JP2001302977A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition and a coating exhibiting sufficient matte effects, having a good touch feeling and causing no environmental problems. SOLUTION: The coating composition comprises polyamino acid particles and inorganic particles, where the polyamino acid particles and the inorganic particles give when mixed together an apparent bulk density of 0.02-0.30 g/ml at 23 deg.C in a main solvent of the coating composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition capable of obtaining a coating film having a high-grade feel.

[0002]

2. Description of the Related Art In recent years, it has been demanded that coating materials used for sheets and fibers such as vinyl chloride and artificial leather, and for parts such as furniture, automobile interiors, personal computers, etc. satisfy a high-grade preference. Improves design properties such as dyeing properties and moisture absorption / desorption properties to give a good texture and feel,
There is a demand for imparting unprecedented properties.

As a means for satisfying such a demand, a matting agent such as silica fine particles is conventionally added as disclosed in, for example, JP-A-9-157545 and JP-A-11-49992. Into a matte paint or a semi-gloss paint, for example, as described in JP-A-62-240.
No. 400, as disclosed in JP-A-1-197599, to improve the coating surface by kneading leather powder,
To give a good hand is also described in, for example,
As disclosed in JP-A-2525259 and JP-A-6-346909, gelatin and collagen are kneaded to improve the moisture absorption / release properties of a coating film. However, when a natural organic powder such as leather powder or collagen powder alone is added to the coating composition for the purpose of giving a good touch, in order to obtain a sufficient matting effect, a large amount of the natural organic powder is added. Needed.

To solve these problems, for example, Japanese Patent Application Laid-Open No. 7-70600 discloses that an apparent bulk specific gravity is 0.02.
Oil absorption of 1.70 to 4.00 ml at 0.12 g / ml
A method using a collagen powder is described, and JP-A-8-73752 discloses an apparent bulk specific gravity of 0.0
A method is described in which collagen powder of 2 to 0.30 g / ml, titanium dioxide-coated mica, and silica particles are contained in a paint. However, even with this method,
A sufficient matting effect and good touch could not be satisfied at the same time.

[0005] Furthermore, since collagen powder derived from a natural product is used, the occurrence of an environmental problem that odor is generated cannot be ignored. Regarding odor, for example, Japanese Patent Application Laid-Open No. 7-41733 describes that a urea-aldehyde resin powder or a melamine-aldehyde resin powder is added to a coating material in order to suppress odor generation. The odor could not be suppressed.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a coating composition and a paint having a sufficient matting effect and a good feel, and satisfying environmental issues.

[0007]

As a result of various studies to achieve the above object, the present inventors found that the apparent bulk specific gravity at 23 ° C. in the main solvent used for the coating composition showed a matte effect and a touch. It is found that it is a necessary requirement for compatibility. That is, in the present invention, the apparent bulk specific gravity of the additive composition measured in the main solvent in the solvent used in the coating composition is not the bulk specific gravity measured in a dry powder state, but the bulk specific gravity is the most suitable for the finish of the coating. This was done after finding that the effect was large.

The object of the present invention is to (1) contain polyamino acid particles and inorganic particles, and
When the polyamino acid particles and the inorganic particles are mixed with the polyamino acid particles and the inorganic particles, in a main solvent in the coating composition, at 23 ° C., 0.02 to 0.3
A coating composition comprising polyamino acid particles and inorganic particles having an apparent bulk specific gravity of 0 g / ml. (2) The coating composition according to the above (1), wherein the main solvent is at least one selected from water, hydrocarbon, aromatic, alcohol, ketone, ether and cellosolve solvents. object. (3) Main solvents are hexane, cyclohexane, ethyl acetate, butyl acetate, amyl acetate, ethylene glycol ethyl ether acetate, toluene, xylene, methyl alcohol, isopropanol, n-propanol,
Butanol, acetone, methyl ethyl ketone, cyclohexanone, isopropyl ether, methyl cellosolve,
The coating composition according to the above (1) or (2), which is at least one selected from ethyl cellosolve, ethylene glycol, and diethylene glycol. (4) The apparent bulk specific gravity of the polyamino acid particles is 0.3 to 2.
0 g / ml, and the apparent bulk specific gravity of the inorganic particles was 0.1.
The coating composition according to any one of the above (1) to (3), wherein the amount is from 0.5 g / ml to 0.5 g / ml. (5) The average particle size of the polyamino acid particles is 0.5 to 20 μm
m, the average particle size of the inorganic particles is 0.01 to 5 μm,
(1) wherein the average particle size of the polyamino acid particles is larger than the average particle size of the inorganic particles.
The coating composition according to any one of (1) to (4). (6) The coating composition according to any one of the above (1) to (5), wherein the polyamino acid particles and the inorganic particles are added as a previously mixed mixture. (7) The coating composition according to any one of (1) to (6), wherein the inorganic particles are inorganic particles having a Mohs hardness of 5 or more. (8) The inorganic particles include oxides, nitrides, metal salts, mica,
The coating composition according to any one of the above (1) to (7), wherein the coating composition is at least one kind of particles selected from talc. (9) When the polyamino acid particles are tyrosine and the amino acid is 100
The coating composition according to any one of the above (1) to (8), wherein the particles are particles of 4.0 or less polyamino acids per 0 particles. (10) A paint, wherein the coating composition according to any one of (1) to (9) is a paint. Achieved by

Hereinafter, the present invention will be described in detail. In the present invention, polyamino acid particles and inorganic particles are added to the coating composition in order to impart a matte effect and a good hand. In the present invention, the coating composition refers to a composition containing a film-forming material and a solvent.

First, the polyamino acid used in the present invention will be described. In the present invention, the polyamino acid refers to a relatively low molecular weight protein obtained by decomposing a high molecular weight natural protein. The polyamino acid particles are obtained by pulverizing the polyamino acid into particles.

Representative examples of the polyamino acids in the present invention include: (1) a polyamino acid separated from the resulting hydrolyzate by enzymatically decomposing gelatin using an enzyme such as gelatinase or proteinase; and (2) a polyamino acid such as gelatinase or proteinase. Examples include polyamino acids and the like, which are obtained by enzymatically decomposing a gelatin extraction residue using an enzyme and separating the resulting decomposed product. As described above, typical methods for obtaining a polyamino acid include a method for directly decomposing gelatin and a method for obtaining from a gelatin extraction residue, and from the viewpoint of effective utilization of resources, a method for obtaining from a gelatin extraction residue. Are very advantageous and preferred.

Here, gelatin is an inducible protein obtained by heating collagen in water to irreversibly convert it to water-soluble, and by denaturation by heating, hydrogen bonds between polyamino acid chains of collagen molecules are cleaved. Refers to a substance produced by breaking the tertiary structure of collagen molecules, and a gelatin extraction residue refers to a substance obtained by subjecting ossein to acid-base treatment and then performing hot water extraction, which is commonly used in the production of gelatin, three to five times. And refers to water-insoluble substances remaining after the gelatin is no longer extracted. When the gelatin extraction residue is decomposed by an enzyme, a crude product of a polyamino acid is obtained.The crude product usually contains fats, inorganic salts, metal ions, and the like. By removing it, the polyamino acid of the present invention can be obtained. Gelatin used for preparing the present invention is not particularly limited, for example,
Alkali-treated gelatin (cow bone, chicken bone or animal skin gelatin), acid-treated gelatin (pig skin gelatin) and the like can be mentioned.

The weight average molecular weight of the polyamino acid can be measured by a conventional method using gel permeation chromatography. The weight average molecular weight of the polyamino acid of the present invention is 1000 to 1000 in terms of polyethylene glycol as a standard substance. Preferably 50,000, and 3
More preferably, it is 2,000 to 20,000.

The polyamino acid used in the present invention preferably contains not more than 4.0 tyrosine per 1000 amino acids. Tyrosine is an amino acid that is originally involved in the cross-linking between polyamino acids, and from the viewpoint of uniform quality, it is preferable that tyrosine is not contained.However, the availability of raw materials for production and the effective use of materials are considered. Considering the points and the like, it is not advantageous to completely remove tyrosine, so that tyrosine remains, but even in this case, tyrosine is 4.0 per 1000 amino acids.
It is preferable that the number is not more than the number. If the number is 4.0 or less, sufficient uniformity of quality can be obtained. Further, 3.0
The number is preferably at most 2.0, particularly preferably at most 2.0.

The polyamino acid has a number of tyrosine per 4.0 amino acids of 4.0 or less and a weight average molecular weight of 1
When it is 000 to 50,000, it is easily dissolved in water even at room temperature. If the water solubility of the polyamino acid is high, uniformity of quality can be produced and the generation of odor can be reduced. This is considered to be because the substance generating the odor is easily removed. Tyrosine content of polyamino acid 1000
When the number is more than 4.0 per unit, the solubility in water is reduced, so that uniformity of quality and removal of odor cannot be sufficiently obtained.

The polyamino acid used in the present invention is preferably made water-insoluble by, for example, crosslinking between molecules by ionic bonds or covalent bonds. Water-insoluble methods include (1) making a derivative with a hydrophobic substituent added,
(2) There is a method such as cross-linking, but it is preferable that the polyamino acid is made water-insoluble by cross-linking in order to minimize the intrinsic properties of the polyamino acid as much as possible. Here, the term "water-soluble at normal temperature" means that 100 g of a substance is stirred in 1 liter of pure water at 23 ° C. for 24 hours, then filtered through No. 2 filter paper, and the amount of the substance remaining on the filter paper after drying is 0%. It means that it is less than 0.5 g. The term “water-insoluble” means that the amount is 0.5 g or more.

As the cross-linking agent, a cross-linking agent composed of an inorganic metal salt and an organic cross-linking agent that forms a covalent bond can be used. Examples of the crosslinking agent composed of an inorganic metal salt include agents used in the conventional tanning method, for example, a chromium tanning agent, an alum tanning agent, and a zirconium tanning agent.
Organic crosslinking agents include vegetable tannins and JP-A-49-51945, which are known as hardeners in the photographic industry.
JP-A-51-59625, JP-A-62-262854, JP-A-63-184741 and JP-A-8-0220.
No. 94, hardening agents having a carbamoyl ammonium group, aldehydes such as formalin, and the like.
A vinyl sulfone hardener described in JP-A-314049 can be used. Also, a polyamino acid synthesizing reagent such as carbodiimide or a polyamino acid synthase such as trans-glutaminase can be used. Preferred cross-linking agents are those in which the cross-linking reaction to gelatin proceeds relatively quickly and sufficiently, and is a cross-linking agent excellent in stability over time, zirconium sulfate, zirconium salts such as zirconium chloride oxide, a hardening agent having a carbamoyl ammonium group, 1-ethyl-3-
Water-soluble carbodiimides such as (3-dimethylaminopropyl) -carbodiimide monohydrochloric acid are exemplified. These crosslinking agents may be used alone or in combination of two or more.

The amount of the crosslinking agent used in the present invention is not particularly limited because it is determined by the required water absorption of the polyamino acid composition.
Preferably, it is used in a range of 20 mmol. The form of the crosslinked product is preferably solid from the viewpoint of handling. In the present invention, by using a zirconium atom and a sulfate ion as a crosslinking agent, it is possible to obtain a preferred solid cross-linked product, zirconium sulfate,
Preferably, zirconyl sulfate is used, with zirconium sulfate being most preferred. In the case of zirconium sulfate, the molar ratio between the zirconium atom and the sulfate ion is 1/10 to 1
0 is preferable, and 1 to 5 mmol per 1 g of the polyamino acid.
It is preferred to use.

The time and temperature of the cross-linking reaction vary depending on the type of the cross-linking agent and the concentration of the polyamino acid and are not specified. However, if the cross-linking reaction is carried out too quickly, a uniform reaction product cannot be obtained. In some cases, it may be appropriately selected depending on the type of the crosslinking agent and the concentration of the polyamino acid. In general, the reaction may be completed at 23 ° C. for about 1 to 40 hours.

In carrying out the crosslinking reaction, a dispersant may be used. Examples of the dispersant that can be used include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. These can be used alone or in combination.

The amount of fats and oils contained in the polyamino acid of the present invention is preferably 5% or less, more preferably 3% or less. Oils and fats in polyamino acids can be determined by quantifying components extracted with hexane as oils and fats. (See Paragraph 22 of the Photographic Gelatin Test Method, 7th Edition (issued by the Joint Council for the Method of Photographic Gelatin Test)).

The crude product of polyamino acid obtained by decomposing the gelatin extraction residue can be defatted by, for example, a coagulation sedimentation method using a polymer coagulant such as chitosan, an ion exchange resin method,
A high-performance oil adsorbent method, a pulp filtration method, a heated flotation method, an activated carbon method, a coagulation sedimentation method by pH adjustment, and the like can be used, and these methods can be combined in consideration of desired product properties and cost. Among these, the coagulation sedimentation method using chitosan, the ion exchange resin method and the high performance oil adsorbent method are particularly preferred.

To perform degreasing using chitosan, first, an aqueous solution of chitosan is added to an aqueous solution of a crude product of a polyamino acid and stirred. Chitosan is added, for example, in an amount of 0.03 to 1.0 g, preferably 0.1 to 0.5 g, per 100 g of a crude product of a polyamino acid. In addition, chitosan is
Chitin, which is an organic skeletal substance such as arthropods, annelids, and molluscs, is a polysaccharide containing an amino group obtained by hydrolyzing chitin with a concentrated alkali. Typically, a 5-10% aqueous solution of the crude polyamino acid product is made at 40-60 ° C.
A 1-1.0% aqueous solution of chitosan or an aqueous dispersion is added, and the mixture is stirred for 0.2-1.0 hours, and then left standing for 0.1-0.5 hours to form a floc having a high fat content. This can be removed by centrifugation. Since the degreasing effect can be enhanced by increasing the amount of chitosan used, the amount of chitosan used is adjusted according to the fat content of the raw material. The high-performance oil sorbent used in the high-performance oil sorbent method is a product for specifically adsorbing fats and oils in products for environmental pollution such as oil spill. There are a sheet form, a roll form and a particle form, which are commercially available from Organo Co., Ltd., Mitsui Toatsu Chemical Co., Ltd. and the like.

The ion exchange resin method is preferable because it can remove not only degreasing but also inorganic ions and heavy metal ions contained in the crude product of the polyamino acid of the present invention. Is decided. When washing materials such as fibers coated with the coating composition of the present invention, calcium ions have a large effect on soil removal, so that the content of calcium ions contained in the polyamino acid used in the present invention is 1% by mass. %, Preferably 5000 ppm or less, more preferably 1000 ppm or less. In addition, since iron ions cause discoloration of polyamino acids due to rust, the iron content is set to 500% by mass.
ppm or less.
It is preferable that the content be not more than ppm. These ions can be reduced by ion exchange, but a raw material having a low content of calcium and iron may be used.

When the polyamino acid of the present invention is subjected to ion exchange treatment, it is preferable to use a strongly acidic cation exchange resin and a strongly salted cation exchange resin in a known manner. The ion exchange resin is, for example, a crude product of polyamino acid 10
Use 20-150 liters for 0 kg. Typically, a 5 to 10% aqueous solution of a previously defatted crude polyamino acid product is prepared at 40 to 60 ° C., and a space flow rate (SV) of 2 to 15 is supplied to an ion exchange column filled with a strongly acidic ion exchange resin.
, And then the effluent is treated in the same manner with a strongly basic ion exchange resin. Diaion SK-1B, Amberlite 1R-120, 1
R-122, XE-100, Dowex 50 and the like can be used as appropriate. In addition, strong basic ion exchange resins include Diaion SA-10A, SA-11A and SA-2.
0A, Amberlite 1RA-400, IRA-40
1, IRA-410, IRA-411, Dowex 50, etc. can be used as appropriate.

The polyamino acid of the present invention may be used alone or in combination with another compound.
Examples of other mixable compounds include natural polysaccharides such as dextran and agar, proteins such as casein and albumin, and hydrophilic colloids such as hydrophilic polyvinyl compounds such as polyvinyl alcohol, polyacrylamide, and polyvinylpyrrolidone.

The polyamino acid particles of the present invention can be produced by carrying out the crosslinking uniformly, in an extremely productive and efficient manner so that their physical properties can be controlled. That is, a raw material polyamino acid is dissolved in water, and a cross-linking reaction is performed in a solution by treating with a single or a plurality of cross-linking agents to obtain a gel-like substance or a water-insoluble substance, which is dried and pulverized. Thus, the polyamino acid particles of the present invention can be obtained.

To the polyamino acid particles of the present invention, inorganic substances, pigments, dyes, etc. can be added for the purpose of adjusting the hardness, coloring and the like. These additives can be added before or after the crosslinking reaction.

The polyamino acid particles of the present invention have a water absorption of 2.
It is preferably from 0 to 30. More preferably, 2.
0 to 10. If the water absorption is less than 2.0, sufficient moisture absorbing ability cannot be obtained, and if it is more than 30, a sticky feeling will be obtained at high humidity. The water absorption of the particles was measured by the method described below. A particle sample (1.0 g, WA) is taken in a centrifuge tube, immersed in water 50 times or more for 1 hour or more to absorb water, centrifuged at 300 G for 10 minutes, and a water-containing sample after removing a supernatant is weighed. (WB), and was calculated by the following equation. Water absorption = {(WB-WA) / WA}

The apparent bulk specific gravity of the polyamino acid particles of the present invention is preferably from 0.3 to 2.0 g / ml, and more preferably from 0.35 to 0.8 g / ml.
If the apparent bulk specific gravity is less than 0.3, the particles may flutter or float during production, making mixing difficult. On the other hand, if it is larger than 2.0, sedimentation occurs during mixing at the time of production, and the particles are separated and mixing becomes difficult. In addition, the apparent bulk specific gravity in the present invention is a value measured according to JIS K6721.

Hereinafter, the method for preparing the polyamino acid particles of the present invention will be described more specifically, but the method for preparing the polyamino acid particles of the present invention is not limited by the following description. A polyamino acid is dissolved in pure water to prepare a polyamino acid aqueous solution. The cross-linking agent is dissolved in a water-miscible organic solvent such as pure water or ethanol, and mixed with an aqueous solution of polyamino acid so as to be 0.01 to 10 mmol per 1 g of polyamino acid. At this time, a surfactant, a pigment, a dye, and the like may be allowed to coexist. After mixing, the mixture is allowed to stand for a certain period of time until the crosslinking reaction sufficiently proceeds. If a precipitate is obtained after standing,
After thoroughly washing with pure water or a water-miscible organic solvent such as ethanol or acetone, for example, crushing in a mortar or the like, drying under heating, reduced pressure or freeze-drying, and then a water-miscible organic solvent such as ethanol or acetone And then crushed with various pulverizers such as a hammer mill, a jet mill and a mortar, and dried under heating or reduced pressure. Depending on the compatibility of the form of use later, drying may be carried out as a mass, but powdering is more advantageous in terms of drying. The dried powder is again finely pulverized using a hammer mill or the like, and then sieved as required, whereby particles having a certain particle size distribution can be obtained.

The average particle diameter of the polyamino acid particles of the present invention is preferably 0.5 to 20 μm, more preferably 1 to 15 μm. Further, 2 to 13 μm
Is more preferred. The average particle size of the polyamino acid particles of the present invention is determined by Coulter Coulter Counter TA
Measured using -11.

Next, the inorganic particles used in the present invention will be described. The inorganic particles used in the present invention are preferably at least one selected from inorganic particles having a Mohs hardness of 5 or more. Specific compounds constituting the particles include titanium oxide, silicon oxide, zirconium oxide, oxides such as aluminum oxide, nitrides such as titanium nitride and silicon nitride, metal salts such as calcium carbonate and magnesium carbonate, natural mica, Examples include, but are not limited to, synthetic mica, talc, clay, and the like. The inorganic particles of the present invention are preferably oxides, more preferably silicon oxide, titanium oxide and aluminum oxide, and most preferably silicon oxide. These compounds can be used alone or in combination of two or more. When the Mohs hardness of the inorganic particles in the present invention is less than 5, the surface energy of the particles is small, and the desired compatibility with the polyamino acid particles may not be exhibited. In addition, the particles themselves have low strength, and may be broken by contact such as impact, and this may serve as a starting point to cause damage or the like.

The apparent bulk specific gravity of the inorganic particles of the present invention is 0.1.
It is preferably from 1 to 0.5 g / ml, more preferably from 0.11 to 0.3 g / ml. The average particle size of the inorganic particles of the present invention is preferably 0.01 to 5 μm, and more preferably 0.015 to 3 μm.
In addition, the average particle diameter of the inorganic particles of the present invention is a laser diffraction scattering method when the average particle diameter is smaller than 1.0 μm, and when the average particle diameter is 1.0 μm or more, a Coulter counter TA-II manufactured by Coulter Co., Ltd. Measured. The polyamino acid particles of the present invention and the inorganic particles have a mixing ratio of 99: 1 to 1
1:99 (mass ratio) can be used. A more preferred mixing ratio is from 90:10 to 10:90, particularly preferably from 80:20 to 30:70.

When the polyamino acid particles and the inorganic particles contained in the coating composition containing the polyamino acid particles and the inorganic particles of the present invention are mixed with each other, when the particles are mixed, they are mixed at 23 ° C. in a solvent used for the coating composition. In 0.
It has an apparent bulk specific gravity of 02 to 0.30 g / ml.
In the present invention, a more preferable apparent bulk specific gravity is 0.1.
05 to 0.29 g / ml, particularly preferably 0.1 to 0.29 g / ml.
０．２0.28 g / ml.

The main solvents used in the coating composition of the present invention include water, saturated hydrocarbons, aromatics,
Alcohol-based, ketone-based, ether-based, and cellosolve-based solvents include, for example, water, hexane, cyclohexane, ethyl acetate, butyl acetate, amyl acetate, ethylene glycol ethyl ether acetate, toluene, xylene, methyl alcohol, ethyl alcohol, isopropanol, Preferred are n-propanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, isopropyl ether, methyl cellosolve, ethyl cellosolve, ethylene glycol and diethylene glycol.

In the present invention, the main solvent used in the coating composition refers to a solvent used in a large amount by volume among solvents used in the coating composition, and excludes a solvent used only in a small amount. A thing. The average particle size of the inorganic particles of the present invention is preferably smaller than that of the polyamino acid particles. This is because it is considered that the adsorption of the inorganic particles on the surface of the polyamino acid particles acts to achieve both the matting effect and the feel of the present invention. Therefore, rather than separately adding the polyamino acid particles and the inorganic particles of the present invention to the coating composition, first,
Mixing the polyamino acid particles and the inorganic particles to form a single composition and then mixing it with the coating composition further enhances the effect. The coating composition of the present invention,
For example, it can be a paint, a surface treatment material, and a surface treatment agent. The coating composition of the present invention may further contain additives used in the coating composition.

The coating composition of the present invention is generally based on a film-forming element called a so-called solid synthetic resin such as a vinyl chloride resin, an epoxy resin, an acrylic resin, a urethane resin, a phenol resin and a vinyl acetate resin, It comprises a coating film sub-element such as a plasticizer, a curing agent, an emulsifier or a thickener, a pigment and a coating film forming auxiliary element, and is selectively used depending on the type of coating film to be formed. In addition, the coating film forming elements include drying oils such as linseed oil, eno oil, cinnamon oil, improved drying oils such as urethanized oils, epoxidized oils, and other liquid synthetic resins such as saturated polyesters and urushi. Natural resins such as natural phenol, rosin, shellac and koval, processed resins such as ester rubber and lime rosin,
There are cellulose derivatives such as nitrose cellulose, acetyl cellulose and acetyl butyl cellulose, rubber derivatives such as chlorinated rubber and cyclized rubber, and water-soluble binders such as polyvinyl alcohol, carboxymethyl cellulose and casein.

Examples of the pigment include titanium white, zinc white, lithopone, lead white, cadmium, red iron, toluidine red, graphite, iron yellow, titanium yellow, benzene yellow, chromium oxide, phthalocyanine green, konjo, carbon Color pigments such as black, and extender pigments such as metal powder pigments and light powders can be used.

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 [Polyamino acid particles] Polyamino acid was produced by the following steps: (a) Alkali-treated gelatin (manufactured by Konica Gelatin)
Was dissolved in warm water at 50 ° C., and 0.1% of alkali-treated gelatin was dissolved.
Adding 0.1-0.3% by weight of alkaline protease,
The treatment is performed at 50 ° C. for 1 hour to 3 days. (B) A residue obtained by extracting gelatin from ossein is immersed in water, an alkali protease of 0.01 to 0.3% by weight of the residue is added, and the mixture is treated at 50 ° C. for 1 hour to 3 days, and then treated with chitosan. Degreasing. It was done by doing.

A polyamino acid having a tyrosine content number and a molecular weight per 1000 amino acids shown in Table 1 obtained by the production method of the above (a) and (b) shown in Table 1 was purified at 50 ° C. by 5 times the mass ratio. It was dissolved in water to obtain a polyamino acid aqueous solution. An aqueous solution obtained by dissolving the amount of the crosslinking agent shown in Table 1 in the mass ratio of the polyamino acid to the aqueous solution of polyamino acid in pure water so as to be equivalent to the amount of the polyamino acid aqueous solution. Was slowly added with stirring. In Table 1, the crosslinking agent (C) was CH ₂ = CHSO ₂ CH ₂ CH
₂ is a _{CONHCH 2 CH 2 NHCOCH 2 CH 2} SO 2 CH = CH 2. The prepared solution was placed at 25 ° C. for 24 hours, and the resulting gel was freeze-dried and pulverized while washing with acetone in a mortar. After drying, it was further pulverized using a hammer mill. Particles having a certain particle size distribution were collected using a sieve during the pulverization, and the sample No.
1, 2, 3, 4, and 9 were obtained. Also, using bovine dermal gelatin instead of the polyamino acid of the present invention, sample No.
12 was obtained. Sample N was used except that no crosslinking agent was used.
Sample No. 14 was obtained in the same manner as o.3. Table 1 shows the average particle size and apparent bulk specific gravity of the obtained sample.

A polyamino acid having a tyrosine content number and a molecular weight of 1,000 amino acids shown in Table 1 obtained by the above-described production methods (a) and (b) shown in Table 1 was added to a 50 ° C. In pure water to obtain a polyamino acid aqueous solution. An aqueous solution obtained by dissolving the amount of the crosslinking agent shown in Table 1 in the mass ratio of the polyamino acid to the aqueous solution of polyamino acid in pure water so as to be equivalent to the amount of the polyamino acid aqueous solution. Was slowly added with stirring. The resulting white precipitate was filtered, washed well with pure water and then with acetone, dried in a desiccator under reduced pressure, and ground using a hammer mill. After washing with pure water and acetone, it was dried once again under reduced pressure in a desiccator and further pulverized using a hammer mill. Particles having a certain particle size distribution were collected using a sieve during the pulverization, and sample Nos. 5, 6, 7, 8, 10, and 11 were obtained. In addition, a sample No. 13 was similarly obtained by using bovine dermal gelatin instead of the polyamino acid of the present invention. Table 1 shows the average particle size and apparent bulk specific gravity of the obtained sample.

The odor of the obtained samples Nos. 1 to 14 was measured. Odor is measured by the odor measurement device "Odor Sensor
SF-105 "(manufactured by Mutual Pharmaceutical Co., Ltd.) and 900
After heating the sealable measuring bottle of 45 ml to 45 ° C., 1 g of sample particles were added thereto, and the sensor part of the odor sensor was further inserted, and while maintaining the temperature at 45 ° C., the odor in the measuring bottle after 20 minutes was measured. The strength was measured. According to this method, a sample having an odor exhibits an odor intensity of 30 or more. Odor was evaluated from the obtained odor intensity according to the following evaluation criteria. Table 1 shows the obtained results. [Evaluation criteria] The odor was evaluated according to the following evaluation criteria. When the odor intensity is 30 or more ×, 10 or more and less than 30, Δ 5 or more 10
Less than ○ and less than 5 were rated ◎.

[0044]

[Table 1] [Inorganic particles] The inorganic particles used are shown in Table 2.

[0045]

[Table 2]

Using the polyamino acid particles shown in Table 1 and the inorganic particles shown in Table 2, particle mixture compositions A to J comprising the polyamino acid particles and inorganic particles shown in Table 3 were prepared. The mixing of the polyamino acid particles and the inorganic particles was performed at 2500 rpm for 5 minutes using a machine such as a Henschel mixer. In the solvent mixture shown in Table 3 of the obtained mixed composition, 23
The apparent bulk density at ℃ was measured. The addition amount of the polyamino acid particles and the inorganic particles was shown by mass ratio (%) when 100 g of the composition was prepared.

The composition containing the polyamino acid particles and the inorganic particles and the solvent are mixed by adding the composition to a solvent 10 times the amount (by mass) and stirring and dispersing the mixture with a three-one motor. Was.

[0048]

[Table 3]

As a base resin, a vinyl chloride resin is used.
g, solvent 45 g, silicon-based defoamer 0.02 as auxiliary agent
g, 35 g of the compositions A to J shown in Table 3 were mixed to prepare a coating material. As the solvent, compositions A to J shown in Table 3 were used.
Was used. Apply this paint to a thickness of 500μ
By coating on a polycarbonate plate of m, coating samples A to J were adjusted, and the feeling of touch was evaluated. The evaluation of the feeling of touch was made by 20 randomly selected individuals who actually touched the coated sample, and the sensitivity was evaluated according to the following evaluation criteria. [Evaluation Criteria] 5: Very excellent. 4: Excellent 3: Normal 2: Inferior 1: Very inferior Also, the odor intensity was measured, and the odor was evaluated from the obtained odor intensity according to the evaluation criteria shown above. Table 4 shows the obtained results.

[0050]

[Table 4]

[0051]

The coating composition comprising the polyamino acid and the inorganic particles of the present invention has a good touch and suppresses the generation of odor.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 BA192 CD021 CF021 CG001 DA001 DB001 DG001 HA216 HA286 HA316 HA446 HA526 HA536 HA546 JA02 JA05 JA18 JA20 JA21 JA26 JA33 JA56 KA06 KA08 KA20 LA03 MA07 MA08 MA10 NA01 PA19 PB02

Claims (10)

[Claims] 1. A main solvent in a coating composition containing polyamino acid particles and inorganic particles, wherein the polyamino acid particles and inorganic particles are mixed with the polyamino acid particles and inorganic particles. At 23 ° C.
A coating composition comprising polyamino acid particles and inorganic particles having an apparent bulk specific gravity of 2 to 0.30 g / ml. 2. The coating according to claim 1, wherein the main solvent is at least one selected from water, hydrocarbons, aromatics, alcohols, ketones, ethers and cellosolves. Composition. 3. The main solvent is hexane, cyclohexane, ethyl acetate, butyl acetate, amyl acetate, ethylene glycol ethyl ether acetate, toluene, xylene, methyl alcohol, isopropanol, n-propanol, butanol, acetone, methyl ethyl ketone,
The coating composition according to claim 1 or 2, wherein the coating composition is at least one selected from cyclohexanone, isopropyl ether, methyl cellosolve, ethyl cellosolve, ethylene glycol, and diethylene glycol. 4. The polyamino acid particles have an apparent bulk specific gravity of 0.
The coating composition according to any one of claims 1 to 3, wherein the coating composition has a bulk density of 3 to 2.0 g / ml and an apparent bulk specific gravity of the inorganic particles of 0.1 to 0.5 g / ml. 5. The polyamino acid particles having an average particle size of 0.5 to 0.5.
The average particle size of the inorganic particles is 20 μm, the average particle size of the inorganic particles is 0.01 to 5 μm, and the average particle size of the polyamino acid particles is larger than the average particle size of the inorganic particles. The coating composition according to any one of the above. 6. The coating composition according to claim 1, wherein the polyamino acid particles and the inorganic particles are added as a premixed mixture. 7. The coating composition according to claim 1, wherein the inorganic particles are inorganic particles having a Mohs hardness of 5 or more. 8. The coating composition according to claim 1, wherein the inorganic particles are at least one kind of particles selected from oxides, nitrides, metal salts, mica, and talc. object. 9. The coating composition according to claim 1, wherein the polyamino acid particles are particles comprising a polyamino acid having tyrosine of 4.0 or less per 1,000 amino acids. 10. A paint, wherein the coating composition according to claim 1 is a paint.