JP6931304B2 - Fibroin composition - Google Patents

Description

The present invention relates to a composition containing fibroin and the like.

Fibroin is a material having properties such as moisturizing properties, and is used as a material for cosmetics and the like.

For application in such applications, it would be advantageous if fibroin could be used in the form of a liquid (eg, solution or dispersion).

However, it is difficult to dissolve or disperse fibroin in a liquid, and even if it can be temporarily dissolved or dispersed, it immediately aggregates and precipitates, making it difficult to obtain a liquid fibroin that is stable over time. Met.

In Patent Document 1 (Japanese Unexamined Patent Publication No. 2-113066), one or a mixture of polyols selected from the group consisting of divalent or higher polyvalent alcohols, polymers thereof, and polyvinyl alcohols is used in solution concentration. 0.10 to 5.0% (weight), antifungal / preservative in solution concentration 0.02 to 1.0% (weight), and chelating agent in solution concentration 0.02 to 1.0% (weight) A uniform solution of silk fibroin aqueous solution containing (weight) is disclosed.

Japanese Unexamined Patent Publication No. 2-113066

An object of the present invention is to provide a composition containing fibroin and a liquid.

As described above, conventionally, it has been difficult to efficiently obtain a solution or dispersion of fibroin that is stable over time.

Although the above-mentioned Patent Document 1 discloses an aqueous solution of fibroin in a uniform solution state, it assumes stability due to bacterial contamination, and does not assume stability of fibroin itself in a solution.

Further, in Patent Document 1, a polyhydric alcohol having a divalent value or higher is used in a very small amount as a stabilizer for dissolving an antifungal / preservative in water. As described above, conventionally, water has been mainly used as a medium for dispersing or dissolving fibroin.

Under these circumstances, the present inventors can unexpectedly disperse or dissolve fibroin in the polyol by using the polyol as a medium from a completely different viewpoint from Patent Document 1, and such It has been found that the dispersed or dissolved state is relatively stable, and that the dispersed or dissolved state of fibroin can be maintained even if the fibroin is once passed through such a dispersed or dissolved state and then diluted with water or the like.

In addition to the above, the present inventors have obtained various new findings as described below, and have completed the present invention through further diligent studies.

That is, the composition of the present invention contains fibroin and a liquid, and usually satisfies the following conditions (1) and / or (2).
(1) The liquid contains polyol in a proportion of 30% by mass or more with respect to the whole liquid (2) Fibroin contains polyol as a liquid in a proportion of 30% by mass or more with respect to the whole composition. May usually be dispersed or dissolved in the liquid.
Further, in the composition of the present invention, the liquid is selected from, for example, C _2-4 alkane diol, di to tri C _2-4 alkane diol, C _3-6 alkane triol, and di to tri C _3-6 alkane triol. It may contain at least one polyol obtained.
In the composition of the present invention, the proportion of fibroin may be, for example, about 0.001 to 20% by mass with respect to the entire composition.
The composition of the present invention may be a composition having a turbidity of 80 NTU or less when diluted 10-fold with 1,3-butylene glycol.
The present invention also includes a method of producing the composition by mixing fibroin and the liquid.

INDUSTRIAL APPLICABILITY The present invention can provide a composition containing a novel fibroin.
In such compositions, fibroin is usually dispersed or dissolved in the liquid.
And such a dispersed or dissolved state is relatively stable and can be maintained for a long period of time.
Further, the composition of the present invention can efficiently maintain a dispersed or dissolved state even when another liquid (water or the like) is newly added. Therefore, using the composition of the present invention once prepared, various compositions having excellent dispersion or dissolution stability of fibroin can be provided depending on the intended use and the like.

[Composition]
The composition of the present invention (fibroin composition) includes fibroin and a liquid. Then, this liquid is composed of a specific liquid as described later.

(Fibroin)
Fibroin is a protein (scleroprotein), and may be a protein normally secreted by silk moths [for example, various insects such as silk moths (for example, silk moths, wild silk moths, etc.), spiders, bees, etc.].

In particular, fibroin may be made from silk moth cocoons (for example, silk fibroin), and may be made from, for example, cocoons, cocoons, processed cocoon threads (silk threads, etc.), residual threads of processed cocoon threads, etc. good.

The molecular weight of fibroin is not particularly limited and may be appropriately selected depending on the intended use. For example, the weight average molecular weight may be 8000 or more, 15000 or more, 20000 or more, 22000 or more, 25000 or more. The upper limit of the weight average molecular weight is not particularly limited, but may be, for example, 200,000, 180,000, 140000, 100,000, 95,000, or the like. An appropriate range of weight average molecular weight may be set by appropriately combining these upper limit values and lower limit values (the same applies hereinafter).

Fibroin having a relatively low molecular weight (hydrolyzed fibroin, etc.) may be suitable for applications that require penetration into the skin. Fibroin having a relatively low molecular weight may usually easily aggregate or precipitate in a liquid such as water, but in the present invention, even a fibroin having a relatively low molecular weight can be used in combination with a specific liquid described later. , Such aggregation and precipitation can be efficiently suppressed, and a stable composition can be formed.

The molecular weight is not particularly limited, but can be measured by, for example, the following method.
HLC-8320GPC (manufactured by Tosoh Corporation), columns GF-310-HQ, GF-710-HQ and 0.1M sodium acetate aqueous solution / acetonitrile = 75/25 (mass ratio) as the eluent using polyacrylic acid as a standard substance. It can be measured by the GPC (gel permeation chromatography) method using GF-1G-7B (manufactured by Tosoh Corporation).

The shape of fibroin is not particularly limited, and may be, for example, powder (powder granules).

As the fibroin, one synthesized (purified) by a known method may be used, or a commercially available product may be used.

(liquid)
The composition (liquid composition, fibroin mixture, fibroin composition) includes a liquid (sometimes referred to as liquid (B)). In the present invention, as such a liquid (liquid component), a liquid containing at least a polyol (sometimes referred to as polyol (B1)) is used.

The polyol may be in a solid state at room temperature (for example, a solid polyol capable of holding a liquid in a mixed state with another liquid) as long as the composition can be liquid, but it may be usually in a liquid state.

Polyols (polyols) have two or more hydroxyl groups. The number of hydroxyl groups contained in the polyol is not particularly limited as long as it is 2 or more, and may be, for example, 2 to 10, 2 to 8, 2 to 6, 2 to 4, 2 to 3.

When the polyol has a boiling point, the boiling point of the polyol (boiling point of 1 atm) is not particularly limited, but may be, for example, 450 ° C. or lower, preferably 400 ° C. or lower, more preferably 350 ° C. or lower, and 300 ° C. or lower. It may be.
The lower limit of the boiling point (boiling point of 1 atm) of the polyol is not particularly limited, but may be, for example, 100 ° C., 130 ° C., 150 ° C., 180 ° C. or the like.

Specific polyols include, for example, glycols (diols) and polyols having 3 or more hydroxyl groups.

Examples of the glycol include alkanediol [or alkylene glycol, for example, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol (for example, 1,4-butanediol, 1,3-butanediol, 2,3). -Butanediol), pentanediol (eg 1,5-pentanediol), hexanediol (eg 1,6-hexanediol), heptanediol (eg 1,7-heptanediol), octanediol (eg 1,7-heptandiol) _{C 2-10} alcan diols such as 2-ethyl-1,3-hexanediol), preferably C _2-6 alcan diols, more preferably C _2-4 alkane diols], poly alkane diols [eg, dialcan diols]. (Or dialkylene glycol, eg diethylene glycol, dipropylene glycol, etc.), trialcandiol (or trialkylene glycol, eg triethylene glycol, tripropylene glycol), tetraalkanediol (or tetraalkylene glycol, eg tetraethylene glycol) ) Etc.] and so on.

Examples of polyols having 3 or more hydroxyl groups include alkane triol {eg, alcan triol [eg, glycerin, butane triol (eg, 1,2,4-butane triol), hexane triol (eg 1, 2, 6). -Hexanetriol) such as C _3-10 alcantriol, preferably C _3-6 alcantriol], etc.}, polyalcan polyols {eg, polyalcantriol [eg, polyglycerin (eg, diglycerin, triglycerin), etc.) Polyalcantriol, preferably di-tri C _3-6 alcantriol] and the like.

The polyol may be used alone or in combination of two or more.

Among these polyols, in particular, C _2-4 alkanediol (for example, ethylene glycol, propylene glycol, 1,3-butanediol, etc.), poly C _2-4 alcandiol (for example, diethylene glycol, dipropylene glycol, triolethylene, etc.) Di-tri C _2-4 alcandiol such as glycol), C _3-6 alcan triol (eg glycerin), poly C _3-6 alcan triol (eg di-tri C _{3-6 such as diglycerin, triglycerin)} Alcantriol) and the like are preferable.

The liquid may contain a large amount (high concentration) of polyol. For example, the ratio of the polyol to the whole liquid may be 30% by mass or more, preferably 40% by mass or more, further preferably 50% by mass or more, particularly 60% by mass or more, particularly preferably 70% by mass or more, and 75% by mass. It may be mass% or more, 80 mass% or more, 90 mass% or more, and the like.

The liquid may contain other liquids (liquids that are not polyols) as long as they contain polyols. Other liquids (sometimes referred to as other liquids (B2), etc.) are not particularly limited, but water, alcohols [or monools, for example, Cs such as alkanols (eg, methanol, ethanol, 1-propanol, isopropanol, etc.) _1-4 Alkanol), etc.] and the like.

Other liquids may be used alone or in combination of two or more. In particular, other liquids may contain at least water.

When the liquid contains other liquids, the ratio of the other liquids to the total liquid is, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, particularly preferably. It may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 10% by mass or less, and the like.

In particular, even when the liquid contains water as another liquid, the ratio of water to the entire liquid may be the above ratio.

When the liquid contains other liquids, the ratio of the polyol to the other liquid is, for example, the former / latter (mass ratio) = 99.9 / 0.1 to 30/70, preferably 99.5 / 0.5. ~ 40/60, more preferably 99/1 to 50/50, especially 98.5 / 1.5 to 60/40, particularly preferably 98/2 to 70/30, most preferably 97.5 / 2.5. It may be about 75/25, 99.9 / 0.1 to 80/20, 99.5 / 0.5 to 85/15, 99.9 / 0.1 to 90/10, 99.5. It may be /0.5 to 93/7 or the like.

(Other ingredients)
The composition of the present invention may contain fibroin and a liquid, and may contain other components depending on the intended use. Other ingredients include, for example, moisturizers, fragrances, pigments, vitamins, preservatives, fungicides, stabilizers (antioxidants, UV absorbers, etc.), thickeners, surfactants, emulsifiers, dispersants. Additives such as.
Other components may be used alone or in combination of two or more.

In the composition of the present invention, as will be described later, fibroin is usually dispersed (or dissolved) in a liquid, but a dispersant (or dispersion stabilizer) or the like for such dispersion (dissolution) is used. Can be guaranteed in a dispersed state without using.

(Aspect of composition)
In the composition, the ratio of fibroin (concentration, ratio of fibroin to the whole composition) is not particularly limited, but is, for example, 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably 0. It may be about 01 to 10% by mass.

In the composition, the proportion of polyol (ratio of polyol to the whole composition) is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, particularly 55% by mass or more, particularly preferably 60. It may be mass% or more, most preferably 70 mass% or more, and may be 75 mass% or more, 80 mass% or more, 90 mass% or more, and the like.

When the composition (or liquid) contains other liquid, in the composition, the ratio of the other liquid (for example, water) (the ratio of the other liquid to the whole composition) is, for example, 70% by mass or less, preferably 70% by mass or less. 65% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, particularly preferably 45% by mass or less, most preferably 40% by mass or less, 30% by mass or less, 25% by mass or less, It may be 20% by mass or less, 10% by mass or less, and the like.

In the composition, the ratio of the liquid (the ratio of the liquid to the entire composition) is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, particularly 60% by mass or more, particularly preferably 70. It may be 80% by mass or more, most preferably 75% by mass or more, and may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, and the like.

In the composition, the proportion of the polyol may be, for example, 30 parts by mass or more, preferably 40 parts by mass or more, and more preferably 50 parts by mass or more with respect to 1 part by mass of fibroin.

In the composition, the proportion of the polyol is not particularly limited with respect to 1 part by mass of fibroin, but may be, for example, 10000 parts by mass or less, preferably 8000 parts by mass or less, and more preferably 5000 parts by mass or less.

In the composition, the present form of fibroin is not particularly limited, but usually, fibroin may be dispersed (and / or dissolved) in the liquid (in the form of a composition (dispersion liquid) in which fibroin is dispersed in the liquid). There may be). In other words, in the composition of the present invention, fibroin may form or form a dispersion system (and / or a dissolved solution system) dispersed in a liquid.

In such a dispersion, the dispersibility of fibroin is often relatively good, and the dispersed state can usually be maintained for a long period of time.

In the composition of the present invention, fibroin is often stably dispersed (or dissolved). Therefore, the composition of the present invention is suppressed from precipitation and agglutination, and is often relatively less turbid.

The turbidity of the composition of the present invention is 80 NTU or less, preferably 70 NTU or less, more preferably 60 NTU or less in the composition (diluted solution) diluted 10 times (mass times) with 1,3-butylene glycol. It may be 50 NTU or less, 40 NTU or less, 30 NTU or less, 20 NTU or less.

The turbidity is not particularly limited, but can be measured using, for example, a turbidity meter (for example, "HACH turbidity meter 2100AN" manufactured by HACH).

(Manufacturing method of composition)
The method for producing the composition of the present invention is not particularly limited, and can be produced, for example, by mixing fibroin and a liquid (and, if necessary, other components).

When mixing other liquids (such as water), fibroin, polyol and other liquids may be mixed, preferably after mixing fibroin and polyol (with some of the other liquids). [Part (residual) or all of other components] may be mixed (post-added).

When such post-addition is performed, the ratio of various components may be the above-mentioned ratio in the finally obtained composition, or a second composition described later may be obtained.

In the mixing, the fibroin may be in a solid state, or a liquid in which fibroin is dissolved or dispersed in a predetermined solvent in advance may be used.
In such a case, the predetermined solvent may be the other liquid (water or the like). When fibroin is dissolved or dispersed in a predetermined solvent, the ratio of the predetermined solvent is not particularly limited, but for example, 0.1 part by mass or more, 0.5 part by mass or more, and 1 part by mass with respect to 1 part by mass of fibroin. It may be 3 parts by mass or more, 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, and the like.
The upper limit of the predetermined solvent is not particularly limited, but may be, for example, 10000 parts by mass, 1000 parts by mass, 100 parts by mass, or the like.

[Use of composition]
The composition of the present invention contains fibroin and a liquid, and can be used as it is for various purposes.
As described above, such a composition is usually in the form of a composition (dispersion liquid) in which fibroin is dispersed in a liquid, and even if it is used as it is, it is highly applicable to various uses.

On the other hand, according to the composition of the present invention, the dispersed state of fibroin once formed can be maintained even if a liquid other than a polyol (another liquid) or the like is further added. Examples of such other liquids (second liquids) include water, alcohol, and the like, as described above. Other liquids may be used alone or in combination of two or more.

That is, by using the composition of the present invention (first composition), a desired composition containing fibroin (second composition) can also be obtained.

Therefore, the present invention also includes a composition (second composition) in which other components (other liquids and the like) are further added (mixed) to the composition (first composition).

In such a second composition, the proportion / type of fibroin or polyol may or may not be selected from the same range as that of the composition (first composition).
In particular, as described above, the dispersed state once formed is retained even when water or the like is subsequently added, so that the proportion of the polyol or other liquid (water or the like) in the second composition is not necessarily the same. It does not have to be in the range of.
Specifically, even if the second composition is diluted with water or the like via the first composition and the proportion of the polyol is outside the above range (does not satisfy the above range), the dispersion is good. The state is maintained. Therefore, the second composition can be used for various purposes.

For example, when another liquid (for example, water) is added to the first composition, the concentration (ratio) of fibroin or polyol in the second composition is lower than that in the first composition, and the second composition. The concentration (ratio) of other liquids in the composition will be higher.

In such a case, in the second composition, the proportion of polyol may be in the above range or low. As a low ratio, for example, 40% by mass or less, 35% by mass or less, 33% by mass with respect to the whole liquid (the liquid constituting the second composition) and / or the whole composition (the second composition). Hereinafter, it may be 30% by mass or less, less than 30% by mass, 20% by mass or less, 18% by mass or less, 15% by mass or less, 10% by mass or less, and in particular, among these, the first composition. The ratio may not satisfy the predetermined ratio in (for example, less than 30% by mass, 20% by mass or less, 10% by mass or less, etc.).
The lower limit of the proportion of the polyol is not particularly limited, but may be, for example, 0.01% by mass, 0.05% by mass, 0.1% by mass, 0.2% by mass, or the like.

In the second composition, the proportion of the other liquid (such as water) may be in the above range or in high proportion. High proportions include, for example, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, more than 70% by mass, 75% by mass or more, 80% by mass or more, 85% by mass. As mentioned above, it may be 90% by mass or more, and in particular, it may be a ratio that does not satisfy the ratio of the other liquid (for example, more than 70% by mass, 80% by mass or more, etc.).
The upper limit of the proportion of the other liquid in the second composition is not particularly limited, but is, for example, 99.5% by mass, 99% by mass, 98.5% by mass, 98% by mass, 97% by mass, or the like. There may be.

In the second composition, the ratio of fibroin (concentration, ratio of fibroin to the whole composition) is not particularly limited, but is, for example, 0.0001 to 10% by mass, preferably 0.001 to 5% by mass, more preferably 0.001 to 5% by mass. May be about 0.005 to 3% by mass, 2.5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and the like. good.

The second composition can be produced by mixing the first composition with other components. The mixing method is not particularly limited, and a conventional method can be used.
Generally, the second composition may be a liquid obtained by diluting the first composition with at least a liquid containing water (second liquid), and the proportion of polyol or water in the second composition is the second. It may be a ratio that does not satisfy the ratio of the polyol (further water) in the composition of 1 (for example, the ratio of the polyol to the entire liquid or the second composition is less than 30% by mass).

The compositions of the present invention (first and second compositions) can be applied to various uses requiring fibroin.

Examples of such applications include cosmetics (or cosmetics), external preparations (external preparations), detergents, foods and drinks, and may be particularly used for the skin. More specifically, it may be cream, milky lotion, facial cleanser, for hair (hair wash or shampoo, hair rinse, hair liquid, hair restorer, etc.), bath salt, soap, lotion, and the like.

The composition of the present invention may be suitably used as a pack-forming composition (packing agent) or the like. These will be described in detail below.

[Composition for forming a pack]
The pack is formed by the composition.
The pack may be a pack for directly coating the part to be packed (face, etc.), or may be a sheet pack (sheet-shaped pack).

Specific packs (sheet-shaped packs) include wet types and dry types. Such packs are usually composed of a substrate and a pack-forming component (at least fibroin). The pack also includes a film type pack. In such a film type pack, the pack forming component itself forms a film, and usually, it is often not provided with a base material. These packs will be described in detail below.

(Pack with base material)
A pack provided with a base material is composed of a base material and a pack-forming component, and the pack-forming component is formed of the above composition.
More specifically, among the packs provided with a base material, a wet type pack is composed of, for example, a base material and a liquid component coated or impregnated with the base material.
In this type of pack, the liquid component may be at least derived from the composition. The liquid component may contain a moisturizing component and the like.
The wet type pack is also called, for example, a sheet mask, a sheet pack, a lotion pack, a face mask, or the like. Such a pack may be used by taking a folded pack out of a container or a bag and unfolding it.

Further, among the packs provided with the base material, the dry type pack is, for example, a base material coated or impregnated with a liquid component, dried, and then the volatile component (liquid component) of the liquid component is added. It may be removed (dried).
In this type of pack, the liquid component may be at least derived from the composition. The liquid component may contain a moisturizing component and the like.
In addition, the dry type pack may be one that adheres to the skin by containing a liquid component (for example, lotion) at the time of use, and specifically, it is called a dry pack, a dry pack, or the like. There is.

In a pack provided with a base material (a pack using a base material), the base material may be any conventional base material used for sheet packs, and may be, for example, a woven fabric or a non-woven fabric. .. The base material may have a shape corresponding to the part to be packed. For example, the base material may be in the shape of any face mask cut out from the eyes, nose, mouth and the like. Further, the base material may have a single shape, or base materials having different shapes may be combined. For example, the base material may be a one-part base material that covers the entire face, and is a base material for the upper face (for example, a base material that covers the eyes and nose) and a base material for the lower face (for example, the mouth). It may be a two-part base material separated from the base material around the surface and the base material covering the chin.

The thickness of the base material is not particularly limited, but is preferably 0.01 to 5.0 mm from the viewpoint of ease of use and portability.

In a pack using a base material (for example, wet type or dry type), the amount of the composition applied is not particularly limited, and a desired amount of fibroin (for example, fibroin content of 5 to 6000 ^{mg / m 2} , preferably 10 to 5000 mg) is used. It may be coated or applied so as to be (about / m ^2).

(Film type pack)
The pack also includes a film type pack (fibroin-containing film). Such a film type pack may be a pack for directly coating the part to be packed.
In this type of pack, the pack itself may be derived from the composition. Further, the film type pack may contain a moisturizing ingredient or the like.
The film-type pack can also be used as a skin protective film for sensitive skin or a part to be packed having a skin disease, and may have characteristics such as being able to make up after film formation (coating).
The thickness of the film type pack may be, for example, 0.05 to 50 μm, preferably 0.1 to 40 μm, and more preferably 0.1 to 30 μm.
The film type pack may be formed on a release paper (release film, etc.), but usually does not include a base material (woven fabric, non-woven fabric, etc.) constituting the pack itself.

As described above, various packs can be formed by using the composition. In particular, according to the composition, a pack having a good feel and texture can be efficiently formed. Further, in the film type pack, a good film (for example, a smooth film having no unevenness on the surface) in which the generation of gel, foreign matter, etc. is suppressed due to the dispersed state of fibroin in the composition is efficiently produced. Can form well.

The pack may retain the liquid as long as it contains (adheres) fibroin, and may have some or all of the liquid (polypoly or the like) removed (dried).

The following formulation is shown as a specific example of a composition (or a composition used for forming a pack) for forming a pack (for example, a wet type pack).
・ Glycerin 4%
・ Pentyl glycol 3%
・ 1,3-butylene glycol 2.4%
・ Trehalose 1%
・ Fibroin 0.2%
・ Scutellaria root extract appropriate amount ・ PEG-60 hydrogenated castor oil 0.5%
・ Hydroxyethyl cellulose 0.1%
・ Ethylhexyl glycerin 0.1%
・ Methylparaben 0.05%
・ Phenoxyethanol 0.02%
・ Appropriate amount of tocopherol ・ Amount that makes the whole water 100%

Compositions of such formulations contain a large excess of water, which contains fibroin and a polyol (eg, at least one selected from glycerin, pentyl glycol, 1,3-butylene glycol). After obtaining the composition (first composition), it may be mixed (may be obtained as a second composition).
The timing of mixing other components (trehalose and the like) is not particularly limited, and may be mixed at the time of preparation of the first composition, or may be mixed with water in the first composition.

(Manufacturing method of pack)
The method for producing the pack is not particularly limited as long as it is formed of the composition (or is formed using the composition), and can be appropriately produced depending on the form of the pack and the like.

In such a method, it is sufficient that the composition (first composition) containing the polyol at the predetermined ratio can be used (via), and the first composition may be used as it is. , Or a composition obtained by diluting the first composition (second composition) can also be used.

In the second composition, the proportion of polyol is usually smaller than the proportion in the first composition due to dilution, but the proportion of polyol (after dilution) in the second composition satisfies the above proportion. It may or may not be satisfied. As described above, even if the proportion of polyol does not satisfy the predetermined proportion due to dilution by once passing through the first composition (for example, even if the proportion of polyol becomes less than 30% by mass). , The dispersed state of fibroin, etc. is maintained, and a good pack can be formed.
For example, a pack provided with a base material (sheet-like pack, for example, wet type pack, dry type pack) is, for example, on a base material (base material sheet, sheet-like base material) at least the composition (or the above-mentioned composition). It can be obtained through a step of coating (or impregnating or adhering) a liquid component containing the composition.

The coating method is not particularly limited as long as it can adhere to or contain the composition (or fibroin constituting the composition) on the substrate, and for example, dipping or dipping the composition in the substrate. Examples include spraying and brushing.

The dry type pack can be produced after coating and further undergoing a drying step (or a step of adhering or containing fibroin) to dry the volatile component. The volatile component may be the liquid in the composition.

Further, a film type pack can be obtained, for example, by film molding (sheet molding) the composition. The film forming method (film forming method) is not particularly limited, and a conventional forming method (for example, casting method, brush coating, etc.) can be used. For example, a film (fibroin-containing film) may be formed by coating the composition on a release film and then drying it.
Further, when a film-type pack is formed directly on the part to be packed, the film-type pack is packed by coating the part to be packed with the composition (further drying it if necessary). Can be formed on the site.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

(Example 1)
A suspension or aqueous solution of fibroin [a suspension or solution containing 0.01 g of fibroin powder (weight average molecular weight 65,000) and 0.29 g of water] and 5.0 g of glycerin as a liquid component are mixed. A mixed solution (composition) of fibroin and glycerin was obtained.

The property of the mixed liquid was a dispersion (viscous dispersion) in which fibroin, which is a solid component, was dispersed in the liquid, and gelation and precipitation did not occur. The turbidity of the diluted solution obtained by diluting the mixed solution 10-fold with 1,3-butylene glycol was measured and found to be 10.5 NTU.
After that, even if the mixed solution was left at room temperature for 3 months, phenomena such as gelation and precipitation did not occur, and the turbidity of the 10-fold diluted solution was measured in the same manner, but no change was observed.

On the other hand, the water suspension or aqueous solution of fibroin used for preparing the mixed solution gelled when left at room temperature for 1 month, and the fluidity could not be maintained.

(Examples 2 to 7 and Reference Examples 1 to 2)
A mixed solution was obtained in the same manner as in Example 1 except that the types and amounts of the liquid components were changed as shown in Table 1 below.

In Reference Example 2, a mixed solution was obtained by mixing 5.0 g of water with the fibroin suspension or solution.

(Example 8)
3.0 g of water was mixed with the mixed solution obtained in Example 2 and diluted to obtain a mixed solution (diluted solution).

(Example 9)
3.0 g of water was mixed with the mixed solution obtained in Example 3 and diluted to obtain a mixed solution (diluted solution).

(Example 10)
5.0 g of water was mixed with the mixed solution obtained in Example 7 and diluted to obtain a mixed solution (diluted solution).

Table 1 below summarizes the properties of the obtained mixed solution (and diluted solution). In Table 1, the meanings of the liquid symbols are as follows.
GL: Glycerin BG: 1,3-Butanediol DPG: Dipropylene glycol EtOH: Ethanol In Table 1, "3.0 g" of the water mass "3.29 g" of Examples 8 and 9 is used for dilution. The amount of water used, and "5.0 g" out of the mass "5.29 g" of water in Example 10, is the amount of water used for dilution.

As is clear from the above table, it was found that fibroin can be efficiently dispersed in a composition containing a specific liquid (glycerin, 1,3-butanediol, dipropylene glycol) at a specific concentration.

Further, as is clear from the results of Examples 8 to 10, it was confirmed that the dispersed state of fibroin in the composition obtained in Examples can be maintained even when diluted with water.
The mixed solution obtained in Examples 2 to 10 did not undergo gelation or precipitation as in Example 1, and the turbidity of the diluted solution diluted 10-fold was also low (for example, Example 1). The turbidity of the diluted solution obtained by diluting the mixed solution obtained in Example 3 with 1,3-butylene glycol 10-fold was 14.7 NTU).
After that, even if the mixed solution obtained in Examples 2 to 10 was left at room temperature for 3 months, no phenomenon such as gelation or precipitation occurred, and the turbidity of the 10-fold diluted solution was measured in the same manner. However, no change was observed.

(Example 11)
Water suspension or aqueous solution of fibroin [suspension or solution containing 0.02 g of fibroin powder (weight average molecular weight 65,000) and 0.58 g of water] and 1.0 g of 1,3-butanediol as a liquid component. Was mixed to obtain a mixed solution (composition) of fibroin and 1,3-butanediol.
The property of the mixed liquid was a dispersion (viscous dispersion) in which fibroin, which is a solid component, was dispersed in the liquid, and gelation and precipitation did not occur.
Then, 8.42 g of water was further added to the obtained composition and diluted to obtain a mixed solution (diluted solution).
The obtained diluent maintained a dispersed state.
The composition and properties of the composition (mixed solution) before and after dilution with water are as follows.

(Reference example 3)
A mixed solution was obtained in the same manner as in Example 11 except that the order of adding water was changed in Example 11.
That is, water suspension or aqueous solution of fibroin [suspension or solution containing 0.02 g of fibroin powder (weight average molecular weight 65,000) and 0.58 g of water], 1,3-butanediol as a liquid component 1. 0 g and 8.42 g of water were mixed at a time to obtain a mixed solution (composition) of fibroin, 1,3-butanediol and water.
In the obtained mixed solution, fibroin, which is a solid component, was precipitated, and a composition in which fibroin was dispersed could not be obtained.

A summary of these results is shown in Table 2 below.

As is clear from the results in Table 2 above, the properties after dilution of Example 11 and Reference Example 3 were completely different even though the composition of the composition was exactly the same.

The result is that in the composition containing fibroin, a good dispersion state can be obtained by adjusting the polyol concentration to a predetermined concentration (the concentration in the liquid or the composition is 30% by mass or more). After that, it can be said that even if it is diluted with water or the like and the polyol concentration is out of the predetermined concentration, a good dispersed state can be maintained.

(Examples 12 and 13, Reference Examples 4, 5 and 6)
A non-woven fabric (Asahi Kasei Corporation, Benlyse SE603) was impregnated with an appropriate amount of the compositions obtained in Example 4, Example 5, and Reference Example 2 to obtain a 2 cm square pack (wet type pack).

Further, the wet type pack was dried in a vacuum dryer at 50 ° C. for 24 hours to prepare a 2 cm square pack (drying pack, sheet pack).

Table 3 below summarizes the results of evaluating the fibroin content (adhesion amount) and feel of the pack.
The feel (texture) of the pack was evaluated based on Example 13.

As is clear from the results in the above table, by using the composition obtained in the example, a pack having a better texture can be obtained as compared with the case where the composition obtained in the reference example is used. rice field.
In particular, surprisingly, in Examples 12 and 13, a pack having a good texture could be obtained even though the fibroin content was increased as compared with Reference Examples 5 and 6.

(Example 14 and reference example 7)
Using the composition obtained in Example 2 or Reference Example 2, a film was prepared as follows.
A solution prepared by using a base material lined with paper on aluminum foil and using 0.0005 g of carbomer and 0.0005 g of fatty acid sorbitan ester in the composition obtained in Example 2 or Reference Example 2 as the base material was prepared. A film (thickness 1 μm) was prepared by applying 2 g of each solution on a base material formed of a 2 cm square frame and drying with a hot air dryer and a vacuum dryer at 50 ° C. for 1 hour.

The film formed by using the composition obtained in Example 2 was a smooth film with no unevenness on the surface.
On the other hand, the film formed by using the composition obtained in Reference Example 2 was a film having an uneven surface and a rough surface.

According to the present invention, a composition containing fibroin can be provided.

Claims (7)

A non-gelled liquid composition containing fibroin and a liquid and satisfying the following conditions (1) and / or (2).
(1) The liquid contains a polyol in a proportion of 30% by mass or more with respect to the whole liquid (2) the polyol as a liquid is contained in a proportion of 30% by mass or more with respect to the whole composition. The composition according to claim 1, wherein fibroin is dispersed or dissolved in a liquid. Claim that the liquid comprises at least one polyol selected from _{C 2-4} alkane diols, di to tri C _2-4 alkane diols, C _3-6 alkane triols, and di to tri C _{3-6 alkane triols.} The composition according to 1 or 2. The composition according to any one of claims 1 to 3, wherein the ratio of fibroin is 0.001 to 20% by mass based on the whole composition. The composition according to any one of claims 1 to 4, wherein the ratio of fibroin is 0.001 to 10% by mass based on the whole composition. The composition according to any one of claims 1 to 5 , wherein the turbidity when diluted 10-fold with 1,3-butylene glycol is 80 NTU or less. The method for producing the composition according to any one of claims 1 to 6 by mixing fibroin and a liquid.