JPH01165388A - Modified plastic by wood fiber, paper manufacturing resource, waste paper resource and edible vinegar - Google Patents

Abstract

PURPOSE:To obtain a modified plastic, utilizable as a coating, adhesive, and screen, polarizing plate, etc., by solidification, by treating a cellulosic waste with edible vinegar or plastic raw material or plastic material. CONSTITUTION:A paper manufacturing cellulosic waste, such as paper manufacturing waste or crushed wood pieces, is mixed and stirred in an edible vinegar at 1:<=50 weight ratio and then allowed to stand with microorganisms present in the mixture at a temperature range where the microorganisms are active to convert the mixture into a pulpy substance, which is then filtered. A plastic raw material or plastic material is added to the resultant filtrate, mixed and stirred with the microorganisms present in the mixture at a temperature within the range where the microorganisms are active, brewed and then allowed to stand to afford a liquid substance divided into three phases of the first liquid phase, second semipermeable membranous liquid viscous phase having ion exchange properties and third thermosetting liquid viscous phase. The third phase is then separated and collected therefrom.

Description

[Detailed Description of the Invention] Industrial Application Field Paper manufacturing cellulose-based waste resources mainly made of wood fibers that exist in many areas in Japan, i.e., paper manufacturing resources, paper manufacturing waste, paper, natural wood fragments, and other wood fibers The present invention relates to a thermosetting liquid-viscous composition obtained by mixing the filtrate with vinegar, stirring conventional plastic raw materials and plastic materials with the filtrate, and separating the resulting modified product consisting of three phases.

Previous attempts have been made to use paper manufacturing waste, wood chips, and other paper manufacturing cellulose-based waste, but in both cases, the fibers themselves have been used and either powdered or made into plate-like materials. However, there have been no attempts 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 own limitations, and it has been desired to find an effective method for their use.

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention has been made as a result of intensive research, and has been developed by treating cellulose-based waste resources 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 involves mixing papermaking resources, papermaking waste, paper, natural wood fragments, and other main fibers with a vinegar solution, stirring the mixture, allowing it to stand with bacteria in a temperature range where the bacteria can be active, and then filtering the mixture. The first phase is a liquid phase, and the second phase is an ion-exchange semipermeable membrane, which is obtained by mixing the filtrate and plastic raw materials or plastic materials at a temperature range where bacteria can be active, stirring, brewing, and leaving to stand. A third-phase liquid-viscous substance separated from a liquid-viscous phase and a three-phase encapsulated modified product of the liquid-viscous phase, which is a third phase, and contains cellulin, enzymes,
The present invention relates to a thermosetting liquid-viscous composition containing 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.

(a) Brown wrapping paper, cement paper (hereinafter referred to as p1)
, (b) Newspaper, cardboard (hereinafter referred to as p2), (c) low-grade, high-grade printing paper, gravure paper (hereinafter referred to as p3), (d) Wood fiber (hereinafter referred to as p4) pl, p2, P3, p4 The composition contained mainly in organic matter is α-cellulose, β-cellulose, hemicellulose,
S, P, S as inorganic substances such as lignin, extracts, ink, etc.
i, -AIO,, C1, and other metals, which also include the residues of substances used during the papermaking process, and are mainly composed of original wood parts, 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.

Table 1: Bacterial cells from secondary petroleum products and representative fungi included in the methanation resources of these petroleum raw materials Of the Bacillus and Candida genera, the fungi that were specifically confirmed using a microscope were Japanese yeast (No. 2).
(shown in Figure a), the same Ca used in the petroleum industry.
ndida Arbarea (substrate n-paraf
fin) (Fig. 2b), Bacillus amylobata, which promotes methane fermentation, cellulose metanicus (Fig. 2c), and Bacillus comessi (Fig. 2), which plays a major role in the bacterial semipermeable membrane described below.
(Fig. d), this completely releases the fiber bundles, which are bacteria that create a thin layer that suppresses Bacillus amylobata.
Bacillus-Felsineus
s) (Figure 2e), Bacillus metanicus (Figure 2f)
, Bacillus amylobata, which promotes the decomposition of pectic substances, and Bacillus lus-me centericus, which completely decomposes pectic substances (94% to 96%).
sentricus-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. Second
In addition to those listed in the table, the effects are unknown (Figure 3a).
The presence of several enzymes according to Figure 3b) was confirmed.

Table 2 Examples of plastic raw materials or plastic materials used in the present invention include the following.

HCI, CH, = CHCl, C, H,, CH, CHO.

CH, COOH, C2H4, HOCH, -CH, OH.

C, H, OH, HCHO, furfural, isocyanate, melamine, epoxy compound, acrylic compound, H,
C--CH,.

HOOC--COOH, NH, Co(NH).

HOOC(CH2)COOH, etc., reaction intermediate products in the manufacturing process of plastics, urethane resins, melamine resins,
thermos such as polyester resin, silicone resin, etc.
etting plastics.

Acrylic resin, polymethyl methacrylate resin, ABS
resin, polyethylene resin, polypropylene resin, thermoplastics such as nylon, etc.

The thermosetting liquid-viscous composition, which is a fiber and plastic modified product 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 standing still, the temperature may be in any range as long as the bacteria can be active, but it is generally preferred to carry out the reaction at a temperature of 100°C or lower, particularly room temperature to 60°C or lower, and the mixing time is set to a temperature that does not exceed the mixing time. This may be carried out until the mixture becomes pulp-like (porridge-like), but it is generally carried out for 3 hours or more. After allowing this to stand for a while, it is filtered to obtain a filtrate.

Plastic raw materials (monomers, reaction intermediate products, etc.) and plastic materials, which will be described later, are added to the filtrate.

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, there are a liquid first phase (a), a second phase (b) which is a semipermeable membrane-like liquid saccharide having ion exchange properties, and a third phase (c) which is a thermosetting liquid viscous phase.

In addition, Figure 1a is a diagram showing the potential potential of a clasp-modified product consisting of three phases, which was measured by the method described later. The vertical axis Y is the potential potential, or It represents the depth dimension from below to the bottom, and shows each phase state band of three-phase separation. N, (-a-) indicates the negative dust in the first phase, (-b-) indicates the ion dissolution phenomenon in the second phase, and N, (-〇-) indicates the negative dust in the third phase. show. Since a large amount of protons (H+) are transiently released from the third phase to the first phase, p shows an instantaneous positive value, and the first and third phases show stable negative values. It can be seen that the second phase (-b-) exhibits an unstable electric 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 with a third
One wire was fixed in the second phase, and the other wire was placed in the second phase, and measurement was performed with a galvanometer (μA order) while using a potentiometer to prevent the dipole phenomenon of the electrode from spreading. The electrode of the third main port of the pair is a trend characteristic measured by inserting a changeover switch in the middle of the first phase.

Below are the modified products of the 1st phase, 2nd phase and 3rd phase (Figure 1b)
Let's talk about.

■, 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. ).

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 phenol, which undergoes polycondensation and releases water to produce a polymeric substance.

Since formalin and gluconic acid are contained in the aldehydes in the filtrate, it is thought that novolak-type phenol-modified products are produced, rather than novolak-type chain polymers. The filtrate contains enzymes, cellulose, and hemicellulose.

Contains lignin and other components. Therefore, the actual reaction is likely to be even more complex.

The resulting modified product has a viscosity of 25 sec/25°C [Ford cup (FC: #4)], a specific gravity of 1.05 to 1.25, and a p
H3°7, reddish brown in color, and has better acid resistance and heat resistance than novolac type phenol, and has very good adhesion (to metals, etc.).

2. Urethane resin modified product Based on cellulose from papermaking resources, due to the presence of a large amount of cellulose nitrogen in the filtrate, amide bonds are formed, deformed, and further esterified, producing polycondensates with amide. Conceivable. This modified product has a viscosity of 3O-40sec/25
°C (FC: #4), specific gravity 0.9-1.02, pH 2,
8-3.5, pale yellow pink color.

As mentioned above, the filtrate contains components such as enzymes, cellulose, hemicellulose, lignin, metal salts, and vinegar components, and is complex, so it is thought that the reactions thereof are wide-ranging.

For example, when a three-phase slime phase is molded, each of the mixed plastics is transformed into an unprecedented special plastic that has both two-dimensional bonding and three-dimensional bonding properties. This fact is confirmed by physicochemical properties and microscopic cross-sectional examination.

(2) Ion-exchange semipermeable membrane mucus phase (second phase) The ion-exchange semipermeable membrane mucus phase (second phase) refers to the liquid-viscous phase that develops above the liquid-viscous phase (third phase).

Bacteria (Bacillus comessi, Acetobacter, Yeast,
Butanol bacteria), metal salts based on paper resources, chitin, cellulose, etc. are densely concentrated.

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 state of contact between the third phase liquid-viscous phase and the second phase, and Figure 1d is the first phase.
It is a micrograph of the contact surface state of a phase liquid phase and a 2nd phase.

Then, a vinyl compound is generated from the liquid-viscous phase of the third phase by metals and enzymes, and this is carried into the liquid phase of the first phase (the first
Figure e). FIG. 1e is a microscopic photograph of the reaction state obtained by taking out the first, second, 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 basically consists of enzymes and protons (H
It is a liquid containing a large amount of +).

The acetic acid, water produced by a portion of the vinyl compound passing through, and the enzyme solution mentioned above also contain formaldehyde, ethyl alcohol, methanol, and the like.

These are also released into the air as gases.

In addition, it contains large amounts of enzymes, cellulose, and bacterial cells.
Therefore, the liquid has an optical rotation close to that of protein (left optical rotation of 10° to 1
2°), is an electrolytic solution, and has an ultrasonic vibration of 10MH~2
It is a high energy liquid with a vibration frequency of 7MH.

The above-mentioned properties can be provided to many industries as a rust remover with peeling properties and as a metal surface treatment agent.

Example Production examples of the present invention are shown below.

Production Example 1 Waste paper (brown wrapping paper 20 kg) crushed into 3000 kg of vinegar
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 substance (porridge-like substance). The gruel was heated at about 40°C for 3
I let it rest for a day. It was confirmed that bacteria present in the waste paper, mainly Bacillus amylobacter, Bacillus ferucineus, Bacillus metanicus, Bacillus mecenterix 1, and acetic acid bacteria remaining in the vinegar were present in the gruel. This brewed gruel is squeezed to obtain a filtrate. The filter tube was aged again for 3 days at about 40°C. Ethylene glycol (Dainippon Ink Co., Ltd. D-290-7
0-Burnock 1 liquid, hydroxyl value 204.0H%6
．． 2NC equivalent (15.3) was added, stirred for 3 hours, and then allowed to stand for 3 days to obtain a plastic modified product separated into 3 phases.

Only the third phase of this modification is separated. This product is a modified urethane that combines cellulose, dissolved chitin, lignin, ethylene glycol, and cyanates derived from waste paper.
Contains enzymes, metal salts and vinegar components as main components, viscosity 30sec/25°C (FC: #4), specific gravity 2.0.
The pH was 3.5, and the liquid was pale yellow to reddish pink. This product has the property of being able to be combined in two and three dimensions, and can be used as a paint,
It can be used as an adhesive, and the solid material obtained by thermosetting this slime can be used as an optical material for screens, wavelength cut screens, polarizing plates, etc. It can also be used as a fiber that does not carry any static electricity. It has an excellent property of being able to

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 pancreatic juice filler containing bacterial cells, metal salts, and chitinous substances as main components, and had high viscosity and ion exchange properties.

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 3 FC: Fort Cup No. 3 There are various types ranging from those in a codified state to those in a heat-cured solid state. In view of these characteristics, the scope of industrial use is extremely wide-ranging. For example, FIG. 4 shows a cross section of iron (Fe) coated with a compound phase as a paint. Figure 5 is a micrograph of a cross-section of Fe and Fe bonded using a compound phase as an adhesive.The properties of the compound phase shown in these images show stress due to the difference in expansion coefficient, which is a drawback of conventional paints and adhesives. Difficulties caused by the influence of strain or when the expansion coefficients of adherends differ were resolved, and the results shown in Tables 4 and 6 were obtained. The compound phase can be cured into a solid, and is mainly used as an optical material, which can be molded into screens, wavelength cut screens, and polarizing plates. Figure 6 is a microscopic photograph of the composite phase processed into fibers.
A major revolution in the textile industry. As shown in Tables 3 and 4.5.6.7 of the various test data above, a major feature is that the scope of industrial use is wide-ranging. This is an invention of a modified material that can be used as a base material for all industrial fields by modifying a material.

Table 4: Organic reagent dissolution test of compound phase (third phase) film moldings (baked at 300°C) Table ■ = insoluble, S = soluble, ps = partially soluble
The present invention is a plastic modified product obtained 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 substances, and the third phase separated from it, the thermosetting composition, is used as a paint.

It can be used as an adhesive or assimilated into screens, polarizing plates, etc., and can be said to be an extremely excellent invention for utilizing cellulose waste.

[Brief explanation of the drawing]

FIG. 1 (FIG. 1a to FIG. 1e) is a drawing and a micrograph showing the properties and state of a modified three-phase plastic. FIG. 1a shows the electrical potential of the modified plastic containing the first to third phases. X: Each phase state band of three-phase separation Y: 11! Potential Q: Zero potential potential a: 1st phase, liquid phase b = 2nd phase, for ion exchange semipermeable membrane (bacteria zone) C: 3rd phase, compound phase N1: 1st phase, liquid phase potential potential N2: Third phase, compound phase Potential potential p: Potential potential due to the movement of protons from the third phase to the first phase Figure 1b is a three-phase inclusive external state diagram. FIG. 1c is a microscopic photograph showing the state of the contact surface between the second phase ion exchange semipermeable membrane and the third phase liquid-viscous phase. FIG. 1d is a microscope photograph showing the state of the contact surface between the second phase ion exchange semipermeable membrane and the first phase liquid phase. FIG. 1e is a photomicrograph of a bounding cliff of an ion exchange semipermeable membrane. Figure 2 is a micrograph of fungi, Figure 2a is Japanese yeast, and Figure 2b is candida-Arb. nea (n-paraf fin), Figure 2C is Bacillus amylobata, Cellulose Metanicus, Figure 2D
Figure shows Bacillus-Comessi, Figure 2e shows Bacillus-Felsineus, 2nd f1g
is Bacillus-Metanicus, and Figure 2g is Bacillus.
llus −+1 esentricus −pectn
It is a micrograph of ovus. Figure 3 is a microscopic photograph of the enzymes contained, Figure 30 and Figure 3b are enzymes whose actions have not been elucidated, Figure 3c is brecolate oxidase, Figure 3d is catalase, Figure 3e is trans-ketolase, Figure 3f shows trans-amylase, Figure 3g shows α-amylase, Figure 3h shows β-amylase, Figure 31 shows peptinase, Figure 3j shows helizozyme,
The third figure shows triphosphate isomerase, and Figure 31 shows four microscopes of hydrase. FIG. 4 is a microscopic photograph of the contact surface between the upper paint and gold scraps (Fe).・Figure 5 is a four-microscope photograph of the interface between gold Jσζ (Fe+Fe) and adhesive. Figure 6 is a microscopic photograph of the delicately processed third phase liquid-viscous phase.

Claims (1)

[Claims] Paper manufacturing resources, paper manufacturing waste, paper, natural wood fragments, and other wood fibers are mixed with a vinegar solution, stirred, and left to stand at a temperature range where the bacteria can be active together with the bacteria present in the raw materials.Then, the mixture is filtered, The filtrate and plastic raw material or plastic material are mixed, stirred, and allowed to stand in a temperature range where bacteria can be active, resulting in a liquid phase as the first phase and an ion exchange semipermeable membrane liquid viscosity as the second phase A third-phase liquid-viscous substance separated from the three-phase encapsulated modified product of the liquid-viscous phase and the third phase, which contains cellulin, enzymes, metal salts, plastic-modified polycondensates, and vinegar components as main components. A thermosetting liquid-viscous composition containing.