JPH05320358A - Keratin protein article molded by high-pressure molding - Google Patents

Abstract

PURPOSE:To obtain a keratin protein molded article having excellent toughness, engraving suitability and feeling to finger and useful as artificial ivory, artificial tortoise shell, stamp material, etc., by compounding powdery keratin, etc., with a specific amount of a binder and molding the obtained composition under high pressure. CONSTITUTION:The keratin protein molded article is produced by the high- pressure molding of a composition composed of (A) preferably 70-95wt.% of powdery or fibrous keratin having an average size of >=0.1mum, e.g. hoof, horn, beak, claw, scale, carapace, fwr, feather, wool or hair of birds and animals and (B) <50wt.% in total (based on the total composition) of arbitrary additives such as a binder (e.g. partially decomposed protein or gelatin), a cross-linking agent (e.g. epoxy resin), etc.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to an artificial ivory, a tortoiseshell, a piano machine, a stamping material, a decorative board, a decorative article, which is obtained by high-pressure molding of a mixture of powdered or fibrous keratin or containing it as a main component. The present invention relates to a high-pressure molded product such as a tire and a sheet, and modified particles obtained by crushing the product.

[0002]

Conventionally, tortoise shells, buffalo horns, ivory, etc. have been heavily used as materials for seals, piano keyboards, ornaments, etc. However, due to the changing social background of international animal protection, these natural materials are imported. In addition, it is becoming difficult to use these materials, and there is a demand for the development of alternative materials for them and the development of studless tire treads that solve dust pollution caused by the use of spiked tires.

As such alternative materials, for example, methyl methacrylate resin, unsaturated polyester resin and the like, magnesium hydroxide, aluminum hydroxide, titanium oxide,
Molded articles made from inorganic fillers such as calcium carbonate: or artificial ivory in which egg shells are hardened with milk casein has been developed. However, these materials are hydrophilic,
The required qualities of maintaining both hydrophobicity and satisfying toughness, engraving property, finger touch property, etc. are far below.

Recently, crushed silk thread, wool, chicken feathers, etc., which have been pulverized into powder form, are dissolved in an organic solvent to make keratin,
It seems that attempts have been made to extract hard proteins such as collagen into thin membranes and stack them in multiple layers to obtain an alternative to the tortoise shell, but research has just begun and is still sufficient. It doesn't seem to have achieved any good results.

[0005]

[Problems to be Solved by the Invention] Therefore, a molding material having various physical properties, touch, engraving workability and the like which cannot be achieved by conventional alternative materials, and artificial ivory, seal, piano obtained by processing the material. It is an object of the invention to obtain a molded processed product such as a kenban or a tortoiseshell ornament.

[0006]

SUMMARY OF THE INVENTION According to the invention, the above object of the invention is a composition comprising powder or fibrous keratin and optionally less than 50% by weight of the total amount of binder and other additives added in total. It can be achieved by a high-pressure molded product of keratin protein obtained by high-pressure molding.

[0007] In the present invention, the powdered or fibrous keratin or a compound containing it as a main component is directly molded into a molded product by high pressure molding, and the inherent properties of the keratin material can be utilized as they are.

The keratin used in the present invention includes hoofs, horns, beaks, nails, scales, shells, animal hair, feathers, wool of birds and animals.
Powder or fiber such as hair, average size is 0.1μm
The above is about several mm. As used herein, the term average size refers to the average particle size for particulates and its average major axis for fibrous materials. Such powder or fiber can be obtained by directly pulverizing or freeze-pulverizing the above-mentioned natural material or after pretreatment. (Japanese Patent Application 3-1
25661).

These powdery or fibrous keratins are used alone or as a mixture of two or more kinds,
Greater than 50% by weight, up to 100% by weight, preferably 70-95% by weight, based on the total weight of the compound subjected to high pressure molding
Used in proportion. If the amount exceeds 95% by weight, the strength may be poor, so the amount should be up to 95% by weight depending on the purpose of use, while if it is less than 50% by weight, the natural feeling tends to be impaired.

The binder optionally added is a natural material selected from a partially decomposed protein, gelatin, glue, casein, milk, egg white, starch, cystine, cysteine, thioglycolate, rosin, sap, natural rubber and / or the like. Epoxy resin, melamine resin, urea resin, polyester resin, acrylic resin, polyurethane resin, polyamino resin, polycarbonate resin, polyvinyl chloride resin,
Synthetic resin selected from polyamino acid resin, polyolefin resin, etc. and SBR, IR, BR, CR, EPM, E
It is a synthetic rubber such as PDM and is used in the form of one kind or a mixture of two or more kinds thereof.

In addition to the above components, other known additives such as resins, fillers, dyes, pigments, reinforcing agents, crosslinking agents and catalysts can be added as optional components. However, the total amount of these binders and additives should be less than 50% by weight of the total formulation, otherwise undesired and undesired.

In a particularly preferred embodiment, a small amount of a crosslinking agent or a coupling agent is added. Examples of the cross-linking agent include 2,4-tolylene diisocyanate prepolymer adduct, epoxy resin or compound, silane coupling agent, organometallic coupling agent, melamine, formalin, benzoguanamine, urea, thioglycolate, cysteine, and diamine. Oils and fats having a heavy bond are preferably used, and during molding, a crosslinking reaction is carried out by reaction with reactive functional groups such as hydroxyl, carboxyl and amino groups on the keratin surface, resulting in a molded product with exceptionally fastness. Be done.

In the present invention, the above-mentioned compound is directly molded by high pressure molding. At this time, entanglement between keratin particles or fibers and repolymerization are simultaneously performed, and in the presence of a crosslinking agent, keratin molecules are arbitrarily crosslinked with each other. The high pressure molding is, for example, a method using a solid ultra-high pressure press; an ultrahigh pressure molding method such as a warm isotropic pressure pressing method (WIP method) or a cold isotropic pressure pressing method (CIP method); or injection molding or compression molding. It can be carried out by the high pressure molding method of
Maximum pressure 10,000 kgf / cm ² , temperature -20
~ 200 ℃ warm isostatic pressing method or 6,000kgf /
cm ² , cold isostatic pressing at room temperature, and solid ultra-high pressure pressing method of 10 ton / cm ² are preferable.

In molding, it is usually preferable that the compound is used as a uniform composition, but it is also carried out on a tree-ring layered product if desired.

By the method of the present invention, artificial ivory having excellent appearance, feel, water absorption, oil absorption, fastness, and engraving property, seal material, piano machine, tortoise shell ornament, decorative plate, printing material, tire, etc. A molded product useful as a molded product of the above can be obtained.

The present invention will be described below with reference to examples.

[Example 1] Seal material (artificial buffalo horn) Composition W / W% Fine beef hoof powder 70.0 Beef bone powder 10.0 Epoxy resin (Epicoat 1004) 20.0 (softening point 97 ° C powder) Total 100. 0

20 g of epoxy resin powder and 10 g of beef bone powder
Was charged into a thunder kai machine and crushed for 1 hour. This beef hoof powder 7
0 g was added and mixed uniformly. A part of this mixture was filled in a cylindrical mold with an inside diameter of 18 mm and a height of 150 mm equipped with a deaerator, and while degassing from the middle, pressurization and temperature increase were continued from above and below at 200 kg / cm ² × 130 ° C. Held for hours. The obtained molded product was removed from the mold and the suitability for the stamp material was evaluated.

[0018] By adjusting the appearance, it was confirmed that the material has a performance equivalent to that of buffalo horn, which is a natural material.

[0019]

Example 2 Artificial tortoise shell W / W% Bird bone chicken feather (white) Fine powder 85.0 〃 (black) 〃 5.0 Hexamethylene diisocyanate (HMDI) prepolymer 10.0 Total 100.0

10 g of HMDI prepolymer was added to 1 part of acetone.
Dissolve in 00g, add 2 kinds of bird bone chicken fine powder to this,
Dispersed evenly. Acetone was immediately removed at room temperature under reduced pressure, and the surface of the feather powder was treated with the HMDI prepolymer.
This treated feather powder is uniformly filled in a stainless steel container having an inner diameter of 100 mm and a height of 50 mm, and the temperature and pressure are gradually increased by an ultrahigh pressure press machine at 100 ° C. and 100 ton /
It was held at cm ² for 1 hour and compression molded. The obtained molded product had a translucent luster. This was compared with a natural tortoiseshell harvested from the turtle.

[0021]

In order to artificially form a striped pattern, it is possible to laminate the feather fine powder so that the ratio of white and black is changed stepwise or alternately.

[0023]

[Example 3] Tire tread (keratin tire) composition W / W% Pig hair (chopped product) 40.0 Surface treatment Beef hoof powder 20.0 〃 Silane coupling agent (terminal vinyl group) 2.0 〃 Small Total 62.0 NR (natural rubber) 36.5 Sulfur 1.0 Vulcanization accelerator DPG 0.3 〃 MBT 0.2 Total 100.0 (Note) DPG (diphenylguanidine); MBT (2-
(Mercaptobenzothiazole)

The keratins of and were surface-treated with a silane coupling agent diluted with ethyl acetate and dried. This surface-treated product was added to the composition of and kneaded with a kneader. This kneaded product is processed by the WIP method (war
135 ° C x 8,000 kgf / cm ² x 30 on the tire tread with misostatic pressing)
It was held for minutes and vulcanized and molded.

The obtained molded product was formed into a flat piece having a 3 cm × 5 cm square and no pattern, and its physical properties were evaluated. For comparison, a commercially available normal rubber tire 165SR13
The radial tire tread portion and a commercially available 165R13 studless tire tread portion as a studless rubber tire are used to perform a comparison test on the same section.

[0026]

Test Method Slip Resistance Index Tests were carried out using a constant speed type rotating disk type friction tester. Ice having a smooth surface was fixed on a rotating disk having a diameter of about 20 cm, and a test piece of 3 cm x 5 cm was pressed against this with a constant load (500 g). The frictional force applied to the test piece when the rotating disk was rotated at a constant speed was detected by the load cell. The value (index) is shown when the frictional force of the comparative sample is 100, and the larger the value, the better the frictional force, that is, the slip resistance.

Abrasion resistance index In the above test method, the asphalt was used as the material for the surface of the rotating plate, and the abrasion resistance ratio of the comparative sample was calculated as 100 from the residual amount ratio (abrasion resistance ratio) when rotating for a certain period of time. The value (index) when The larger the value, the better the wear resistance.

The keratin tire according to the present embodiment is an all-weather studless tire that has slip-proof properties on all road surfaces such as a rain-free road surface, an ice-snow road surface, and an oil-wet road surface that are completely pollution-free. In addition, even when it is discarded, it can be returned to the soil as a good organic fertilizer, and it hardly harms the environment.

Claims (4)

[Claims] 1. A high-pressure molded product of keratin protein obtained by high-pressure molding of a mixture comprising powder or fibrous keratin, and optionally a total amount of the binder and other additives in a total amount of less than 50% by weight. 2. Keratin is used for hoofs, horns, beaks, nails of birds and animals.
The molded product according to claim 1, which is a keratin powder or fiber such as scales, shells, animal hair, feathers, wool, and hair, having an average size of 0.1 µm or more. 3. The binder is a partially decomposed protein, gelatin, glue, collagen, casein, milk, egg white, starch,
Natural materials and / or epoxy resins, melamine resins, urea resins selected from cystine, cysteine, thioglycollate, fats, rosins, sap, natural rubber (NR), etc.
Polyester resin, acrylic resin, polyurethane resin,
A synthetic resin selected from polyamino resin, polycarbonate resin, polyvinyl chloride resin, polyamino acid resin, PVA, polyolefin resin and the like, and synthetic rubber such as SBR (styrene butadiene rubber), IR (isobrene rubber) and BR (butadiene rubber). The molded product according to item 1. 4. The molded article according to claim 1, wherein the additive is a cross-linking agent. [0001]