JPH0248573B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial application field: Mix vinegar with papermaking cellulose-based waste resources, mainly wood fibers, which exist in large quantities in Japan, such as papermaking resources, papermaking waste, paper, natural wood fragments, and other wood fibers, and filter the resulting mixture. The present invention relates to a thermosetting liquid-viscous composition obtained by stirring conventional plastic raw materials and plastic materials with a liquid and separating the resulting modified product consisting of three phases. Prior Art Previous attempts have been made to utilize paper manufacturing waste, wood chips, and other cellulose-based paper manufacturing wastes, but in all cases, the fibers themselves have been used and have been pulverized or made into plate-like materials. However, no attempt has been made to modify and utilize the fibers. Problems to be Solved by the Invention Therefore, the conventional use of these cellulose-based waste resources has its limits, and it has been desired to find a method for effectively using or utilizing them. Means for Solving the Problems In order to solve the above-mentioned problems, the present invention has been developed as a result of intensive research, in which cellulose-based waste resources are treated together with vinegar and plastic raw materials or plastic materials, and the resulting precipitated phase is useful. The present invention was achieved by obtaining new knowledge that it is a modified product. That is, the present invention provides paper manufacturing resources, paper manufacturing waste, paper,
Mix natural wood chips, other wood fibers, and vinegar solution.
The mixture is stirred and left to stand with the bacteria in a temperature range where the bacteria can be active, then the mixture is filtered, and the filtrate and the plastic raw material or plastic material are mixed and stirred at a temperature range where the bacteria can be active, stirred, and allowed to stand. A third phase liquid-viscous substance separated from a three-phase encapsulated modified product of a liquid phase as the first phase, an ion-exchange semipermeable membrane liquid-viscous phase as the second phase, and a liquid-viscous phase as the third phase, obtained by Cellulose,
The present invention relates to a thermosetting liquid-viscous composition containing an enzyme, a metal salt, a plastic-modified polycondensate, and a vinegar component as main components. Other wood fibers used in the present invention, such as papermaking resources and papermaking waste, include, for example, the following. (b) And colored wrapping paper, cement paper (hereinafter referred to as p1), (b) Newspaper, cardboard (hereinafter referred to as p2), (c) Low-grade and high-grade printing paper, gravure paper (hereinafter referred to as p3), (ni) ) Wood fiber (hereinafter referred to as p4) The composition contained in p1, p2, p3, and p4 is mainly composed of organic substances such as α-cellulose, β-cellulose, hemicellulose, lignin, extracts, and ink, and inorganic substances such as S, P, and Si. , -AlO ₃ , Cl, and other metals, which also include the residues of substances used during the papermaking process, and are mainly composed of original wood parts, bone marrow parts, and papermaking residues. In addition, the fungi present here that work to loosen the fibers in the vinegar solution of the present invention to cellulose and form the modified products of the present invention, which are included in the extract, are the secondary fungi contained in petroleum. It is similar to bacterial components in petroleum products, and they are shown in Table 1.

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[Table] Among the representative fungi of the genus Bacillus and Candida that are included in the methanation resources of petroleum raw materials, the fungi that were specifically confirmed using a microscope are Japanese yeast (shown in Figure 2a), which is used in the petroleum industry. Candida Arborea (substrate n-paraffin) (Fig. 2b), which is the same as that used for methane fermentation, Bacillus amylobacter that promotes methane fermentation, Cellulose methanicus (Fig. 2c), and Bacillus that plays a major role in the bacterial semipermeable membrane described below. - Bacillus-Comessi (2nd d.
(Figure), this is a bacterium that creates a thin layer that suppresses Bacillus-Amylobacter.
(Fig. 2e), Bacillus Metanicus (Fig. 2f),
Bacillus amylobacter promotes the decomposition of pectin, and Bacillus mesentericus completely decomposes pectin (94% to 96%).
mesentricus-pectnovus) (Fig. 2g). Enzymes derived from the bacterial cells used in the present invention are also present in the filtrate, and these enzymes are classified according to their functions and their actions are shown in Table 2. In addition to those listed in Table 2, the presence of several enzymes whose effects have not been elucidated (Figure 3a) and (Figure 3b) was confirmed.

[Table] Examples of the plastic raw materials or plastic materials used in the present invention include the following. HCl, CH ₂ = CHCl, C ₂ H ₂ , CH ₃ CHO,
CH ₃ COOH, C ₂ H ₄ , HOCH ₂ −CH ₂ OH,
_C6H5OH , HCHO, _furfural , isocyanate, melamine, epoxy compound, acrylic compound, H3C- _-CH3 , HOOC- _-COOH ,
Reaction intermediate products in the plastic manufacturing process such as NH ₃ CO (NH), HOOC (CH ₂ ) COOH, thermosetting plastics such as urethane resin, melamine resin, polyester resin, silicone resin, acrylic resin, polymethyl methacrylate resin, ABS resin,
Thermoplastics such as preethylene resin, polypropylene resin, and nylon. The thermosetting liquid-viscous composition of the modified fiber and plastic of the present invention is produced as follows. First, wood fibers such as waste cellulose are mixed in vinegar at a weight ratio of 1:50 or less, stirred, left to stand together with the waste cellulose and bacteria present in the vinegar, and then filtered to form a plastic attack agent. Obtain the filtrate. During this reaction, especially when left standing, the temperature may be in any range as long as the bacteria can be active, but it is generally below 100℃, especially between room temperature and 60℃.
It is preferable to carry out the mixing for a period of at least 3 hours or more, and the mixing time may be until the mixture becomes pulp-like (porridge-like). After allowing this to stand for a while, it is filtered to obtain a filtrate. Adding plastic raw materials (monomers, reaction intermediate products, etc.) and plastic materials to the filtrate, which will be described later,
When stirred and fermented for several hours or more, a liquid substance separated into three phases is obtained (Figure 1b). The temperature during this stirring and brewing is the same as in the above case. The three phases are, in order from the top, a liquid first phase (a), a second phase (b) that is a semipermeable membrane-like liquid viscous substance having ion exchange properties, and a third phase (a thermosetting liquid viscous phase). c). In addition, Figure 1a is a diagram showing the potential potential of the encapsulated modified product from the three phases, which was measured by the method described below. The vertical axis Y is the potential potential, and It represents the depth dimension from the bottom to the bottom, and shows each phase state band of three-phase separation. N ₁ (-a-) indicates the degree of negativity of the first phase, (-
b-) represents the ion dissolution phenomenon of the second phase, N ₂
(-c-) indicates the degree of negativity of the third phase. p shows an instantaneous positive value because a large amount of protons (H ⁺ ) are transiently released from the third phase to the first phase.
Phase and 3rd phase show stable negativity. Second phase (-
It can be seen that b-) shows an unstable potential potential due to the movement of protons. The measurement method shown in Figure 1a is to prepare three thermocouple (nickel silver-Cu) sensors with Teflon covers.
One wire was fixed in the third phase and the other wire was placed in the second phase, and measurements were taken with a galvanometer (μA order) while using a potentiometer to prevent the dipole phenomenon of the electrodes from spreading. The third electrode in the pair is a trend characteristic measured by inserting a changeover switch halfway into the first phase. The modified products of the first, second and third phases (Fig. 1b) will be described below. Liquid-viscous phase (3rd phase) The filtrate made from vinegar and cellulose is mixed with plastic raw materials or plastic materials, stirred, and left to stand still. It is a sediment-brewing method. The reaction product with the filtrate, which is the third phase, is estimated to be as follows. 1 Modified Phenol Resin As is known, when formalin acts on phenol, methylolization occurs at the ortho and para positions of the phenol, which undergoes polycondensation and releases water to produce a polymeric substance. Since formalin and glyconic acid are contained in the aldehydes in the filtrate, it is thought that the phenol modified product is not a novolac type but a novolac chain polymer type. Note that the filtrate contains enzymes, cellulose, hemicellulose, lignin, and other components. Therefore, it is thought that the actual reaction will be even more complicated. The resulting modified product has a viscosity of 25 sec/25°C [Food Cup (FC: #4)], a specific gravity of 1.05 to 1.25, and a pH of 3.7.
It has a reddish-brown color, and has better acid resistance and heat resistance than novolac type phenol, and has very good adhesion (to metals, etc.). 2 Modified urethane resin Based on cellulose from papermaking resources, it is thought that due to the presence of a large amount of cellulose-based nitrogen in the filtrate, amide bonds are formed, deformed, and further esterified to form a polycondensate with amide. It will be done. This modified product has a viscosity of 30~40sec/25℃ (FC: #4) and a specific gravity of 0.9~
1.02, pH 2.8-3.5, pale yellow-pink color. As mentioned above, the filtrate contains enzymes, cellulose, hemicellulose, lignin, metal salts,
Since components such as vinegar are present and complex, their reactions are thought to be wide-ranging. For example, when a three-phase slime phase is molded, each of the miscible plastics is transformed into a unique, unprecedented plastic that has both two-dimensional bonding and three-dimensional bonding properties. This fact is confirmed by physicochemical properties and microscopic cross-sectional examination. Ion-exchange semipermeable membrane mucus phase (second phase) The ion-exchange semipermeable membrane mucus phase (second phase) refers to a liquid-viscous phase that is formed on top of the liquid-viscous phase (third phase). Bacteria (Bacillus cometsii, Acetobacter,
yeast bacteria, butanol bacteria), metal salts based on paper resources,
Refers to areas where chitin, cellulose, etc. are densely packed. The second phase acts as a semipermeable membrane for protons (H ⁺ ). Figure 1b is an external state diagram, Figure 1c is a microscopic photograph of the contact surface between the third liquid viscous phase and the second phase, and Figure 1d is the contact surface between the first liquid phase and the second phase. This is a microscopic photograph of the condition. Then, a vinyl compound is generated from the liquid-viscous phase of the third phase by the metal and the enzyme, and this is carried into the liquid phase of the first phase (Fig. 1e). Figure 1e shows the first phase and the second phase.
This is a microscopic photograph of the reaction state obtained by taking out the phase and third phase components and simulating them on a slide. It is observed that substances are released from the inside of the third phase, which has a high concentration, through the membrane (second phase), and through the pores, to the outside, where the concentration is low. Figure 1b shows that after mixing and stirring the filtrate and the plastic raw material and allowing it to stand still, it is dominated by the ion-exchange semipermeable membrane mucus phase (second phase), with a third phase at the bottom and a second phase at the middle.
It is a drawing showing a state divided into three phases consisting of an upper first phase, where a is the first phase, b is the second phase, and c is the third phase. Then, by molding the second phase, a molded article having semiconducting properties is obtained. Liquid Phase (First Phase) The first phase is a liquid phase, and is basically a liquid containing a large amount of enzyme and protons (H ⁺ ). acetic acid, water produced by a portion of the vinyl compound passing through, and other enzyme solutions such as formaldehyde,
Contains ethyl alcohol, methanol, etc. These are also released into the air as gases. Additionally, it contains large amounts of enzymes, cellulose, and bacterial cells. Therefore, the liquid has an optical rotation similar to that of a protein (left optical rotation of 10° to 12°), is an electrolytic solution, and is a high-energy liquid having an ultrasonic vibration frequency of 10 MH to 27 MH. The above-mentioned properties can be provided to many industries as a rust remover with peeling properties and as a metal surface treatment agent. Examples Production examples of the present invention are shown below. Manufacturing Example 1 Waste paper crushed into 3000 kg of vinegar (and 20 pieces of colored wrapping paper)
weight%, newspaper 50% by weight, high-grade printing paper 30% by weight)
7 kg was added and the mixture was stirred for 3 hours to obtain a pulp-like (porridge-like) product. The gruel is heated to about 40℃
It was left to rest for 3 days. It was confirmed that bacteria present in the waste paper, mainly Bacillus amylobacter, Bacillus ferucineus, Bacillus metanicus, Bacillus mesentericus, and acetic acid bacteria remaining in the vinegar, were present in the gruel.
This brewed gruel is squeezed to obtain a filtrate. The filtrate was aged again for 3 days at about 40°C. Ethylene glycol, a raw material for urethane (Dainippon Ink Co., Ltd. D-290-70-Burnock 1 liquid, hydroxyl value 204,
Add OH% 6.2 NC equivalent 15.3) and stir for 3 hours.
After aging for a day, a modified plastic product separated into three phases is obtained. Only the third phase of this modification is separated. This product contains cellulose, dissolved chitin, lignin, modified urethane in which ethylene glycol and cyanates derived from waste paper are combined, enzymes, metal salts, and vinegar components as main components, and has a viscosity of 30 seconds/25℃.
(FC: #4), specific gravity 2.0, pH 3.5, pale yellow to reddish pink liquid and mucus. This substance has the property of being able to be bonded two-dimensionally and three-dimensionally, and can be used as a paint or adhesive.Also, this slimy substance can be thermally cured into a solid state to be used as a screen, wavelength cut screen, etc.
It can be used as an optical material such as a polarizing plate,
Furthermore, it has the excellent property that it can be made into a fiber that does not carry static electricity at all. The first phase is an electrolytic liquid containing vinegar components, cellulose, enzymes, bacterial cells, formaldehyde, vinyl compounds, alcohols, and water as main components, and the second phase contains cellulose, enzymes, and water. It was a semipermeable liquid slime with high viscosity and ion exchange properties, containing bacterial cells, metal salts, and chitinous substances as main components. Production Examples 2 to 9 Modified products were obtained in the same manner as in Example 1 except that the plastic raw materials or plastic materials shown in Table 3 below were added. Table 3 shows the properties and uses of the obtained modified product.

[Table] Phase 3 Industrial use of liquid-viscous phase There are various types ranging from liquid-viscous to heat-cured solid phase. In view of these characteristics, the scope of industrial use is extremely wide-ranging. For example, Figure 4 shows a cross section of iron (Fe) coated with a liquid viscous phase as a paint. Figure 5 uses liquid-viscous phase as adhesive.
This is a microscopic photograph of a cross section of Fe and Fe bonded together. The properties of the liquid-viscous phase they exhibit indicate the influence of stress and strain due to the difference in expansion coefficients, which is a drawback of conventional paints and adhesives, or the effects of stress and strain on the bonding of adherends. The difficulty in the case of different expansion coefficients was resolved, and the results shown in Tables 4 and 6 were obtained. The liquid-viscous phase can be hardened into a solid, and is mainly used as an optical material, which is molded into screens, wavelength cut screens, and polarizing plates. Figure 6 is a microscopic photograph of a liquid-viscous phase processed into fibers.Fibers with no static electricity were created, which would bring about a major revolution in the textile industry. As shown in the various test data results and Tables 3, 4, 5, 6, and 7 above, the major feature of this product is that it can be used in a wide range of industrial applications.
This is an invention of a modified product that utilizes natural waste resources and natural resources to modify plastic raw materials and plastic materials and uses them as base materials for all industrial fields.

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[Table] Effects of the Invention The present invention is produced by treating paper resources, paper waste resources, paper, natural wood fragments, and other wood fibers with bacteria in vinegar, and adding and reacting plastic raw materials or plastic materials to the filtrate. This modified product consists of three different components, and the third phase, a thermosetting composition, is used as paints, adhesives, and when solidified, it can be used as screens, polarizing plates, etc. It can be said that this invention is an extremely excellent invention for utilizing cellulose waste.

[Brief explanation of drawings]

FIG. 1 (FIG. 1a and FIG. 1b) is a drawing showing the properties and state of a modified three-phase encapsulated plastic. FIG. 1a shows the potential potentials of phase 1 to phase 3 encapsulated plastic modifications. X...Each phase state band of three-phase separation, Y...Potential potential, O...Potential potential zero, a
...First phase, liquid phase, b...Second phase, ion exchange semipermeable membrane phase (bacteria zone), c...Third phase, liquid-viscous phase,
N ₁ ... 1st phase, liquid phase potential, N ₂ ...
Third phase, liquid-viscous phase potential potential, p... Potential potential due to the movement of protons from the third phase to the first phase. FIG. 1b is a three-phase inclusive external state diagram. Figure 2 is a microscopic photograph of fungi, Figure 2a is Japanese yeast, and Figure 2b is candida-Arbonea (n-
paraffin), Figure 2c is Bacillus-Amylobacter,
Cellulose-metanics, Figure 2d is Bacillus-
Comessi, Fig. 2e is Bacillus-Felsineus, Fig. 2
Figure f is Bacillus-metanics, Figure 2g is
It is a micrograph of Bacillus-mesentricus-pectnovus. Figure 3 is a microscopic photograph of the enzyme contained;
Figures 3a and 3b are enzymes whose actions are unknown,
Figure 3c is glycolate oxidase, Figure 3d
Figure 3e shows catalase, Figure 3e shows trans-ketolase, Figure 3f shows trans-amylase, Figure 3g shows alpha-amylase, Figure 3h shows beta-amylase,
Figure i is peptinase, Figure 3j is lysozyme, Figure 3k is triphosphate isomerase, Figure 3 is
Figure l is a microscopic image of hydrase. Figure 4 is a micrograph of the contact surface between the upper paint and metal (Fe). Figure 5 is a microscopic photograph of the contact surface between metal (Fe+Fe) and adhesive. FIG. 6 is a microscopic photograph of the third phase liquid-viscous phase processed into fibers.

Claims (1)

[Claims] 1. Mix paper resources, paper manufacturing waste, paper, natural wood fragments, and other wood fibers with vinegar solution, stir, and let stand at a temperature range where bacteria can be active together with bacteria present in the raw materials. Then, filter the mixture. The first phase is a liquid phase, and the second phase is an ion-exchange semipermeable membrane liquid, which is obtained by mixing the filtrate and plastic raw material or plastic material at a temperature range where bacteria can be active, stirring, cultivating, and standing still. A third-phase liquid-viscous substance separated from a three-phase encapsulated modified product of the viscous phase and the third phase, the liquid-viscous phase, comprising cellulose, cellulose,
A thermosetting liquid-viscous composition containing an enzyme, a metal salt, a plastic modified polycondensate, and a vinegar component as main components.