KR20110117967A - Manufacturing method of pulp of source for transparent high density paper, a pulp and transparent high density paper manufactured by the method - Google Patents

Abstract

The present invention comprises the steps of (a) washing red algae, (b) ozone treating the washed red algae, (c) bleaching the ozone treated red algae with bleach, and (d) converting the bleached red algae into fibers. A method for producing transparent high density paper stock pulp from red algae comprising the step of converting and the pulp and transparent high density paper produced thereby. In the present invention, unlike the conventional pulp manufacturing method using red algae, the internal gel extraction process is omitted. According to the present invention, the production process is simplified compared to the existing method, thereby reducing the production cost, and the yield of pulp obtained from red algae. It can be increased by more than 50% compared to the existing method, and the thermal shortening of the paper manufactured using such a pulp is more than two times improved compared to the existing method, it is possible to produce a transparent high-density paper that is friendly to the human body and the environment. The transparent high density paper produced in this way can be used as various paper products requiring transparency and high density physical properties such as tracing paper.

Description

FIELD OF THE INVENTION A process for producing transparent high density paper stock pulp from red algae and pulp and transparent high density paper produced thereby.

The present invention relates to a method for producing transparent high density paper stock pulp from red algae, and to pulp and transparent high density paper produced thereby.

Generally, fibers obtained by mechanically or chemically treating a plant raw material are called pulp. In fact, in addition to wood, cotton, hemp, flax, jute, german hemp, manila hemp, cedar, bamboo, straw, esparto, bamboo, bagasse, etc., are used as pulp raw materials. However, the requirements to be provided as industrial raw materials should be abundant in quantity, easy to collect, transport and store, inexpensive and excellent in quality.

Wood, which is a major pulp feed material, is mainly composed of cellulose, hemicellulose, and lignin, and these components constitute the cell wall and the intercellular layer and are present in more than 90% of all species. Subcomponents include resins, essential oils, fats and oils, extracts such as tannins and flavonoids, and other inorganic substances. Among them, cellulose is present in the largest amount of organic compounds present in nature, and is the main component of the plant cell wall. Cellulose is a polymeric material that is insoluble in water, dilute acids and alkalis at room temperature. In order to industrially use wood cellulose, it is used as wood sugar by manufacturing paper through hydrolysis, bleaching, refining, etc., or by hydrolyzing wood, and making and using cellulose derivatives through various chemical treatments. Doing. Various operations are performed from the raw material to the pulp, but it can be largely classified into preparation of pulp raw material, pulping, and purification of pulp.

In the process of processing a wood raw material in the state which is easy to pulp, there are operations, such as cutting, peeling, and sorting, and this is performed suitably according to the kind of raw material. The process of obtaining fibers from the raw material after the preparation process is called a pulping process and is the most important process in pulp production. Fibers can be obtained by destroying the composite intercellular layer of wood, which is a pulp material, with a wood mill or by softening it with water vapor and then breaking it using physical force. The pulp obtained by simple mechanical treatment without chemical treatment is called mechanical pulp. Mechanical pulp has high yield and low production cost, but it is not suitable as a raw material of high grade paper because of high lignin content.

Treatment of the pulp feedstock with ligignin chemicals dissolves the complex intercellular layer and dissociates it into fibrous form. Pulp prepared in this way is called chemical pulp. In the manufacture of chemical pulp, not only the lignin in the intercellular layer of the raw material, but also most of the membrane lignin is removed, and at the same time, many hemicelluloses are dissolved and some cellulose is degraded. Chemical pulp has high quality, i.e., high purity of cellulose, but has a disadvantage of low yield and high production cost compared to mechanical pulp. Chemical pulp production methods include sulfurous acid method, soda method and sulfate method. The selection process is a process of washing and screening fibers obtained from the raw material after the pulping process to remove parts and contaminants that are not completely pulped, and then bleaching as necessary. Specific refinement treatments are performed for those requiring high quality, such as rayon pulp.

The above is the description about the general process of manufacturing pulp from wood raw materials. However, as the depletion of wood resources around the world becomes severe, the task of the industry is to produce paper stock pulp while protecting forests and the environment. As a solution to this problem, a technique for producing paper pulp from non-woody plant fibers mainly on first and second year plants has attracted attention.

Non-woody plants that can be used as a raw material for papermaking include bark, flax, hemp, cotton, manila hemp, rice straw, bagasse and the like. In general, non-woody plants are high in pectin, hemicellulose, minerals, low in lignin, and chemical, semi-chemical, and mechanochemical methods are used when pulping, with very mild conditions compared to wood. Unbleached or bleached pulp can be obtained.

Non-wood pulp has different properties depending on its fiber type, chemical composition, and the type and amount of non-fibrous cells. Therefore, the paper made by non-wood pulp alone or by proper blending with wood pulp can easily control the strength, durability, electrical characteristics, gloss, dimensional stability and printing performance, which can be used for various purposes. Therefore, the use range is also wide. However, the conventional non-wood pulp has to go through a difficult process, and there is a problem that the environment is polluted because toxic chemicals are used even when producing pulp.

Therefore, the present inventors have developed a method for producing paper using red algae as a pulp material, and have seven registered patents as related patents. Recently, a patent for 'how to prepare pulp with a high content of internal gel extract from red algae' has been registered as patent No. 0811194.

However, the patent must be accompanied by the extraction process of the internal gel component of red algae, the manufacturing process is somewhat complicated and the production cost is high, and the transparent high density paper is not satisfactory for physical properties such as thermal extension and opacity, and improvement is required. come.

The present invention is to overcome the inefficient problem in the production process that the paper produced using the conventional red algae as a transparent high-density paper that can be used as a tracing paper, does not have suitable physical properties and must include a gel extraction process as essential And a method for producing a pulp capable of producing transparent high density paper from red algae, a pulp produced thereby, and a transparent high density paper.

The object of the present invention is (a) washing the red algae, (b) ozonating the washed red algae, (c) bleaching the ozone treated red algae with bleach, (d) the bleached red algae It can be achieved by providing a method for producing a transparent high-density paper stock pulp from red algae comprising the step of converting the fiber into fibers. Here, the method for producing a transparent high density paper stock pulp of the present invention may further include a step of curing with a curing agent before step (c), after step (d), before step (c) and after step (d).

In the present invention, the red algae may be any one or more selected from the group consisting of Locust spruce, Dolphin spree, gambling spruce and Noodle sprouts tree, but includes all red algae in which minimal fibers are present.

In the present invention, '(a) washing red algae' is a pretreatment step in which red algae are first washed with water to remove foreign substances such as salt, and then, hydrogen peroxide is treated. In the washing step, the hydrogen peroxide treatment is preferably treated by immersing in a hydrogen peroxide solution at a concentration of 1 to 5% for a sufficient time for 5 minutes or more, and when immersed in a hydrogen peroxide solution at a concentration of 3% '(b) ozone treatment step' In the ozone treatment is maximized the effect is more preferable. This is because when hydrogen peroxide treatment is performed on red algae before the ozone treatment step, the pH of the surface of the red algae is weakly acidic, and the oxidizing effect of the ozone treatment can be maximized.

In the present invention, '(b) ozone treatment of washed red algae' is a process of treating red algae that has undergone the washing step into an ozone reactor, which is most important in the process of the present invention for producing transparent high density paper pulp from red algae. Corresponds to the process. Ozone has a specific gravity about 1.5 times greater than oxygen, condenses into a dark blue liquid at -112 ° C, and has a freezing point of -251.4 ° C. It is known as a strong oxidizing agent and a disinfectant. In order to obtain transparent high-density paper pulp from red algae, the inventors have repeatedly studied that the ozone-treated black-blue color can be bleached close to green or yellow close to white. Such ozone treatment is preferably treated with 1-5% ozone relative to the weight of the red algae dry matter. This is because L ^* , a ^* , b ^* values of the initial red algae measured by the method proposed in the present invention vary depending on the storage and distribution of dried red algae. Red algae that are exposed to sunlight between distributions and occasional rains may be slightly bleached. These red algae are sufficient for a small amount of ozone treatment, while red algae stored in confined spaces require a lot of ozone treatment. Therefore, ozone treatment for red algae generally requires ozone treatment of about 1% of its own weight in the case of highly sunlight-bleached raw materials, and up to 5% ozone treatment is required for red algae that have not received sunlight at all. The chromaticity can be satisfied.

In the present invention, the ozone treatment is “Ozone-treated red algae are dried to have a water content of about 3 to 8% and powdered (40 mesh screen, 150 mesh screen not passed), and then 15 g is collected to obtain a light source of 6500 ^o K. When measured by a colorimeter under the conditions, it is preferable that the L * (brightness index) value is 40 or more, and the b * (yellowness value) is 15 or more '. When treated under such conditions, it is possible to produce a transparent high density paper pulp with excellent physical properties (more than 7.0 km of thermal length, less than 40% opacity).

The present invention may further include a step of curing with a curing agent before step (c), after step (d), before step (c) and after step (d). The curing agent serves to cure the gel component (daikon) present in the red algae, and when the curing agent is treated before the step (c) of bleaching using a bleaching agent, only the surface of the red algae in the bleaching step (c) There is an effect that can be treated to bleach. If the curing agent is treated after the step (d) of converting the bleached red algae into fibers, the dehydration and red paper properties of the red algae fiber may be improved. This is because treatment of red algae fibers with a curing agent causes hydrophilic groups to be bonded to the main body, thereby improving dehydration and shortening the dehydration rate. In other words, if the dehydration speed is high in the process of making paper, the pressing process (pressing the pressure to remove the water) is smooth, thereby reducing the drying energy during drying. In the present invention, the curing agent may preferably use a basic medicine, at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ) and ammonia (NH ₃ ) It is more preferable to use basic chemicals.

In the present invention, the step (b) bleaching the ozone-treated red algae with a bleaching agent is preferably one or more bleaches selected from the group consisting of chlorine dioxide (ClO ₂ ) and hydrogen peroxide (H ₂ O ₂ ). It is preferable to bleach at a temperature of 70 ° C. or lower in order to prevent the red algae (milk) component from melting and forming a sticky surface. If bleached at a temperature of 70 ° C. or higher, as described above, the red algae (milk) component melts and makes the surface sticky, which makes the subsequent papermaking process difficult.

In the present invention, '(d) converting the bleached red algae into fibers' is a step of mechanically cutting red algae that has undergone the bleaching step into a fiber form. This fiberization step is a step of collecting the size of the red algae passes through the 40 mesh screen, the size of the fiber does not pass through the 150 mesh screen.

Through the above steps, transparent high density paper stock pulp can be prepared from red algae. The transparent high density paper pulp prepared as described above may be made of transparent high density paper according to a general papermaking method. When the paper is made using the transparent high-density paper red algae pulp of the present invention, it is possible to produce transparent high-density paper having a thermal length of more than 7.0 km and a transparency of 40% or less.

In the present invention, a method for producing a transparent high density paper pulp from red algae is omitted from the internal gel extraction process, unlike the conventional pulp manufacturing method. According to the present invention, the production process is simplified compared to the existing method, thereby reducing production costs. In addition, it is possible to produce transparent high density paper which is friendly to human body and environment. The transparent high density paper produced in this way can be used as various paper products requiring transparency and high density physical properties such as tracing paper.

1 is a flow chart showing a method for producing a transparent high density paper stock pulp from the red alga of the present invention.

Hereinafter will be described in more detail through embodiments of the present invention. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Example  1. Effect of ozone treatment

In the present invention, when the ozone treatment is not carried out to specifically examine the contents of the ozone treatment technology, which is a key component, when the ozone treatment is performed outside the conditions of the present invention, the case where the ozone treatment is performed within the conditions of the present invention is classified. The experiment was conducted.

Gelidium dried and imported from Morocco for this experiment Corneum red algae species were imported and used as material. The dried red algae was submerged to remove soil and foreign substances and then subjected to ozone treatment. As the ozone treatment method, a sufficiently hydrated red algae was placed in a rotating barrel and ozone gas was injected into the barrel. Specific reaction conditions were adjusted based on the color change of the red algae. The color change of red algae after ozone treatment was measured as follows.

a) Ozone treated red algae was dried in an oven at 105 ° C. for 2 to 3 hours and treated to have a water content of 3 to 10%.

b) The dried red algae was ground with a mixer, filtered through a 150 mesh screen, and approximately 15 g of the sample passing through the 40 mesh screen was taken.

c) After filling the sample evenly in a 9cm diameter petri dish, measure the color with a contact colorimeter. At this time, the white background paper was laid at the bottom of the patissier to make the whole background white.

d) The colorimeter was KONICA MINOLTA CM-600, and the light source measured the values of L * (brightness index), a * (redness) and b * (yellowness) using D65 (Daylight 6500 ^o K).

Table 1 shows chromaticity measurements according to the experimental group of the present invention. Samples 1 to 3 are cases where ozone treatment is not performed, and samples 4 to 6 are cases where ozone treatment is performed. Samples 4, 5 and 6, which are the result of ozonation, have different L * and b * values. Sample 4 has an L * value of less than 40 and a b * value of less than 15. Samples 5 and 6 have an L * value of 40 or more and a b * value of 15 or more.

Chromaticity measurement result Sample number Ozone Treatment L * a * b * Sample 1 X 30.38 3.86 4.46 Sample 2 X 32.82 3.56 5.32 Sample 3 X 35.24 3.52 8.42 Sample 4 O 38.22 3.14 11.79 Sample 5 O 41.05 3.03 17.28 Sample 6 O 43.72 2.88 18.23

Table 2 shows the physical properties of the six types of experimental samples. As can be seen in the table below, the thermal modulus values representing the strength of the paper were 8.13 km and 8.25 km, respectively, in samples 5 and 6, with sample 1 (4.58 km), sample 2 (5.63 km) and sample without ozone treatment. 3 (4.87 km) and ozone treatment, L * value was less than 40, b * value was less than 15 compared to Sample 4 (6.44 km), it was confirmed that the apparently high. In addition, when ozone treatment (L * value is 40 or more and b * value is 15 or more) such as Samples 5 (23.7%) and 6 (28.2%), Sample 1 (45.8) having no ozone treatment %), Sample 2 (43.2%), sample 3 (45.8%) and opacity compared to sample 4 (38.6%) treated with ozone but with an L * value of less than 40 and a b * value of less than 15. Significantly lower, it could be confirmed that it is more preferable to prepare a transparent high-density paper.

Physical property measurement result Basis weight
(g / m ² ) Thermal insulation
(km) Opacity
(%) Sample 1 60.2 4.58 45.8 Sample 2 62.3 5.63 43.2 Sample 3 59.8 4.87 45.8 Sample 4 60.2 6.44 38.6 Sample 5 63.5 8.13 23.7 Sample 6 60.8 8.25 28.2

In conclusion, in the production of high density tracing paper using red algae, ozone treatment is more effective than no ozone treatment, and ozone is treated to have L * value of 40 or more and b * value of 15 or more. It could be confirmed through Example 1 that the effect was even more excellent than otherwise.

Example  2. Effects of Ozone Treatment and Curing Agent Treatment

In the present Example, the effect when the hardening agent process was further added to ozone treatment was examined. The experimental group consisted of six kinds. Sample 1 is a registered patent No. 0811194, which the present inventors have applied for previously, such as 'method of preparing pulp with high content of internal gel extract from red algae', performs a gel extraction process, and an ozone treatment process and a curing agent treatment process Corresponds to the experimental group not conducted. Sample 2 corresponds to an experimental group in which no extraction step, ozone treatment step, and curing agent treatment step were performed. Sample 3 corresponds to an experimental group in which only the ozone treatment step was performed without performing the extraction step and the curing agent treatment step. Samples 4 to 6 correspond to the experimental group that performed the ozone treatment step and the curing agent treatment step (after bleaching, after fiberization, after bleaching and after fiberization).

Specific experimental conditions are as follows. Red algae Gelidium Corneum was used, and the extraction process was carried out in a water bath at 120 ℃ temperature. All samples were subjected to bleaching, primarily with 5% chlorine dioxide and with 5% hydrogen peroxide. The ozone treatment was carried out so that the L * value was 40 or more and the b * value was 15 or more, and the curing agent treatment was performed for 30 minutes at room temperature by adding 1% sodium hydroxide to the dry weight. Fibrosis was passed through a 40 mesh screen followed by shattering of the red algae subjected to bleaching process in a blender, and the fiber formation in the step of collecting the fibers do not pass through a 150 mesh screen to red algae is produced Jiro plants having a basis weight of 60g / m ^2, measured physical properties of the paper Was used for.

The experimental results are shown in Table 3 below.

Effects of Ozone Treatment and Curing Agent Treatment Extraction process Ozone Process L * / b * Hardener
Process Basis weight
(g / m ² ) Thermal insulation
(km) Opacity
(%) Dehydration time
(second) Sample 1 O X 25.5 / 1.3 X 61.8 4.36 73.8 62.3 Sample 2 X X 30.4 / 4.5 X 62.3 5.63 55.2 98.5 Sample 3 X O 41.1 / 17.3 X 61.2 7.07 31.8 43.2 Sample 4 X O 43.7 / 18.2 After bleaching 60.8 7.54 28.6 38.4 Sample 5 X O 42.3 / 17.9 After fibrosis 59.9 8.24 29.7 26.4 Sample 6 X O 42.7 / 18.1 After bleaching
After fibrosis 60.8 8.02 25.2 24.8

As shown in Table 3, when only the extraction process was performed without the ozone process or the curing agent treatment process (sample 1), the thermal shortness indicating the strength of the paper was 4.36 km, and the opacity to confirm the transparency was measured to be 73.8%. It was confirmed that it was not suitable for use as a transparent high density paper than the test group. In addition, it was confirmed that the samples 4 to 6, which performed both the ozone process and the curing agent treatment process, had more suitable physical properties for use as a high-density paper with a high thermal length and opacity than the sample 3 which performed only the ozone process. . According to the results of the process of curing agent treatment, thermal curing was the highest when the curing agent was treated after fiberization, and the opacity was lowest when the curing agent was treated after bleaching and after fiberization. In addition, when the curing agent was treated it was confirmed that the dehydration rate is faster than 40 seconds. This is because the hydrophilic groups present in the red algae fibers are bonded to each other as the curing agent is treated to reduce the total area of the hydrophilic groups exposed to the outside. If the dehydration speed is fast, the drying time is reduced, which can improve the convenience of the papermaking process in the future.

In conclusion, the ozone treatment of the present invention was confirmed that it is more effective in the production of high-quality transparent high-density paper with the curing agent treatment.

Example  3. Transparent according to the present invention With high density paper  Comparison of marketed products

In this embodiment, an experiment was conducted to compare the physical properties of the transparent high density paper produced according to the method of the present invention and the transparent high density paper currently on the market. The experimental group consisted of two types of high density paper (Gelidium elegance; red algae transparent high density paper 1,2, Geledium corneum; red algae transparent high density paper 3) and two types of high density paper (commercial high density paper 1); Strathmore 300 series tracing paper, commercial high density paper 2; diamond tracing paper).

Specific physical property measurements are shown in Table 4 below.

Transparent red algae With high density paper  Commercially transparent High density  compare Basis weight
(g / m ² ) density
(g / cm ³⁾ Thermal insulation
(km) Opacity
(ISO,%) Manufactured from red algae
Transparent high density paper 1 60.2 0.87 7.03 28.2 Manufactured from red algae
Transparent high density paper 2 84.8 0.91 8.38 24.9 Manufactured from red algae
Transparent high density paper 3 94.3 1.11 8.06 25.9 Clear high density paper sold on the market 1 41 0.91 MD: 6.81
CD: 3.84
(MD × CD) ^1/2 = 5.11 36.5 Commercially available transparent high density paper 2 90 1.13 MD: 6.57
CD: 3.84
(MD × CD) ^1/2 = 4.27 31.7

The transparent high density paper made of red algae was produced in a laboratory and has no orientation, but the transparent high density paper sold on the market has a direction. In Table 4, MD refers to the machine direction, CD refers to the machine vertical direction. In order to compare the thermal shortening of the transparent high density paper made of red algae with the commercially available transparent high density paper, the thermal shortening of the commercially available transparent high density paper (MD × CD) ^1/2 was calculated and compared with each other.

As a result, it was confirmed that the transparent high-density paper made of red algae according to the present invention has excellent physical properties, as compared with the transparent high-density paper currently on the market, having high thermal shortness and low opacity.

Claims (13)

A method for preparing transparent high density paper stock pulp from red algae comprising the following steps:
(a) washing red algae;
(b) ozonating the washed red algae;
(c) bleaching the ozone treated red algae with bleach;
(d) converting the bleached red algae into fibers.
The method of claim 1, wherein the red algae is any one or more selected from the group consisting of Locust spruce, Locust spruce, Gambling and Noodle sprouts.
According to claim 1, wherein the step (a) is pulp production method characterized in that the washing using hydrogen peroxide.
The method of claim 3, wherein the hydrogen peroxide is treated at a concentration of 1 to 5%.
The method of claim 1, wherein the step (b) is a pulp manufacturing method, characterized in that the red algae is treated with 1 ~ 5% ozone to the total weight.
The method of claim 1, wherein step (b) is performed to satisfy the following chromaticity measurement results.

The ozone-treated red algae are dried to a water content of about 3 to 8%, powdered to a size that cannot pass through a 40 mesh screen and a 150 mesh screen, and 15g is collected to obtain chromaticity under a light source condition of 6500 ^o K. Chromaticity measurement results with L * (brightness index) of 40 or more and b * (yellowness) of 15 or more
The method of claim 1, further comprising the step of curing with a curing agent before step (c), after step (d), before step (c) and after step (d).
7. The method of claim 6, wherein the curing agent is a basic drug.
8. The pulp preparation according to claim 7, wherein the basic medicine is at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ) and ammonia (NH ₃ ). Way.
The method of claim 1, wherein the bleaching agent of step (c) is any one or more selected from the group consisting of chlorine dioxide (ClO ₂ ), hydrogen peroxide (H ₂ O ₂ ).
The method of claim 1, wherein the bleach of step (c) is a pulp manufacturing method, characterized in that the treatment at a temperature of 70 ℃ or less.
A transparent high density paper stock red algae pulp produced by the method of any one of claims 1 to 11.
A transparent high density paper produced from the pulp of claim 11 as a raw material.

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