water-repellent performance of the fruit bags (example) and the water-repellent coated fruit bags (comparative example) prepared by PVA coating the raw paper with the PVA coating solution 1 having the effect of preventing discoloration of the PVA layer confirmed by chlorinated fatty acid hydrophobicization Cobb sizing degree was measured in order to obtain the following results. The Cobb size was measured by contacting water to the specimen of the fruit bag for 1800 seconds, removing water, and measuring the amount of water absorbed in the specimen. Table 4 shows the measurement results of the Cobb size.

Cobb size (1800 s_water (g / m ² )) Chlorinated Fatty Acid Hydrophobic Fruit Bond (Example) 8.1 Water-repellent coated fruit bag (comparative example) 70.1

As a result of measuring the Cobb size of the fruit sap of the chlorinated fatty acid hydrophobic fruits and the water-repellent coated fruit bags, it was confirmed that the size of the Cobb of the fruit sap of the chlorinated fatty acid hydrophobic fruits was 1/10 of the size of the Cobb size of the water- It was confirmed that the water-repellent performance of the fruit bag was remarkably excellent.

Experimental Example 3: Measurement of recyclability of fruit bags

The reusability of the chlorinated fatty acid hydrophobic bag was evaluated. For this purpose, the above-mentioned raw materials which have not been subjected to the hydrophobicization, hydrophobic treatment or water-repellent coating of the fatty acid with chlorinated fatty acid were dissociated for 15 minutes using a Tappi Standard Disintegrator, and a Sommerville Screen having a slot width of 150 [ Was used to determine the content of undigested flakes. Table 5 below shows the results of the measurement of the content of the undissolved particles of the raw paper in which the chlorinated fatty acid hydrophobic fruit sealing, the hydrophobic treatment or the water-repellent coating was not performed.

Flake Contents (% by weight) Chlorinated Fatty Acid Hydrophobic Fruit Bond (Example) 2.9 Non-hydrophobic treated and water-repellent coated paper 3.1

Chlorinated Fatty Acid Hydrophobic Fruit Seal, hydrophobic treatment, or water repellent coating were measured. As a result, the content of unsaponifiable powder in the raw paper without the chlorinated fatty acid hydrophobic fruit seal and hydrophobic treatment or water repellent coating was similar It was confirmed that the recycling of chlorinated fatty acid hydrophobic bag was similar to that of untreated paper.

Experimental Example 2: Growth and sugar content of pears using fruit bags

The prepared chlorinated fatty acid hydrophobic fruit seal and water - repellent coated fruit bag were applied to 10 - year - old pear trees of orchard in Naju, Korea. The cultivated pear was harvested and sugar content was measured. Table 6 below shows the results of the sugar content measurement of the cultured pear cultured with the fruit bag.

Brix (° BX) Chlorinated Fatty Acid Hydrophobic Fruit Bond (Example) 13.5 Water-repellent coated fruit bag (comparative example) 11

The sugar content of the cultured red pepper cultivated with the chlorinated fatty acid hydrophobic fruit bag was measured as 13.5 ° BX and the sugar content of the cultured red pepper cultivated with water - repellent coated fruit bag was measured as 11 ° BX. Generally, the sugar content of normal boats is 10 ° BX, and for the finest boats with excellent sugar content, the sugar content is 14 ° BX. Therefore, it has been confirmed that when a boat is cultivated using the chlorinated fatty acid hydrophobic fruit packing of the present invention, it is possible to cultivate a ship having an excellent sugar content higher than that of ordinary.

The specific embodiments described herein are representative of preferred embodiments or examples of the present invention, and thus the scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and other uses of the invention do not depart from the scope of the invention described in the claims.

Claims (10)

a) a base paper having a basis weight of 25-45 g / m ² and having been subjected to hydrophobic treatment; And
b) a polyvinyl alcohol (PVA) coating layer formed on the hydrophobic treated raw paper and subjected to hydrophobic treatment;
And a bag having a basis weight of 20-30 g / m < ² > for wrapping the fruit directly inside the cover,
Said substrate being a substrate comprising cellulose;
The polyvinyl alcohol coating layer is uniformly formed on the raw paper at a density of 1-10 g / m ² ;
A fatty acid ester layer is further uniformly formed at 0.3-0.8 g / m ² on the hydrophobized polyvinyl alcohol coating layer;
The hydrophobic treatment of the base paper and the polyvinyl alcohol coating layer may be carried out in a liquid medium such as lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, , Hydroxycarboxylic acid, stearic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, or behenic acid. Is carried out using a gas grafting method using one chlorinated fatty acid or a mixture of two or more selected from chlorinated fatty acids substituted with chlorine;
The vapor grafting method uses a vapor grafting treatment apparatus equipped with a stainless steel belt containing voids capable of receiving hydrogen chloride generated during a vapor grafting reaction on the outer circumferential surface of a drying roller;
Wherein the fruit is double the fruit. delete delete The method according to claim 1,
Wherein the polyvinyl alcohol coating layer is coated with a polyvinyl alcohol coating solution for vapor-phase grafting reaction containing an alkali metal carbonate slurry. delete delete delete 5. The method according to any one of claims 1 to 4,
The outer surface of the hydrophobic fruit bag had a Cobb size of 8.1 g / m ² after 1800 ° C and a flake content of 2.9% by weight filtered by a screen having a slot width of 150 μm after dissociation for 15 minutes Fruit bag with hydrophobicity.
delete a) a first step of preparing a hydrophobicized paper bag for a fruit bag having a basis weight of 25-45 g / m ² ;
b) adding a polyvinyl alcohol coating solution for forming a polyvinyl alcohol coating layer using a polyvinyl alcohol coating solution for vapor-phase grafting reaction, wherein 2.5% by weight of an alkaline metal carbonate slurry is added in an amount of 77% by weight based on 100 parts by weight of polyvinyl alcohol Step 2;
c) The raw paper on which the polyvinyl alcohol coating layer is formed is hydrophobized using chlorofluorocarbons and a vapor phase grafting method. Cobb size after 1800 seconds is 8.1 g / m ^2. After dissociation for 15 minutes, A third step of producing a fruit envelope with a flake content of 2.9% by weight filtered by the third step; And
d) a fourth step of picking up the fruit sealing bag and the bag for fruit sealing, which have been subjected to the hydrophobic treatment;
Wherein the hydrophobic bag is made from a hydrophobic material.

Images