KR20240037172A - Barrier red algae fiber, manufacturing method thereof, barrier coated paper and barrier sheet containing the same - Google Patents

Abstract

The present invention relates to barrier red algae fibers, a method for producing the same, barrier coated paper and barrier sheets containing the same. The barrier coated paper according to the present invention has oxygen permeation prevention properties and dehydration properties during the coating process compared to conventional wood-derived nanocellulose. Not only is it highly effective, but it is also environmentally friendly as it has biodegradable properties.

Description

Barrier red algae fiber, manufacturing method thereof, barrier coated paper and barrier sheet containing the same}

The present invention relates to barrier red algae fibers, and more specifically, to barrier red algae fibers, a method of manufacturing the same, barrier coated paper and barrier sheets containing the same.

General ‘paper’ is made up of intertwined pulp fibers and has many spaces, making it easy for oxygen and water vapor to pass through. That is, there is no barrier property that can prevent moisture, oxygen, and other substances introduced from the outside from penetrating into the interior. Therefore, most packaging paper is treated with a barrier coating, and the most widely used method is laminating polyethylene (PE), and latex coating is also being considered. These materials are excellent in terms of providing moisture resistance, but because they are petrochemical carbon compounds, they have the disadvantage of being difficult to biodegrade and not being environmentally friendly. Therefore, there is an urgent need to discover new natural materials that can replace petrochemical raw materials and expand their use.

Therefore, many efforts are being made to obtain the barrier properties previously provided by petrochemical raw materials such as polyethylene from eco-friendly materials, and cellulose nanofibrils (Cellulose nanofibrils) are made by dividing cellulose, the most representative eco-friendly material, into nanometer (nm) scale. CNF) is considered a candidate to replace petrochemical raw materials and strengthen the barrier properties of packaging materials. Cellulose nanofibers are sustainable, biodegradable, natural organic polymers that are typically less than 100 nm wide and several μm long. These cellulose nanofibers are known to have a very large aspect ratio, high specific surface area, and excellent strength properties. In addition, cellulose nanofibers are easy to manufacture into films due to the strong hydrogen bonds formed between nanofibers when dried. Since filmized cellulose nanofibers can provide strong barrier properties against oxygen and liquid, it is expected that they can be used as an eco-friendly barrier property strengthening material in the packaging paper field. However, the nanocellulose used to date is a wood-derived nanofiber. Since cellulose does not have excellent dehydration properties, there is an urgent need to discover biodegradable barrier materials with even better dehydration and oxygen penetration prevention properties.

Meanwhile, red algae is a red or purple seaweed that contains red algae and blue-green algae in addition to chlorophyll. It lives in relatively deeper water than other algae, is relatively small in size, and is very diverse, with over 4,000 species. Red algae has a wider habitat range than green and brown algae, growing naturally from shallow water depths to deep water areas where sunlight reaches them. Among seaweeds, red algae contain a large number of fibers called root fibers, and these fibers have a diameter of several microns, which is an almost constant size in all red algae. In addition, red algae fibers have excellent whiteness and opacity, and the bonding ability between red algae fibers is also excellent. The crystallinity of red algae fiber is similar to that of cellulose fiber, and in particular, the thermal properties of bleached red algae fiber are superior to cellulose fiber. Red algae include seaweed, agar-agar, agar-agar, seaweed, agar-agar, agar-agar-agar-agar-agar-agar-agar, agar-agar-agar, agar-agar-agar-agar-agar-agar-agar-agar, agar-agar-agar, agar-agar-agar-agar, agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-agar-and-a-leaf-agar-and-a-leaf-a-leaf-a-sea, agar-agar, and agar-agar. The internal gel extract of red algae is used as a food additive, health supplement, and agar material.

As barrier film-related technology, Korean Patent Publication No. 1999-0034085 discloses a manufacturing method and composition of a cellophane replacement film using carrageenan raw polymer, and Korean Patent No. 1770227 discloses a composition for anti-fouling-moisture-proof barrier coating. Although a manufacturing method and a manufacturing method of an antifouling-moisture resistant barrier film using the same have been disclosed, a barrier coating method using the biodegradable seaweed fiber of the present invention, a barrier sheet containing seaweed fiber, and paper coated with a barrier coating of seaweed fiber are still available. It has not been disclosed about.

The present invention was developed in response to the above-mentioned needs, and the present invention provides barrier red algae fibers with excellent oxygen permeation prevention properties and excellent dehydration properties during the coating process, a method for manufacturing the same, barrier coated paper and barrier sheets containing the same. There is a purpose to doing this.

In order to solve the above-described problems, the present invention provides a barrier red algae fiber including an oval-shaped red algae fiber with a cross-sectional major axis length of 50 to 500 ㎛.

According to one embodiment of the present invention, the oval red algae fiber may have a fiber wall thickness of 50 to 500 nm.

Additionally, the oval red algae fiber may be included in more than 50% by weight of the total weight of the barrier red algae fiber.

In addition, the barrier red algae fiber is formed through red algae, and the red algae may include one or more of Eucheuma cottonii, Eucheuma spinosum, and Gracilaria.

In addition, the present invention relates to (1) adding 1000 to 3000 parts by weight of water to 100 parts by weight of a mixture of 0.1 to 5.0 wt% of sulfuric acid and 95 to 99.9 wt% of red algae, followed by adding 1,000 to 3,000 parts by weight of water at 60 to 120°C for 1 to 5 hours; removing carrageenan or agar and obtaining the remaining red algae residue by reacting for a while, and (2) 400 to 600 parts by weight of water and 0.5 to 0.5 to 100 parts by weight of the red algae residue obtained in step (1). Barrier red algae comprising the step of adding 5.0 parts by weight of a bleaching material, adjusting the pH to 3-5, and reacting at 60-95°C for 0.5-5 hours to bleach and wash the red algae residue to obtain barrier red algae fiber. Provides a fiber manufacturing method.

According to one embodiment of the present invention, the bleaching material may be any one or more of chlorine dioxide, sodium hypochlorite, chlorine, ozone, and oxygen.

Additionally, the present invention provides paper and a barrier coated paper comprising a barrier coating layer coated on at least a portion of the surface of the paper and comprising the barrier red algae fibers described above.

According to one embodiment of the present invention, the barrier coating layer may further include a polymer, and the barrier coating layer may include 10 to 99% by weight of the polymer and 1 to 90% by weight of the barrier red algae fiber.

In addition, the polymers include poly vinyl alcohol (PVA), starch, nanocellulose, chitin, poly-L-lactic acid (PLLA), stereo complex polylactic acid (sc-PLA), and poly-(3-hydroxy buthyrate) (PHB). ), PBS (Poly Butylene Succinate), PCA (Poly caprolactone), and PGA (Poly glycolic acid).

Additionally, the barrier coating layer may have a basis weight of 1 to 100 g/m2.

In addition, the barrier coating layer may further include any one or more of PAM (poly amidoamine), a wet strength enhancer, and a hydrophobizing agent.

In addition, the wet strength enhancer may include one or more of epoxy emulsion and epichlorohydrin, and the hydrophobizer may include one or more of AKD (alkyl ketene dimer), ASA (alkenyl succinic acid), and rosin. You can.

Additionally, the present invention provides a barrier sheet containing the barrier red algae fibers described above.

The present invention was developed in response to the above-mentioned needs, and the barrier red algae fiber according to the present invention, its manufacturing method, barrier coated paper and barrier sheet containing the same have oxygen permeation prevention properties and dehydration properties during the coating process, which are derived from conventional wood. It has better effects than nanocellulose.

Figure 1 shows a flow chart of the biodegradable barrier coating method of the present invention.
Figure 2 shows an electron micrograph of Yukima kotoni fibers (A), the results of confirming the thickness of Yukima kotoni fibers using an atomic force microscope (B), and cylindrical nanocellulose from wood cellulose (C), where A is about The fiber thickness of two 100 nm fiber walls overlapping is 200 nm, B represents the surface height of the sample holder, and C represents wood cellulose, which is cylindrical rather than oval, and the fibril width is approximately 100 nm.
Figure 3 is a comparison of Yukima kotoni fiber and cellulose fiber, showing (a) the XRD pattern of Yukima kotoni fiber and cellulose (softwood fiber, which is bleached softwood pulp), (b) Yukima kotoni fiber and cellulose This is the HPLC result analyzing the content of sugars (fructose, glucose, and xylose).

Hereinafter, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts not related to the description are omitted, and identical or similar components are given the same reference numerals throughout the specification.

The barrier red algae fiber according to the present invention is implemented including oval-shaped red algae fiber.

At this time, the oval red algae fiber has an oval shape as shown in FIG. 2.

In addition, the oval red algae fiber may have a cross-sectional major axis length of 50 to 500 ㎛, and preferably a cross-sectional major axis length of 60 to 450 ㎛. If the long axis length of the oval red algae fiber cross section is less than 50㎛, dewatering properties may be reduced during the coating process, and if the long axis length of the oval red algae fiber cross section exceeds 500㎛, oxygen penetration prevention properties may be reduced.

Meanwhile, the term “major axis” used in the present invention refers to the axis having the longest length in the cross section.

Additionally, the oval red algae fiber may have a fiber wall thickness of 50 to 500 nm, and preferably may have a fiber wall thickness of 60 to 450 nm. If the fiber wall thickness of the oval red algae fiber is less than 50 nm, dewatering properties may be reduced during the coating process, and if the fiber wall thickness of the oval red algae fiber exceeds 500 nm, the oxygen penetration prevention property may be reduced.

In addition, the oval red algae fiber may be included in 50% by weight or more of the total weight of the barrier red algae fiber, preferably 60% by weight or more of the total weight of the barrier red algae fiber, and more preferably, the barrier red algae fiber. It may comprise more than 70% by weight of the total weight. If the oval red algae fibers are included in less than 50% by weight of the total weight of the barrier red algae fibers, the oxygen penetration prevention properties and dehydration properties during the coating process may be reduced.

In addition, the barrier red algae fiber according to the present invention is (1) 60 to 120 parts by weight after adding 1000 to 3000 parts by weight of water to 100 parts by weight of a mixture of 0.1 to 5.0 wt% of sulfuric acid and 95 to 99.9 wt% of red algae. Reacting at ℃ for 1 to 5 hours to remove carrageenan or agar and obtain the remaining red algae residue;

(2) Add 400 to 600 parts by weight of water and 0.5 to 5.0 parts by weight of bleaching material to 100 parts by weight of red algae residue obtained in step (1), adjust pH to 3 to 5, and incubate at 60 to 95°C. It is prepared including the step of reacting for 0.5 to 5 hours to bleach and wash the red algae residue to obtain barrier red algae fiber.

At this time, the red algae preferably includes one or more of Eucheuma cottonii, Eucheuma spinosum, and Gracilaria, but is not limited thereto.

In addition, the bleaching material is preferably any one of chlorine dioxide, sodium hypochlorite, chlorine, ozone, and oxygen, more preferably chlorine dioxide or sodium hypochlorite, and even more preferably chlorine dioxide. It may be more advantageous in achieving the goal.

Additionally, the present invention provides paper and a barrier coated paper comprising a barrier coating layer coated on at least a portion of the surface of the paper and comprising the barrier red algae fibers described above.

At this time, the barrier coating layer may further include a polymer, and the barrier coating layer may include 10 to 99% by weight of the polymer and 1 to 90% by weight of the barrier red algae fiber. As the polymer and the barrier red algae fiber satisfy the above content range, it can be more advantageous to achieve the purpose of the present invention.

The polymers include PVA (Poly vinyl alcohol), starch, nanocellulose, chitin, PLLA (Poly-L-Lactic Acid), sc-PLA (Stereo Complex Polylactic Acid)), PHB (Poly-(3-hydroxy buthyrate)), It is preferable to include, but is not limited to, one or more selected from PBS (Poly Butylene Succinate), PCA (Poly caprolactone), and PGA (Poly glycolic acid).

Meanwhile, the barrier coating layer can be formed by mixing the polymer and the barrier red algae fiber and coating it on the surface of paper.

At this time, before mixing the polymer and the barrier red algae fiber, secondary bleaching can be performed by mixing hydrogen peroxide and the barrier red algae fiber, adjusting the pH, and then heat treating.

At this time, the secondary bleaching can be performed by mixing 0.5 to 5.0% by weight of hydrogen peroxide and 95 to 99.5% by weight of the barrier red algae fiber, the pH can be adjusted to pH 10 to 13, and the heat treatment is performed at a temperature of 60 to 60. It can be performed at 95°C for 0.5 to 5 hours.

Meanwhile, the barrier coating layer may have a basis weight of 1 to 100 g/m2.

In addition, the barrier coating layer may further include any one or more of PAM (poly amidoamine), a wet strength enhancer, and a hydrophobizing agent. The wet strength enhancer may include one or more of epoxy emulsion and epichlorohydrin, and the hydrophobizer may include one or more of AKD (alkyl ketene dimer), ASA (alkenyl succinic acid), and rosin. , but is not limited to this.

Meanwhile, the present invention provides a barrier sheet containing the barrier red algae fibers described above.

The barrier coating layer may be formed solely from the barrier red algae fibers described above, or may be formed including a predetermined polymer and the barrier red algae fibers.

According to one embodiment of the present invention, the barrier sheet may further include a polymer, and in this case, the barrier sheet may include 10 to 99% by weight of the polymer and 1 to 90% by weight of the barrier red algae fibers described above. there is. As the polymer and the barrier red algae fiber satisfy the above content range, it can be more advantageous to achieve the purpose of the present invention.

The polymers include PVA (Poly vinyl alcohol), starch, nanocellulose, chitin, PLLA (Poly-L-Lactic Acid), sc-PLA (Stereo Complex Polylactic Acid)), PHB (Poly-(3-hydroxy buthyrate)), It is preferable to include, but is not limited to, one or more selected from PBS (Poly Butylene Succinate), PCA (Poly caprolactone), and PGA (Poly glycolic acid).

Meanwhile, before mixing the polymer and the barrier red algae fiber, secondary bleaching can be performed by mixing hydrogen peroxide and the barrier red algae fiber, adjusting the pH, and then heat treating.

At this time, the secondary bleaching can be performed by mixing 0.5 to 5.0% by weight of hydrogen peroxide and 95 to 99.5% by weight of the barrier red algae fiber, the pH can be adjusted to pH 10 to 13, and the heat treatment is performed at a temperature of 60 to 60. It can be performed at 95°C for 0.5 to 5 hours.

Meanwhile, the barrier sheet may have a basis weight of 1 to 100 g/m2.

In addition, the barrier sheet may further include any one or more of PAM (poly amidoamine), a wet strength enhancer, and a hydrophobizing agent. The wet strength enhancer may include one or more of epoxy emulsion and epichlorohydrin, and the hydrophobizer may include one or more of AKD (alkyl ketene dimer), ASA (alkenyl succinic acid), and rosin. , but is not limited to this.

Hereinafter, the present invention will be described in more detail using examples. These examples are only for illustrating the present invention in more detail, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[Example]

Example 1-1. Manufacture of barrier red algae fiber (Eucheuma cottonii fiber)

Yukima kotoni fiber (barrier red algae fiber) was manufactured using a manufacturing method according to the flow chart disclosed in FIG. 1.

a. After adding 300 g of dried Yukima Kotoni, a red algae fiber, to water to 6,000 g of water to achieve a weight ratio of 20:1 (water: Yukima Kotoni), 0.3% by weight of sulfuric acid was added based on the weight ratio of Yukima Kotoni. Added. Afterwards, the temperature was raised for 30 minutes and reacted at 100°C for 3 hours. Carrageenan was sufficiently extracted using a 200 mesh screen, and the remaining residue was called 'Yukima kotoni residue (red algae residue)'. .

b. After adjusting the water: Yukima kotoni residue weight ratio to 5:1, 2% by weight of chlorine dioxide was added based on the dry weight of the Yukima kotoni residue, and the pH was adjusted to 3.5 with acetic acid. Afterwards, the Yukima Kotoni residue was bleached by reacting at a temperature of 90°C for 1 hour and 30 minutes, and the washed material was called 'Yukima Kotoni Fiber (Barrier Red Algae Fiber)'.

In Example 1 of the present invention, it was confirmed from the XRD results and sugar analysis results of Yukima cotoni fiber that Yukima cotoni is composed of cellulose (Figure 3), and after extracting agar from Gracilaria, , ‘Cellulose fibers’ can also be obtained from the remaining solids.

The produced barrier red algae fiber contained 80% by weight of oval red algae fibers with a cross-sectional major axis length of 50 to 500 ㎛ and a fiber wall thickness of 50 to 500 nm.

Example 1-2

Barrier red algae fiber was prepared in the same manner as in Example 1-1, except that Yukima cotoni was changed to Gracilaria. The produced barrier red algae fiber contained 70% by weight of oval red algae fibers with a cross-sectional major axis length of 50 to 500 ㎛ and a fiber wall thickness of 50 to 500 nm.

Comparative Example 2-1

Barrier red algae fiber was prepared in the same manner as in Example 1-1, except that the red algae Organic Macotoni was changed to the red algae Agar agar. The produced barrier red algae fibers were cylindrical fibers with a major axis length of 500 to 800 ㎛ and a fiber thickness of 1,000 to 2,200 nm.

Comparative Example 2-2

Nanocellulose was prepared by passing bleached hardwood pulp 60 times through a super masscolloidor at a concentration of 1.5%. The obtained nanocellulose was a cylindrical fiber with a long axis of 8.2㎛ and a fiber width of 35.2nm.

Preparation Examples 1-1 to 1-2 and Comparative Preparation Examples 1-1 to 1-2. Manufacturing of barrier sheets

Square meters on a cellulose acetate membrane (0.45㎛ pore size, HYUNDAI MICRO, Republic of Korea) filter using the fibers prepared in Example 1-1, Example 1-2, Comparative Example 2-1 and Comparative Example 1-2. A barrier sheet with a basis weight of 10 g/m ² was prepared.

Experimental Example 1: Oxygen permeability (OP) and permeability analysis

For the barrier sheets according to Preparation Examples 1-1 to 1-2 and Comparative Preparation Examples 1-1 to 1-2, oxygen permeability was measured. The oxygen transmission rate was measured for 24 hours at 23 degrees Celsius, 1 atm, and 0 relative humidity using an ultra-precision oxygen analyzer (OX-TRAN Model 2, MOCON, USA). To correct the barrier sheet thickness, the oxygen permeability was calculated by dividing the oxygen permeability by the sheet thickness.

In addition, when manufacturing a barrier sheet with a basis weight of 5 g/m ² on a cellulose acetate membrane (0.45㎛ pore size, HYUNDAI MICRO, Republic of Korea) filter under the same vacuum pressure, the time taken until dehydration no longer proceeds was measured. Dehydration was analyzed.

The results are shown in Table 1 below.

Sample OP (oxygen permeability)
cm ³ ·㎛/m ² ·day·atm Dehydration time (seconds) Manufacturing Example 1-1 95 30.4 Manufacturing Example 1-2 129 37.8 Comparative Manufacturing Example 1-1 1237 42.6 Comparative Manufacturing Example 1-2 234 342.1

As shown in Table 1 above, Preparation Example 1-1 and Preparation Example 1-2, which satisfy all the long axis length, fiber wall thickness, and content of the oval red algae fiber of the present invention, exceed the range of the long axis length and fiber wall thickness of the cross section, and It was confirmed that the oxygen permeability was significantly lower than that of Comparative Preparation Example 1-1 using cylindrical fibers, the long axis length of the cross section and the fiber wall thickness were less than the range, and the dehydration time was significantly faster than that of Comparative Preparation Example 1-2 using cylindrical fibers. You can.

Manufacturing Example 2. Coating 5g of Yukima Kotoni fiber on coating base

After mixing 60% by weight of the Yukima Kotoni fiber and 40% by weight of PVA (polyvinyl alcohol) prepared in Example 1-1, a coating base paper (a coating base paper distributed from a domestic M paper company and has a basis weight of 50 g/m ² (hereinafter referred to as coating base paper) was coated and dried using a coating bar so that the weight of the coating layer was 5g per square meter on a dry basis.

Manufacturing Example 3. Coating 10g of Yukima Kotoni fiber on coating base

After mixing 60% by weight of Yukima Kotoni fiber and 40% by weight of PVA (polyvinyl alcohol) prepared in Example 1-1, the weight of the coating layer was 10g per square meter on a dry basis using a coating bar on the coating base paper. It was coated as much as possible and dried.

Comparative Manufacturing Example 2. Manufacturing of bleached hardwood pulp barrier sheet 1

Bleached hardwood pulp was beaten using a valley beater until it reached 510 ml at Canadian standard freeness, and a barrier sheet of 20 g per square meter was manufactured in the same manner as Preparation Example 1-1.

Comparative Manufacturing Example 3. Manufacturing of bleached hardwood pulp barrier sheet 2

Bleached hardwood pulp was beaten using a valley beater until it reached 95 ml at Canadian standard freeness, and a barrier sheet weighing 20 g per square meter was manufactured in the same manner as Preparation Example 1-1.

Comparative Preparation Example 4. Preparation of microfibrils and nanocellulose

The beaten hardwood fibers of Comparative Preparation Example 3 were used, and the beating was repeated 20 times additionally using a super masscolloidor to form a cylindrical product with a fibril length of 25.5 μm and an average fibril width of 185 nm. Microfibrils (cellulose microfibril (CMF)) were manufactured.

In addition, the beaten hardwood fibers of Comparative Preparation Example 3 were used, and the beating was repeated 60 times additionally using a super masscolloidor to obtain a cylindrical shape with a fibril length of 7.6 μm and an average fibril width of 45 nm. Nanocellulose (cellulose nano-fibrils, CNF) was manufactured.

Comparative Manufacturing Example 5. Manufacture of 10g barrier sheet per square meter using CMF

A barrier sheet weighing 10 g per square meter was manufactured on the nanofilter using the CMF prepared in Comparative Preparation Example 4.

Comparative Manufacturing Example 6. Manufacture of 10g barrier sheet per square meter using CNF

A barrier sheet weighing 10 g per square meter was manufactured on the nanofilter using the CNF prepared in Comparative Preparation Example 4.

Comparative Manufacturing Example 7. Coating 10g of CMF on coated base paper

After mixing 60% by weight of the dry CMF prepared in Comparative Manufacturing Example 4 and 40% by weight of PVA (polyvinyl alcohol), the coating was coated on the coating base paper using a coating bar so that the weight of the coating layer was 10g per square meter on a dry basis and dried. I ordered it.

Comparative Manufacturing Example 8. Coating 10g of CNF on coating base

After mixing 60% by weight of dried CNF and 40% by weight of PVA (polyvinyl alcohol) prepared in Comparative Manufacturing Example 4, the coating was coated on the coating base paper using a coating bar so that the weight of the coating layer was 10g per square meter on a dry basis and dried. I ordered it.

Comparative Manufacturing Example 9. Film Manufacturing

At Extruder (Multi-Layer T-die Extrusion Film Production Line, Hankook EM, Korea), under conditions of 160~180℃, PLA (1.2~1.6% stereoisomer of D-isomer lactide (PLA-4032D) and 220kDa After heating (average molecular weight), a film weighing 10 g per square meter was prepared.

Comparative Manufacturing Example 10. Coated base paper

Coated base paper weighing 50g per square meter was purchased from a domestic company M and used.

Experimental Example 2. Oxygen permeability (OP) analysis

The components of Preparation Examples 1-1, 2, and 3 and Comparative Preparation Examples 2 to 10 and their oxygen permeability were measured (measured using the oxygen permeability measurement method in Experimental Example 1).

Table 2 discloses the oxygen permeability (OP) results of the film. Considering that the oxygen permeability of PVDC (polyvinylidene chloride), a polymer barrier film with excellent oxygen permeability, is 10 to 300 cm ³ ·㎛/m ² ·day·atm, Yukima Kotoni fiber, a biodegradable material (Preparation Example 1- 1) and CNF (Comparative Preparation Example 6) were judged to be able to act as an excellent oxygen gas barrier, and in preparation for this, heavily refined hardwood fibers (Comparative Preparation Example 2, Comparative Preparation Example 3) barrier sheets and It was confirmed that the PLA (Comparative Preparation Example 9) film had very high oxygen permeability, and that the CMF (Comparative Preparation Example 5) film did not serve as an excellent barrier.

Oxygen permeability of barrier sheet or film Sample type form OP (oxygen permeability)
cm ³ ·㎛/m ² ·day·atm Manufacturing Example 1-1 Yukima Kotoni Fiber Barrier sheet 10g/ ^m2 95 Comparative Manufacturing Example 2 Hardwood pulp 510ml CSF Barrier sheet 20g/m ² >10,000 Comparative Manufacturing Example 3 Hardwood pulp 95ml CSF Barrier sheet 20g/m ² >10,000 Comparative Manufacturing Example 5 CMF Barrier sheet 10g/ ^m2 487 Comparative Manufacturing Example 6 CNF Barrier sheet 10g/ ^m2 153 Comparative Manufacturing Example 9 PLA Film 10g/ ^m2 17,792

In Table 3, it was confirmed that when Yukima Kotoni fiber (Preparation Example 3) and CNF were coated on the coating base paper (Comparative Preparation Example 8) at 10 g/m ² , it could act as an excellent oxygen barrier like a PVDC film. However, when a small amount of Yukima kotoni fiber was coated, the oxygen permeability was slightly higher than that of PVDC, as in Preparation Example 2. In contrast, CMF (Comparative Preparation Example 7) still showed significantly higher oxygen permeability than PVDC.

Oxygen permeability after coating on 50g of coating base per square meter Sample type form OP (oxygen permeability)
cm ³ ·㎛/m ² ·day·atm Manufacturing example 2 Yukima kotoni fiber, PVA Coating 5g/ ^m2 318 Manufacturing example 3 Yukima kotoni fiber, PVA Coating 10g/ ^m2 56 Comparative Manufacturing Example 7 CMF, PVA Coating 10g/ ^m2 855 Comparative Manufacturing Example 8 CNF, PVA Coating 10g/ ^m2 128 Comparative Manufacturing Example 10 Chemical pulp coating base paper 50g/ ^m2 >10,000

As described above, it was confirmed that Yukima kotoni fiber and CNF can serve as excellent oxygen barriers. However, in order to manufacture CNF, not only must bleached wood pulp be manufactured first, but also a lot of energy must be administered to manufacture nanocellulose. In contrast to this, Yukima Kotoni fiber has the advantage of requiring less energy as it can be manufactured with only a simple bleaching process.

Experimental Example 3. Dehydration analysis

In order to apply a biodegradable film or coating material as a packaging material, water must be used as a medium. If the dehydration rate of the water used as a medium is delayed, not only does the production speed when manufacturing the film slow down, but it also becomes difficult to coat at a high concentration. difficult. Therefore, it was confirmed whether the dehydration property was excellent.

The dehydration experiment is the time taken until dehydration no longer occurs when a barrier sheet with a basis weight of 5 g/m ² is manufactured on a cellulose acetate membrane (0.45㎛ pore size, HYUNDAI MICRO, Republic of Korea) filter by applying the same vacuum pressure. Measured.

The results of the dehydration analysis are shown in Table 4. As shown in Table 4, CMF (Comparative Preparation Example 5) or CNF (Comparative Preparation Example 6) dehydrates very slowly, so unless a special device is used or a lot of drying energy is used, product production may be disrupted. It is very likely that this will become inevitable.

On the other hand, it was confirmed that Yukima Kotoni fiber has dehydration properties similar to those obtained by beating hardwood pulp, so it can be manufactured using papermaking machines with high productivity and low drying energy.

Dehydration characteristics of biodegradable barrier raw materials Sample reference Dehydration time (seconds) Yukima Kotoni Fiber Manufacturing Example 1-1 30.4 Hardwood pulp 95 ml CSF Comparative Manufacturing Example 3 29.4 CMF Comparative Manufacturing Example 5 189.5 CNF Comparative Manufacturing Example 6 243.7

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiment presented in the present specification, and those skilled in the art who understand the spirit of the present invention can add components within the scope of the same spirit. , other embodiments can be easily proposed by change, deletion, addition, etc., but this will also be said to be within the scope of the present invention.

Claims (13)

A barrier red algae fiber comprising an oval-shaped red algae fiber with a cross-sectional major axis length of 50 to 500㎛. According to paragraph 1,
The oval red algae fiber is a barrier red algae fiber with a fiber wall thickness of 50 to 500 nm. According to paragraph 1,
The oval red algae fiber is a barrier red algae fiber comprising 50% by weight or more of the total weight of the barrier red algae fiber. According to paragraph 1,
The barrier red algae fiber is formed through red algae, and the red algae includes any one or more of Eucheuma cottonii, Eucheuma spinosum, and Gracilaria. (1) For 100 parts by weight of a mixture of 0.1 to 5.0% by weight of sulfuric acid and 95 to 99.9% by weight of red algae, add 1,000 to 3,000 parts by weight of water and react at 60 to 120°C for 1 to 5 hours to produce carrageenan or Removing agar and obtaining remaining red algae residue; and
(2) Add 400 to 600 parts by weight of water and 0.5 to 5.0 parts by weight of bleaching material to 100 parts by weight of red algae residue obtained in step (1), adjust pH to 3 to 5, and incubate at 60 to 95°C. A method of producing barrier red algae fiber comprising: reacting for 0.5 to 5 hours to bleach and wash the red algae residue to obtain barrier red algae fiber. According to clause 5,
The bleaching material is any one or more of chlorine dioxide, sodium hypochlorite, chlorine, ozone, and oxygen. paper; and
A barrier coating layer coated on at least a portion of the surface of the paper and comprising the barrier red algae fiber according to any one of claims 1 to 4. In clause 7,
The barrier coating layer further includes a polymer,
The barrier coating layer includes 10 to 99% by weight of the polymer and 1 to 90% by weight of the barrier red algae fiber. According to clause 8,
The polymers include PVA (Poly vinyl alcohol), starch, nanocellulose, chitin, PLLA (Poly-L-Lactic Acid), sc-PLA (Stereo Complex Polylactic Acid)), PHB (Poly-(3-hydroxy buthyrate)), Barrier coated paper containing one or more selected from the group consisting of Poly Butylene Succinate (PBS), Poly caprolactone (PCA), and Poly glycolic acid (PGA). In clause 7,
The barrier coating layer is a barrier coating paper with a basis weight of 1 to 100 g/m2. In clause 7,
The barrier coating layer further includes any one or more of PAM (poly amidoamine), a wet paper strength enhancer, and a hydrophobizer. The method of claim 11, wherein the wet strength enhancer includes at least one of epoxy emulsion and epichlorohydrin, and the hydrophobizer includes at least one of AKD (alkyl ketene dimer), ASA (alkenyl succinic acid), and rosin. Containing barrier coated paper. A barrier sheet comprising the barrier red algae fiber according to any one of claims 1 to 4.