JPS61272272A - Fibroin-coated easily dyeable pigment and its production - Google Patents

Abstract

PURPOSE:To obtain the titled pigment of outstanding coloring matter adsorptivity, color-developing ability, moisture retainability, etc., for use in coatings, cosmetics, foods, etc., by coating the particle surface of aluminum mordant with regenerated fibroin film containing specific proportion of hot water-insoluble fibroin of beta-type structure. CONSTITUTION:The objective pigment can be obtained by hydrolysis of (A) a suspension of aluminum mordant with (B) 0.02-20wt times (based on the particles of the component (A)) of the regenerated fibroin film (e.g., one having >=10% crystallinity) containing >=50wt% of hot water-insoluble fibroin of beta-type structure. This pigment is such that the particle surface of the component (A) is coated with the film of the component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fiproin-coated easily dyeable pigment and a method for producing the same, and more specifically, the present invention relates to a fiproin-coated easily dyeable pigment and a method for producing the same, and more specifically, the present invention relates to a fiproin-coated easily dyeable pigment and a method for producing the same.
It is substantially coated with a film of fiproin that is regenerated by coagulating a solution of fiproin (hereinafter referred to as regenerated fiproin), and has outstanding adsorption activities such as dye adsorption, color development, moisture retention, and fragrance retention. In particular, the present invention relates to a fiproin-coated easily dyeable pigment suitable as a raw material for fine powder uncolored pigments for paints, cosmetics, and foods, and a method for producing the same.

(Prior art) Pigments conventionally used in paints and cosmetics tend to aggregate or precipitate in water dispersion media, and their oil absorption is inhibited in oil dispersion media, causing them to become oily. It has the drawback of poor dispersion and easy coagulation. Furthermore, when these are spread, they absorb moisture and gas from the spreader, causing separation from the spreader and impairing the spreadability. Especially when it comes to cosmetics, etc., they can strip moisture and oil from the skin, causing dehydration, degreasing, dryness, and other rough skin conditions.
It also has drawbacks in smoothness, etc., and it is difficult to achieve a sufficient cosmetic effect if left as is.

For the purpose of modifying such pigments, methods such as Japanese Patent Publication No. 28-260 and Japanese Patent Publication No. 27-299 have been proposed, but such fiproin-adhered pigments have insufficient adhesion and elongation oil absorption. Moreover, the fiproine is easily caked by water, sweat, etc., and is easily separated, making it difficult to produce a good cosmetic effect. On the other hand, silk powder (powder of fiproin alone) is said to have the characteristics of a good silk-like feel, gloss, UV gland absorption, moderate hydrophilicity and lipophilicity, and good adhesion to the skin. For this reason, it has been mixed and used in powdered cosmetics and the like.

However, fibrous silk powder (for example, Japanese Patent Publication No. 40-24920), medium-grained silk powder (Japanese Patent Publication No. 26-4947), etc. produced by conventional pulverization methods are microscopically uniform, and are common pigments for cosmetics. It is impossible to mix with fiproin, and in order to maintain the covering power and gloss of pigments (Merck, titanium oxide, mica, etc.), only a few percent of the pigments are allowed to be mixed, so the original excellent properties of fiproin can be fully expressed. cannot be granted. In order to take advantage of the properties of fiproin, it is ideal to mix it microscopically uniformly, that is, to mix it in such a way that the surface of the pigment particles is hidden (covered) by the fiproin particles. It is completely impossible in terms of diameter.

The present inventors have previously discovered that the particle surface of the base pigment is coated with a regenerated fiproin film, and that at least 50% by weight of the regenerated fiproin is composed of hot water-insoluble fiproin (β-type structure). proposed a fiproin-coated pigment and its manufacturing method (Special Publication No. 1983).
-11577).

The invention relates to white pigments, colored pigments, extender pigments, pearl pigments, etc. for paints or cosmetics, such as talc, kaolin, mica, calcium carbonate, titanium oxide, zinc oxide, titanium mica, kaolin, magnesium carbonate, and iron oxides. , zinc stearate, magnesium stearate, magnesium silicate, organic pigments, or composites thereof as base pigments, while copper-ethylenediamine aqueous solution, copper hydroxide-ammonia aqueous solution, copper hydroxide-alkali-glycerin aqueous solution, lithium bromide aqueous solutions, aqueous solutions of calcium or magnesium or zinc hydrochlorides or nitrates or thiocyanates;
After mixing and dispersing the pigment in an 8 to 20 J 1% by weight fiproin solution obtained by dissolving the refined silk raw material in at least one solvent selected from the group consisting of an aqueous sodium thiocyanate solution or by dialysis after dissolution, Coagulating and precipitating (regenerating) fiproin by at least one of the following treatments: mixing coagulating salts, blowing air, isoelectric focusing, ultrasonication, and stirring at a high shear deformation rate, followed by dehydration, drying, and pulverization. A fiproin-coated pigment and a method for producing the same, characterized in that the particle surface of the pigment (base pigment) is substantially covered with a film of recycled fiproin, and the coating state is usually different from that of guests. uniformity. At least 501% (preferably at least 80%, more preferably at least 90% by weight) of the regenerated fiproin film is composed of fiproin (βm structure) insoluble in hot water.

(Problems to be Solved by the Invention) The fiproin-coated pigment described above has good adhesion, extensibility,
It has excellent dispersibility, miscibility, coating properties, oil absorption, balance between hydrophilicity and lipophilicity, antiperspirant properties, feel, skin protection properties, film stability, etc., and is extremely useful as a pigment for cosmetics, food, and paints. It is useful. However, although the fiproin-coated pigment is significantly superior to conventional pigments in terms of dyeability, it is unsatisfactory in practical terms in terms of the amount of dye being dyed and the water resistance of the dye. In particular, it has little effect on dyes other than acid dyes for clothing and reactive dyes, and it is a national disaster to dye it and use it in cosmetics.

Generally, coloring agents that can be used in the cosmetics and food fields are limited to legal cosmetic dyes and food dyes (including natural dyes), which have poor coloring properties. Statutory dyes and food dyes for cosmetics generally have extremely weak dyeing or coloring power to proteins compared to acid dyes and reactive dyes for clothing, and the previously proposed ATM material does not contain these dyes. Even if it is colored, it has poor solidity, and even when washed with water, the temporarily colored dye is gradually eluted, and especially when a large amount of substrate pigment is blended, it is decolored until it becomes almost colorless.

In order to solve this problem, the present inventors previously proposed fiproin in which N,N-dialkylamine ethyl methacrylate or a copolymer containing this as a main component is fixed to silk powder, and a method for producing the same ( JP-A-57-1
91815).

The polyacrylate-fixed fiproin can be applied to fiproin-coated pigments, as can be easily inferred from the description of the specification, but it goes without saying that it can also be applied to fiproin-coated pigments using the method described above. If a large amount of fiproin is blended or if the dye is a natural pigment, it is not possible to obtain a fiproin-coated pigment that is fully satisfactory in terms of dyeing amount.

In addition, as a method for converting dyes into pigments using silk powder, a cosmetic composition (Japanese Unexamined Patent Application Publication No. 10507/1983) has been proposed in which a pigmented powder of a pigment extracted from Sikon is blended. This method is simply an application of the mordant coloring method using natural pigments for silk fibers, which has been applied since ancient times, to powder, and the dye content is small, resulting in a light color at best, and is generally not required as a coloring pigment. However, it is difficult to obtain a pigment that is far from the level of 5% or more, preferably 10% or more, and more preferably 20% or more.

That is, the mordant color of silk fibers is caused by weak acid salts of aluminum such as aluminum acetate being gradually hydrolyzed into aluminum hydroxide or basic aluminum acetate in an aqueous solution and precipitated in the system. This is an application of adsorption of materials, and voids in silk fibers (Voids: @holes)
For example, an aqueous solution of aluminum acetate is permeated into the dye to cause the hydrolysis, unreacted aluminum acetate is removed by washing with water, and the precipitated remaining aluminum hydroxide or basic aluminum acetate is used as a mordant for dyeing. In the case of aluminum acetate, the amount of aluminum hydroxide or aluminum oxide precipitated by hydrolysis and remaining in the voids is at most 8 to 6% (by weight) of the #4 fiber, and some of this is Since it acts as a mordant, naturally there is only a small amount of shikonin dyed, and the result is a light-colored pigment (Reference, edited by Kitai Shusho, Structure of Tsuzuki Silk Thread, 5
87 pages, published by Shinshu University Faculty of Textile Technology).

(Means for Solving the Problems) The present invention improves all the drawbacks of the prior art, and aims to improve adhesion, extensibility, dispersibility, miscibility,
It has excellent coating properties, oil absorption, balance between hydrophilicity and lipophilicity, anti-perspirant properties, feel, skin protection properties, and film stability, and is especially excellent in dyeing properties and coloring properties, and can be used in cosmetics, food, paints, etc. The object of the present invention is to provide an extremely useful fiproin-coated easy-to-dye pigment and an industrially advantageous manufacturing method thereof.

That is, in the present invention, the particle surface of the aluminum mordant is formed by a recycled fiproin film]5! qualitatively coated, and at least 503 L% of the fiproin coating is β.
Fiproin-coated product dye pigment, which is hot water-insoluble fiproin with a type structure, and an aqueous fiproin solution obtained by dissolving silk fibers, BA glue, aluminum sulfate, aluminum chloride, aluminum nitrate, and acetic acid. a suspension of an aluminum mordant obtained by hydrolyzing at least one aluminum salt selected from aluminum;
Mix fiproin in an amount of 0.02 to 20 times the weight of the aluminum mordant in terms of aluminum hydroxide, or add aluminum salt to the aqueous fiproin solution in the same manner as above to make the same weight. The method for producing a fiproin-coated easily dyeable pigment is characterized in that after mixing, water decomposition is performed, and then, after sufficient stirring, fiproin is coagulated and precipitated, dehydrated and dried, and pulverized.

In the fiproin dyeable pigment of the present invention, the surface of the fine particles of the alkynicum mordant is substantially coated with a film of recycled fiproin, and the state of the coating is generally specific. The fiproin film is composed of at least 50% by weight, preferably at least 90% by weight, of fiproin (β structure) which is insoluble in hot water.

If it is less than 50mji%, the hydrophilicity of fiproin will be extremely strong, the pigment particles will stick and caking with water or sweat, and become secondary particles (particles aggregate to become giant particles), and the water In dispersion media (water-based paints and cosmetics), the film tends to be detached, and in oil dispersion media (oil-based paints and cosmetics), the dispersibility tends to decrease. In addition, the stretch and feel of the fabric when it is made becomes worse.

In the present invention, hot water-insoluble fiproin means: □
Request fiproin that does not dissolve even after boiling in hot water at 100°C for 15 minutes.

The hot water-insoluble fiproin has a substantially β-type structure in which the intermolecular hydrogen bonds of the fiproin are substantially formed. Although the degree of crystallinity of the regenerated fiproin film varies depending on the conditions of the manufacturing process, it is usually 10% or more, preferably 20% or more, and does not exceed 48%.

The crystallinity of the fiproine film in the coated pigment of the present invention is generally the crystallinity of natural silk threads and refined silk raw materials (approximately 60
~55%) The height is also relatively low, and the special public interest rate is
The crystallinity of the regenerated fiproin film obtained by the methods of No. 1 and Japanese Patent Publication No. 27-299 is also extremely high.

The thickness of the regenerated fiproin film is 0.0 with respect to the base pigment.
2 to 20 weight hakama, preferably 0.05 to 2 denbon times. 0.021 [If the amount is smaller, the dyeing property is good, but the particle surface of the base pigment is not substantially covered with the film, and it has good adhesion, spreadability, dispersibility, It is difficult to sufficiently impart and express covering power, skin protection properties, feel, etc., and when the weight exceeds 20%, the content of aluminum mordant is small, so when using this as an easily dyeable pigment, the amount of dyeing However, it has poor color development properties, and only a very pale colored pigment can be obtained, and even if it is used as a white pigment, it has poor hiding power as a pigment.

The thickness of the regenerated fiproin film is usually 0.01 to 50μ.

The fiproin-coated easily dyeable pigment according to the present invention can be used in paints,
In addition to being used as a raw material for coloring pigments for cosmetics and food,
Although it can be applied to a wide range of uses by utilizing the above characteristics, it is preferable to use it in a fine powder form when used as a cosmetic additive or food additive. In this case, the particle size of the fiproin-coated pigment is 0.05 to 100μ, preferably 0.05μ.
-60μ, particularly preferably 0.1-80μ.

When the particle size becomes larger than 100 μm, adhesion to the skin, affinity, spreadability, etc. tend to deteriorate.

The base grains in the fiproin-coated easily dyeable pigment of the present invention are an aluminum mordant. Although commercially available aluminum hydroxide or the like may be used, it is preferable to generate the aluminum salt by hydrolysis in the reaction system in order to develop good mordant power and rake power.

Hydrolysis is generally carried out by adding an alkali such as sodium hydroxide, sodium carbonate, or aqueous ammonia to aluminum chloride, aluminum sulfate, alum, aluminum nitrate, or aluminum acetate. It is also possible to gradually proceed with hydrolysis and precipitate aluminum hydroxide and basic aluminum acetate by simply stirring or leaving the aqueous solution at room temperature without adding it. The maximum particle size of the base pigment is usually 0.08
~100μ.

The coating state of the fiproin film of the present invention is determined by dyeing with the acid dye Tartrange N8 or the silk dye Shea 2 Sten dye, and the uniform and clear dyeing state and the base pigment (untreated).
The average molecular weight of the regenerated fiproin in the coated pigment is 50,000 or more, preferably 80,000 or more, as determined by microscopic observation of unstained areas.

This is because if the average molecular weight is too low, the hydrophilicity will become stronger than necessary.

According to the present invention, the fiproin-coated easily dyeable pigment having the excellent features described above can be produced by the method described above.

That is, the solvents for fiproine that can be used in the present invention include copper-ethylenediamine aqueous bath solution, hydroxide silk-ammonia aqueous solution (
Scheweisser's reagent), copper hydroxide-alkali-glycerin aqueous solution (Rohe's reagent), lithium bromide aqueous solution, calcium, magnesium or zinc hydrochloride or nitrate or thiocyanide #salt aqueous solution, sodium thiocyanate water bath solution. Calcium or magnesium hydrochloride or nitrate is preferred from the viewpoint of cost and usage.

The degree of hardness of these aqueous solutions varies depending on the type of solvent used, temperature, etc., but the degree of hardness of metal salts, etc. is usually 10 to 80%.
, Okibe or 20 to 70% by weight, particularly preferably 25 to 70%
It is 60% by weight.

The refined silk raw materials used in the present invention are cocoons, raw silk, cocoon scraps, raw silk scraps, bis, SB cotton, silk cloth scraps, and cape boulet in hot water or enzymatic treatment in the presence of an activator as necessary according to a conventional method. Sericin is removed in the presence of hot water and dried.

The fiproin solution (abbreviated as fiproin solution) prepared by dissolving an appropriate amount of refined silk raw material in the fiproin solvent used in the present invention is prepared by adding the refined silk raw material to the solvent at a temperature of 60 to 95°C, preferably 70S to 85°C. It is obtained by uniformly dissolving it in a device such as a kneader. This fiproin solution can be used without dialysis if it is coagulated using a coagulant salt, but in other coagulation processes it is better to use it after desalting by dialysis. Even when coagulating using a coagulating salt, dialysis is still preferred.

When used without dialysis and when ammonium sulfate or sodium sulfate is used as a coagulating salt, or sodium carbonate is used as a hydrolyzing agent, calcium and magnesium sulfates and carbonates will be mixed in the coagulated product.

~15'i11%, particularly preferably 5-1031i
It is li%.

If it is less than 2"im%, the coagulation time of the fiproin solution becomes long, which is uneconomical, and a non-uniform gel body of silk fiproin is formed on the surface of the substrate particles.
%, it may be difficult to dehydrate the gel body in the next dehydration step.

Furthermore, outside the above ranges, the proportion of fiproin that is insoluble in hot water (β81!) is less structured, and the regenerated fiproin film is prone to stickiness, secondary particle formation, film peeling, etc. in sweat or water dispersion medium. Easy to generate.

In the present invention, the suspension of aluminum mordant is alum,
An aqueous solution of sodium hydroxide, sodium carbonate, or ammonia is gradually mixed without stirring into an aqueous solution of aluminum chloride, aluminum chloride, aluminum acetate, or aluminum acetate, and the pH is 6 to 6.
It is produced by a hydrolysis reaction with the end point being 7. In the case of aluminum acetate, the hydrolysis proceeds even if the aqueous solution is allowed to stand for one or two days, and a precipitate is obtained. When mixing the aluminum mordant suspension and the fiproin solution, the ratio of the recycled fibruin film to the aluminum mordant fine particles is 0.
．． Although it is preferable to double the amount to 0202-2O&, in addition to aluminum hydroxide, a small amount of basic acid salts such as basic aluminum acetate are also formed in the mordant produced by hydrolysis of aluminum salt.

Therefore, the predetermined amount of aluminum salt for defining the above proportions is determined by the amount of aluminum mordant produced, aluminum hydroxide, di(OR), yield lO.
Calculated assuming that it is 0%.

The concentrations of the aluminum salt and alkali used in the reaction do not define the essence of the present invention in any way, but if the concentration of the salt and alkali is too high, the aluminum mordant produced will be coarse. It is not within the range of 100μ, and if it is too thin, the amount of fiproin will be less than 2% when mixed with a fiproin solution, which is not preferable. For this reason, the concentration of the aluminum salt and the alkali used is preferably about 5 to 8011i% on anhydrous basis.

A mixed ore of an aluminum mordant suspension and a fiproin solution, a pre-produced suspension and a fiproin solution may be mixed in a predetermined amount, or after mixing a predetermined amount of aluminum salt and a fiproin solution, an alkali is added while stirring. They may be mixed to form an aluminum mordant in the production system of the fiproin-coated dyeable pigment.

As for the coagulation means of fiproin in the present invention, as mentioned above, when the fiproin solution is not dialyzed, coagulation 14: mixing of salt is carried out, and when desalting is carried out by dialysis, mixing of coagulating salt and rapid shearing are performed. The application may be carried out by stirring at high speeds or a combination thereof.

Coagulating salts are salts that can coagulate fiproin in the fiproin solution, such as sodium chloride,
Examples include potassium chloride, sodium sulfate, potassium sulfate, and ammonium sulfate.

The coagulating salt may be used as is, but the concentration of the coagulating salt in the warm aqueous solution is aimed so that the concentration of the mixed solution with the fiproine aqueous solution is usually 6 to 1 OIj%.

Fiproin solidifies and precipitates even with stirring alone, but in this case it must be done at a fast deformation speed, usually 50/sec.
It is carried out at a shear deformation rate of c or more, preferably 100/sea or more. The stirring time depends on the concentration of the aqueous solution or the shear deformation speed J
Although it differs depending on the conditions such as X, gelation usually takes place for 1 hour or more.

In particular, when aluminum acetate is used as a raw material and hydrolysis is carried out only by stirring or leaving it at room temperature without mixing an alkali, an aqueous solution of aluminum acetate and a fiproin solution are mixed, and this is first mixed with the 1ITI coagulation method. Coagulate fiproin.

The solidified material at this stage is mainly a gel of fiproin containing an aqueous solution of aluminum acetate.
2. By leaving it for a long night, aluminum acetate is hydrolyzed and a fiproin gel containing an aluminum mordant is produced.

After the fibroin solution is coagulated by the above-mentioned coagulation means, the coagulated product (the base particles are covered with gel-like regenerated fiproin) is subjected to a dehydration step to separate it from liquid components (water, etc.). Ru.

It is preferable to use a centrifugal dehydrator for dehydration, and by this dehydration, the regenerated fiproin on the surface of the υ substrate fine particles is usually dehydrated to about 100 to 5001% by weight based on the dried product. After dehydration, it can be easily dried to an absolutely dry state through a drying process. Drying is at room temperature or 60-120°C under normal pressure or reduced pressure.
It will be held in

Fiproin-coated easily dyeable pigments with better dyeing strength and coloring properties can be obtained by drying under reduced pressure at as low a temperature as possible, usually below 80°C.

The thus obtained dried product (aggregate of pigment particles coated with recycled fiproin) is easily pulverized by using a pulverizer such as a hammer mill or jet mill. The particle size (R large particle size) company, usually 0.05-100
μ, preferably 0.05 to 60μ, particularly preferably 0.
It is adjusted to 1 to 80μ.

The thus obtained fiproin-coated pigment of the present invention has at least 501% of the regenerated fiproin film composed of hot water-insoluble fiproin, and has an appropriate balance of hydrophilicity and lipophilicity, antiperspirant properties, moisturizing properties, and water resistance. It has good properties and dispersibility (dispersibility in dispersion media such as water and oil), and is unlikely to cause secondary particles, caking, excessive swelling, etc. due to sweat, etc.
Fiproin can be rendered insolubilized in hot water (
The proportion of hot water-insoluble fiproin, β-type structure conversion rate) was 9.
It can be promoted (increased) to 0% or more, and the above characteristics can be further improved.

As for the β-ization treatment, the powder t-
Heat treatment with saturated steam at 50°C or higher, especially 80-120"O, or in a water bath solution such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, etc., or in an organic solvent such as acetone or alcohol before drying. This is done by processing.

When these β-forming treatments are carried out, it is possible to promote the insolubilization of regenerated fiproin in hot water (increase in the rate of β-type structure) as described above, and further increase the crystallinity of fiproin. It is easy to obtain an attractive fiproin-coated pigment having a hydrophilic and lipophilic performance, antiperspirant properties, dispersibility in the dispersion line, film stability, and dyeing stability.

(Effects of the Invention) The fiproin-coated easily dyeable pigment of the present invention has a structure in which the surface of the fine particles of the aluminum mordant having mordant power and rake power as described above is substantially covered with a film of recycled fiproin. Therefore, it can replace highly eroded colored pigments that are dyed in deep colors and with good water resistance by legal cosmetic dyes, food dyes, and natural dyes. Furthermore, since it is in the form of a fine powder, it has good adhesion to the skin, spreadability,
It has outstanding properties such as feel, moisture retention, PH* impact, covering power, balance between hydrophilicity and lipophilicity, ultraviolet absorption, and skin layer properties. Therefore, it can protect the skin from detachment without the disadvantages seen with conventional pigments, such as dehydration, degreasing, dryness of the skin, and alkalinization of the skin surface.

Furthermore, the regenerated fiproin film is composed of more than 50% by weight of hot water-insoluble fiproin (β-type structure), has a high degree of β structure, and has appropriately oriented molecules, so it is resistant to water and oil. It has excellent uniform dispersibility in total compositions and cosmetics with a dispersion line of , does not cause phenomena such as adhesion, caking, and peeling of secondary particle coating due to sweat.

As mentioned above, the fiproin coated easily dyeable pigment method of the present invention is extremely useful as a raw material for coloring pigments for paints and cosmetics, w4
It is a remarkable product and can provide excellent cosmetic effects and coating effects.

The present invention will be explained in detail below.

The part shown in the examples refers to the it part, and % other than crystallinity (%).
means % by weight. .

Example 1 Silk spinning waste was used as a fip-four-in raw material. 100 parts of this was stirred and kneaded at 95 to 98°C for 8 hours using a solution of 80 parts of Marcel soap and 8000 parts of water, and the remaining layer was mixed. After washing with water, it was dried with hot air at 80°C.

100 parts of a 50% calcium chloride aqueous solution was prepared by mixing 82 parts of calcium chloride (CaOJ2-4H20) with 18 parts of water and heated to 110°C. 10 parts of the refined spinning waste was added to this while stirring for 5 minutes, and the mixture was further stirred for 80 minutes to completely dissolve it.

After cooling the obtained fiptetrayne-calcium chloride solution,
Dialyzed and desalted with cellulose tube, 6% of fiproin
A solution was obtained.

On the other hand, aluminum chloride: 11O19, 6Kg024
1 part was dissolved with water Kl to make 60 parts, and 28% ammonia water was gradually mixed with this while stirring, and a hydrolysis reaction was carried out with the end point of 1H = 6 to 7 to produce aluminum hydroxide: Ajl.
A fine particle suspension containing 7.8 parts (calculated value) of (Ollt)s was obtained. To this was added 1100 parts of a 5% solution of fiproin, and the mixture was stirred at high speed at room temperature to produce a uniformly mixed suspension. Add 8% of sodium sulfate to this suspension while stirring at high speed.
Add and mix 0% aqueous solution to solidify the fiproin solution,
Fiproin was precipitated (regenerated) on the surface of fine particles of aluminum mordant. Next, this was passed through and thoroughly washed with water until no sulfuric acid groups were observed in the p solution. After washing with water, it was centrifugally dehydrated, dried under reduced pressure at 75°C, and then ground in a hammer mill to obtain a fiproin-coated pigment with a particle size of 10 to 80μ.

As a result of measuring this product according to the nitrogen quantitative method of the general test method for cosmetic bases, it was found that the plate of the recycled fiproin coating of the fiproin-coated pigment of the present invention was 0.68% with respect to the aluminum mordant.
6 with X Shigenobu! b. The amount of hot water-insoluble fiproin was 50.1% based on the regenerated fiproin film. The crystallinity of the regenerated fiproin film was 10.1%. Incidentally, the crystallinity of the silk spinning waste (fiproin) powder after scouring was 51%.

Next, dry fine particles of aluminum mordant alone were produced according to Example 1, and conventional fiproin powder (
Silk powder) was mixed at 8% with respect to the aluminum mordant (Comparative Example 1), and the same was mixed at 68% (
Comparative Example 2), aluminum mordant alone (Comparative Example 8)
), 204 parts of aluminum acetate produced by dissolving aluminum hydroxide in acetic acid was dissolved in water to make 4000 parts, 50 parts of silk powder (regenerated fiproin) was stirred and immersed in this, and after being left for two nights, it was washed with water and dried ( Comparative Example 4) was professionally tested for its performance as a cosmetic (powder, etc.) and practical test! It was conducted by 10 people. In addition, each of the microparticles was dyed using a natural dye, shikonin, by a known method.

Crystallinity was measured using X-ray diffraction. The result is the first
Shown in the table.

Table 1 (Note) The above O means very good, 0 means good, Δ means very poor, and × means poor (same as in each table below).

In this way, the fiproin-coated pigment of the present invention has extremely good adhesion to the skin, extensibility (stretchability), and feel, and also dyes shikon pigment in an extremely deep color, making it useful as a coloring pigment for cosmetics. Extremely useful.

Example 2 A 10% solution of fiproin was obtained by scouring, dissolving, and dialysis of silk fabric according to Example 1.

Aluminum nitrate dimu J (No8)a, 9H20
Dissolve 875 parts in water to make 600 parts, gradually mix 10% sodium hydroxide with stirring, and perform hydrolysis in a reaction ending at P4 = 6 to 7 to form a fine particle suspension of aluminum hydroxide. I got it. Next, 400 parts of a 5% solution of fiproin was added and stirred to form a uniform suspension, and then vigorously stirred at mold temperature using a stirring device with a shear deformation rate of 5 Q/sec until fiproin solidified (gelled) and precipitated. Stirred. The system at the initial stage of stirring was an aqueous solution of fiproin with aluminum hydroxide suspended in it, but as stirring continued for 2A-8 hours, fiproin gradually coagulated and precipitated on the particles, and finally the entire system solidified as a single gel-like substance. . The water was removed from the slurry using a centrifugal dehydrator, dried under reduced pressure at 80°C, and then ground to a size of 0.1 to 6 μm using a jet mill. Next, this was subjected to a wet heat treatment with saturated steam at 110° C. for 5 minutes (hot water insolubilization treatment described in 111).

1 of the regenerated fiproin film measured as above.
was 0.28f times the weight of aluminum hydroxide. The performance and dyeability of the fiproin-coated easily dyeable pigment before and after hot water insolubilization treatment according to the present invention were evaluated.
The results are shown in Table 2.

Table 2 Example 8 According to Containment Example 1, silk textile waste was dissolved at twice the strength to obtain a 10% solution of silk fiproin.

204 parts of aluminum acetate prepared by dissolving aluminum hydroxide in acetic acid was dissolved in water to make 800 parts, and 780 parts of a 10% solution of silk fiproin was mixed therewith with stirring. After the mixing was completed, the mixture was vigorously stirred at a stirring speed of 100/sec until fiproin solidified (gelled) and precipitated.

When stirring was continued for 2 to 8 hours, the fiproin gradually became viscous, and finally the entire system solidified as a gel-like substance.

At this point, hydrolysis of aluminum acetate has hardly progressed, and the fiproin gel encapsulates the solution in a swollen state. After this was left for two nights, 1000 parts of a 20% ammonium sulfate water bath solution was added and stirred to crush the gel-like material into fine particles and to perform a beta conversion treatment. Subsequently, water washing, dehydration, and drying were performed in accordance with Example 1, and the jet mill was used to dry the product.
It was ground to IP-5μ.

The base of the regenerated fiproin film of the fiproin easily dyeable pigment obtained had a beta structure ratio of 90.0% and a crystallinity of 26.8%, which was 1.11 times the weight of aluminum hydroxide. In addition, as a base for cosmetics, it has very good feel, adhesion to the skin, spreadability on the skin, and covering properties, and the stainability of Shicon pigments can be dyed in deep colors, making it extremely suitable as a coloring pigment. It was useful.

Example 4 According to Example 2, aluminum sulfate was used as the aluminum salt, and aluminum hydroxide was regenerated (by liquefying the proportion of proine to produce fiproine). It had good adhesion, spreadability, and feel, and also dyed a dark color, making it a useful colored pigment with a degree of crystallinity of 20% or more.

Kanebo I7 Silky Kyo Bijin Co., Ltd.

Claims (10)

[Claims] (1) A fiproin-coated easy-to-dye pigment in which the particle surface of an aluminum mordant is substantially covered with a recycled fiproin film, and at least 50% by weight of the fiproin film is hot water-insoluble fiproin having a β-type structure. (2) The pigment according to claim 1, wherein the regenerated fiproin film has a crystallinity of at least 10%. (3) Regenerated fiproin film is 0.02~
The pigment according to claim 1, which is present in an amount of 20 times by weight. (4) An aluminum mordant obtained by hydrolyzing an aqueous fiproin solution obtained by dissolving silk fibers and at least one aluminum salt selected from alum, aluminum sulfate, aluminum chloride, aluminum nitrate, and aluminum acetate. or a suspension of fiproine in an amount of 0.02 to 20 times the weight of the aluminum mordant calculated as aluminum hydroxide, or add an aluminum salt to the aqueous fiproin solution in the same manner as above. After mixing to the same weight, hydrolysis is carried out, and after thorough stirring, fiproin is coagulated and precipitated.
A method for producing a fiproin-coated easily dyeable pigment, which comprises dehydration drying and pulverization. (5) The method according to claim 4, wherein the hydrolysis is carried out by adding sodium hydroxide, sodium carbonate, or aqueous ammonia, and reaching a pH of 6 to 7 as the end point. (6) The method according to claim 4, wherein the hydrolysis is carried out by leaving aluminum acetate in water for a long time. (7) The method according to claim 4, wherein the solidification and precipitation of fiproin is carried out by stirring at a high shear deformation rate. (8) The method according to claim 7, wherein the shear deformation rate is 50/sec or more. (9) The method according to claim 4, wherein the drying is carried out at 80°C or lower. (10) The method according to claim 4, wherein heat treatment is performed with saturated steam at 50° C. or higher after drying or pulverization.