JP2528096B2 - Modified solids of fibers and plastics - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel fiber-plastic modified solid material, and more particularly to a useful heat-resistant and acid-resistant solid material obtained by aging the fiber-modified plastic material.

Prior Art The inventors of the present invention first mixed paper cellulose-based waste resources, that is, papermaking resources, papermaking waste, paper, natural wood fragments, and other wood fibers with vinegar, and use the filtrate as a plastic raw material and plastic material. We have proposed a fiber- and plastic-modified three-phase comprehensive composition having electrolyzability, ion-conversion property and thermosetting property which can be obtained by stirring (Japanese Patent Application No. 52-91).
461, JP-A-54-26398).

Each phase of the above three-phase composition is, from top to bottom, the first phase liquid phase has an electrolytic property, and the second phase has an ion exchange property as a rust remover or other metal surface treatment agent having peelability such as rust. And, as the ion-exchange semipermeable membrane phase, and the third phase liquid viscous phase has thermosetting property,
It has useful properties as an adhesive and a paint.

Problems to be Solved by the Invention The present inventors have further researched the three-phase comprehensive composition utilizing the waste resources such as the above-mentioned paper cellulosics. It was found that there are limitations in using each method as it is, and there has been a demand for a solution to these effective means.

Means for Solving the Problems As a result of various studies, the inventors of the present invention have conducted aging after the liquid composition of the first phase as it is or after adding a certain metal or metalloid substance or compound to the concentrate. It was found that the solid substance obtained as a product has various activities,
The present invention has been reached.

That is, the present invention, a mixture obtained by mixing and stirring wood fiber and vinegar, and leaving the mixture in a temperature range in which bacteria can act, and filtering the mixture, a temperature range in which the filtrate and a plastic raw material, or a plastic material can act in bacteria. The mixture of the first-phase liquid composition separated from the three-phase modified modified product obtained by mixing, stirring, brewing, and leaving the mixture as it is, or in the concentrate, iron, zinc, aluminum, manganese, copper, chromium, cobalt. ,magnesium,
One or more substances selected from the group consisting of silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur,
The present invention relates to a fiber, a plastic-modified solid material, a method for producing the solid material, and a method for using the solid material, which are preferably added and aged in an amount not more than 1/2 times the total amount.

In obtaining the first phase liquid composition used in the present invention, the following are used as other wood fibers such as papermaking resources and papermaking wastes. That is, (a) brown wrapping paper, cement paper, (b) newspaper, corrugated board (c) low-grade, high-grade printing paper, gravure paper (d) wood fiber. The compositions contained in (a), (b), (c), and (d) are mainly α-cellulose, β-cellulose, hemicellulose, lignin, extract, ink, etc. as organic matter, and S, P, Si, -AlO ₃ as inorganic matter. , Cl, other metals, etc., which include the balance of the substances used during the papermaking process, and mainly consist of the original wood part, the bone marrow part, and the papermaking residue. Vinegar is usually sterilized, but it is found that the activity of the bacteria starts by heating to some extent, and the bacteria include acetic acid bacteria present in vinegar, methane bacteria present in fiber,
Bacillus subtilis etc. are mentioned as the example.

Examples of the plastic raw material or plastic material 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, C 6 H 5 OH, HCHO, Furafuraru, isocyanates, melamine, epoxy compound, acrylic Compound, HOOC (CH ₂ ) COOH and other reaction intermediates in the plastic manufacturing process and thermosetting plastics such as urethane resins, melamine resins, polyester resins and silicone resins.
Acrylic resin, polymethylmethacrylate resin, ABS resin, polyethylene resin, polypropylene resin, thermoplastics such as nylon.

The first phase liquid composition used in the present invention is specifically manufactured as follows.

First, wood fibers such as discarded cellulose are mixed in vinegar at a weight ratio of 1:50, stirred, allowed to stand, and then filtered to obtain a filtrate as a plastic attack agent. During this reaction, the temperature may be in any range as long as the temperature of the bacteria in the vinegar can be activated, especially at 100 ° C.
Hereinafter, it is particularly preferable to carry out at room temperature to 60 ° C. or lower, and the mixing time may be carried out until the mixture becomes pulp-like (porridge-like) by mixing, but it is generally carried out for 3 hours or more. This is left to stand for a while and then filtered to obtain a filtrate.

In the filtrate, a plastic raw material (monomer, reaction intermediate product, etc.) such as the polyester resin or urethane resin,
Add a plastic material, stir for a few hours or more, and brew to obtain a liquid material that is divided into three phases. The temperature in 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 second phase that is a semipermeable membrane-like liquid viscous substance having ion exchange properties, and a third phase that is a liquid viscous phase. The three phases are separated into each.

The first phase liquid composition thus obtained has a liquid volume of 1/2.
The concentration is preferably 1/5 or less, more preferably about 1/10 or less. It is preferable to heat for concentration,
Heating is preferably carried out using a hot plate or the like and boiled, but concentration by drying such as vacuum drying is also possible,
Both heating and drying can be performed in parallel.

The concentrate of the first phase obtained as described above is used as it is, or iron, magnesium, zinc, aluminum, manganese, copper, chromium, cobalt, fluorine, iodine, selenium, calcium carbonate, phosphorus is added to the concentrate. One or more substances selected from the group consisting of sulfur and sulfur are added in the form of powder or the like in an amount 1/2 times or more the amount of the concentrated liquid. At this time, addition while continuing boiling is more preferable.

The concentrated solution or the concentrated solution to which the additive substance such as the metal is added is aged at room temperature, preferably around 35 ° C., for 1 week or more by using a floater or the like. At this time, it is also possible to periodically apply a small amount of the first phase liquid composition. At the end of aging, what was initially a liquid matter has grown throughout, becoming a beige mass due to water content. This is scraped off to obtain the object of the present invention. The obtained fiber-modified plastic solid product of the present invention has the following physical properties.

Optical rotation, left optical rotation 10 ° -12 °, protein nitrogen content of 0.56 mg / l as measured by nitrate ion, iron-zinc solids about 4.
35 mg / l, aluminum solids are about 1.61 mg / l, Al-Fe-Si
Solids are approximately 1.95 mg / l. This solid is heat resistant to temperatures up to 300 ° C., acid resistant to hydrochloric acid and solvent resistant. It is already known that relative group-specific enzymes require metals for activation [BL Vallee, JEO
leman Comprehensive Biochemistry (Compreh
This type of enzyme depends on whether the metal required for activity is tightly bound to the enzyme protein, or whether it is loose and is easily removed by dialysis or the like. Metal enzyme and Metal enzy respectively
It is distinguished from me complex. Currently, nearly 200 kinds of enzymes (excluding heme enzymes) that require metals are known.
There are Mo, Co, Fe, Ca, Mg, Cu, Zn, etc., Zn is found in dehydrogenases with FAD (which is involved in the second substrate) as a prosthetic group, and Zn is various hydrolase. Also exists. Bacillus subtilis secreting branified α-Amylaze, which is often cited, is p
Although it secretes rotease, Zn can be reversibly removed by a metalloenzyme containing Zn. The activity when other metal is bonded instead of Zn depends on the type of metal. Cu is found only in oxidase, which is an oxygen acceptor, and Fe is a dehydratase, which has FAD as a prosthetic group. These existing enzymes have the following properties, and the solid substance of the present invention is considered to be similar to them.

Although any of the above-mentioned plastic raw materials or plastic materials can be used, the first phase composition and the third phase composition to be used later are preferably polyester, polyurethane, phenol resin, melamine resin, epoxy resin, acrylic resin, bakelite, polypropylene. , Silicone, etc. are used.

When the heat-resistant and acid-resistant solid material was added to the third phase liquid viscous material obtained from the fiber and plastic-modified three-phase entrapping structure, and various additives such as metals were similarly added and treated, It has been found that the adhesive efficacy is greatly increased, and that the glass having a glass coating has an improved light transmittance.

As the raw material which is the base of the adhesive strength and glass light transmittance improving agent, any of the materials similar to the third phase liquid viscous material can be used, but the third phase liquid viscous material is preferable.

For these adhesives, for example, 1 g or more of an additive such as a metal powder is added to the third phase liquid viscous material with respect to 100 g of the liquid viscous phase, and the mixture is allowed to ferment for about 10 days, and then the present invention. It can be obtained by adding 0.1 g or more of the heat-resistant and acid-resistant solid substance, and diluting and stirring. At that time, it is preferable to use the same kind of metal as the metal to be adhered as the metal powder as the additive of the adhesive, and the same kind of additive (metal etc.) to be added to the adhesion enhancer is also preferably used. . As the metal powder, the additive includes iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, calcium carbonate, iron oxide and the like.

Similarly, the glass permeability improver can be obtained by adding the Al powder and the heat-resistant and acid-resistant solid material of the present invention to the third phase liquid viscous material. In this case, Al is more preferable as the additive substance added to the solid matter.

The third-phase viscous composition corresponds to the third phase of the three-phase comprehensive composition, and a filtrate made of vinegar and fibrin is mixed and stirred with the plastic material, which is a plastic raw material. After being allowed to stand, as a high-concentration product, precipitation is cultivated at the bottom (third phase) in the production container.

For example, in a modified phenol resin, formalin acts on phenol to cause methylolation at the ortho position and para position of the phenol, and this causes polycondensation to release water to give a polymer. Make a substance. It is considered that formalin and gluconic acid are contained in the aldehydes in the filtrate, and a novolac-type polymer modified with phenol can be formed instead of the novolac type. In addition, the inclusion of enzyme in the filtrate,
Due to the inclusion of cellulose, hemicellulose, lignin and others, the actual reaction is believed to be further complicated.
As for the performance, it is superior in acid resistance and heat resistance to novolac type phenol, and can be very well adhered (to metal etc.). Further, the urethane resin modified product is based on cellulose from papermaking resources, and due to the presence of a large amount of cellulose nitrogen in the filtrate, an amide bond is formed, which is deformed and further esterified to form a polycondensate with an amide. It is thought that the reaction is diverse because the components in the filtrate are complicated. When the three-layer mucus phase is molded and processed, each of the admixed plastics is transformed into a special plastic which has not been heretofore having both two-dimensional bonding and three-dimensional bonding properties.

The solid matter of the present invention is added to the third phase liquid / viscous composition together with other additives, but is added to the third phase composition of 1000 g in an amount of 0.2
By adding a small amount of -10 g, the antistatic property, voltage-charging property, and adhesiveness, especially the adhesiveness of metals and glass can be remarkably improved. In addition, the transparency of glass can be improved.

Action The fiber of the present invention, the plastic modified solid material can be extremely easily produced from a waste material such as cellulose and a composition modified from plastic, and can be excellent in heat resistance and acid resistance, and can be static-free. , Has an effect of ionizing the contained metal to be in a soluble state, can increase the adhesiveness of the metal, and has an effect of improving the light transmittance of the glass.

EXAMPLES Next, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not limited thereto.

Example 1 Crushed waste paper was added to vinegar, and the mixture was stirred for 3 hours to obtain a pulp-like (porridge-like) product. After leaving the porridge-like product at about 40 ° C. for 3 days, squeeze it. Get the liquid. The filtrate was aged again at about 40 ° C. for 3 days, and ethylene glycol (D-290-70-Burnock 1 liquid, Dainippon Ink and Chemicals Co., Ltd., hydroxyl value 204, OH%) as a raw material of urethane was added thereto.
6.2, NC equivalent 15.3) is added, and the mixture is stirred for 3 hours and left to stand for 3 days to obtain a modified product having three phases.

The first phase out of the three phases was taken out by the gradient method, put in a glass container 5 and using a gas or mantle heater.
Heat to about 98 ° C and boil. This operation is performed for 6 hours, and when the liquid volume becomes about 1/5, heating is stopped. The above operation was repeated several times to obtain 1/5 concentrated liquid 100. 100 above concentrated solution
1 kg of Zn powder and Fe powder was gradually added while boiling.

This product was placed in an ovulator and aged at 35 ° C for 10 days. At this time, the surface of the concentrated liquid was raised and proliferated, and the water content of the concentrated liquid was completely removed to become a solid.

When the aged solid was scratched out, 300 g was obtained.
The solid is a beige solid and is analyzed to have heat resistance of 300 to 900 ° C., acid resistance to HCl, and solvent resistance.

In the same manner, with or without Fe-
An aged solid substance was obtained from a material to which Al, Fe-P, Fe-Al-C-Si or the like was added instead of Zn.

 These properties are shown in Table 1.

The resulting aged solids have left optical rotation without additives.
10 ° to 12 °, protein nitrogen content is ammonium ion 0.02mg
/, Phosphate ion 0.05 mg /, nitrate ion 0.56 mg /, nitrate ion 4.35 mg / in iron-zinc solid matter, 1.61 mg / in aluminum solid matter, and 1.95 mg / in Al-Fe-Si solid matter. /Met. 450 times micrographs showing the crystal structure of the aged solid of the present invention are shown in FIGS. 1 to 4.
FIG. 1 is a photomicrograph showing the crystal structure of a solid substance without additives, FIG. 2 is a photomicrograph showing the crystal structure of a solid substance with additive Zn-Fe, and FIG. 3 is an additive Fe- Micrograph showing the crystal structure of the solid in the case of Al, Fig. 4 shows the additive Fe
It is a microscope picture which shows the crystal structure of a solid in the case of -Al-Zn-Si-Co. Metal crystals are, for example, hexagonal for Zn, circular for Fe, and cylindrical for Al, but in FIGS. 2, 3, and 4, these crystals disappear and have a unique crystal structure. It should be noted that although FIG. 1 does not contain any additive, it has a modified crystal structure of the metal contained in the above three-phase liquid viscous material.

As described above, it is apparent that the above-mentioned product of the present invention is a kind of protein and that the additive is modified. In general, the enzyme is mainly composed of protein and is a biocatalyst, so that the product obtained in the present invention is considered to be a kind of bound enzyme.

Also, the maximum activation temperature of ordinary enzymes is around 55 ° C,
On the other hand, the solid substance of the present invention has an activity up to about 300 ° C. and has a maximum activation temperature of 60 to 250 ° C., while it loses its activity at about 0 ° C. Then
The active pH is 3 to 6, and the maximum active pH is 4 to 5.

Next, fiber and plastic modified third phase liquid viscous material 300
Add the following metal powder 200g to, and keep warm at 35 ℃ or more,
After 10 hours, 6 g or more of the heat-resistant and acid-resistant solid material of the present invention obtained above was added, and various adhesives were produced by diluting and stirring. The adhesive effects thereof are shown in Table 2.

Further, the glass transmittance improver is obtained by adding the heat-resistant and acid-resistant solid material obtained in the same manner to 100 g of the same third phase liquid viscous material as described above.
Was added to 10 g of the metal powder shown in Table 3 and treated in the same manner as in the case of the adhesive.

Table 3 shows the transmittance of the glass when this was coated on the glass.

EFFECTS OF THE INVENTION The present invention is an effective use of cellulose-based waste, which is a solid material having heat resistance and acid resistance from a fiber and a plastic modified product, has an action of ionizing a metal, etc., and enhances adhesion. Alternatively, it has excellent effects such as improvement of glass permeability, can also improve viscoelasticity and curability, and is used for plating plastics, plastic magnets, printed circuit boards, adhesives, glass optical transparency improvers, etc. , Various uses can be expected. Further, the manufacturing thereof is extremely easy to operate, and since it is the use of waste, it can be manufactured at low cost, and it can be said that the invention is extremely useful in industry.

[Brief description of drawings]

FIG. 1 is a photomicrograph showing the crystal structure of a solid product of the present invention without additives, FIG. 2 is a photomicrograph showing the crystal structure of solid products of additives Zn and Fe, and FIG. 3 is also an additive. Fe, A
4 is a photomicrograph showing the crystal structure of the solid substance of FIG. 1, and FIG. 4 is a photomicrograph showing the crystal structure of the solid substance of the additive Fe, Al, Zn, Si, Co.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 167/00 PKX C09D 167/00 PKX 201/00 PDC 201/00 PDC C09J 11/08 JBC C09J 11 / 08 JBC C12P 1/00 C12P 1/00 Z

Claims (4)

(57) [Claims] 1. A mixture obtained by mixing and stirring wood fiber and vinegar, and allowing the mixture to stand in a temperature range in which bacteria can act, and filtering the mixture, and the filtrate and a plastic material or plastic material in a temperature range in which bacteria can act. Mixing stirring, brewing, the first phase liquid composition separated from the three-phase comprehensive active modified product obtained by standing, as a concentrate, or in the concentrate, iron, zinc, aluminum, manganese, copper, chromium, Cobalt, magnesium,
A fiber, a plastic-modified solid, which is made by adding and aging one or more substances selected from the group consisting of silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur. 2. A mixture obtained by mixing wood fiber and vinegar, stirring the mixture, and allowing it to stand in a temperature range in which bacteria can act, and filtering the mixture, and a temperature range in which the filtrate and the plastic raw material or plastic material can act in bacteria. The first-phase liquid composition separated from the three-phase comprehensive active modified product obtained by mixing, stirring, brewing, and standing with is concentrated to a liquid volume of 1/2 or less, and the concentrate as it is or in the concentrate, iron , Zinc, aluminum, manganese, copper, chrome,
A process for producing a fiber or a plastic-modified solid comprising a material obtained by adding and aging one or more substances selected from the group consisting of cobalt, magnesium, silicon, fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur. 3. A mixture obtained by mixing wood fiber and vinegar, stirring, and leaving the mixture in a temperature range in which bacteria can act, and filtering the mixture, and the filtrate and the plastic raw material or plastic material in a temperature range in which bacteria can act. In the concentrate of the first phase liquid composition separated from the three-phase comprehensive active modified product obtained by mixing, stirring, brewing and standing, iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, An adhesion-strengthening agent comprising a fiber or a plastic-modified solid material, which is obtained by adding and aging one or more substances selected from the group consisting of fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur. 4. A mixture obtained by mixing and stirring wood fiber and vinegar, and allowing the mixture to stand in a temperature range in which bacteria can act, and filtering the mixture, and the filtrate and the plastic raw material or plastic material in a temperature range in which bacteria can act. In the concentrate of the first phase liquid composition separated from the three-phase comprehensive active modified product obtained by mixing, stirring, brewing and standing, iron, zinc, aluminum, manganese, copper, chromium, cobalt, magnesium, silicon, A glass light transmittance improver comprising a fiber or a plastic-modified solid material, which is made by adding and aging one or more substances selected from the group consisting of fluorine, iodine, selenium, calcium carbonate, phosphorus and sulfur.