JP6884369B2 - Seamless capsule - Google Patents

Description

The present invention relates to seamless capsules.

A seamless capsule is a capsule in which inclusions are seamlessly wrapped in a film (capsule film).

For example, Patent Document 1 states that in the preparation of a seamless soft capsule film, carrageenan, which is the composition of the capsule film, is decomposed by an acidic pH adjuster, and the decomposition is stopped by a neutralizing agent, and the composition of the capsule film is described. A seamless soft capsule produced by gelling alginates in an aqueous gelling aid containing calcium ions as a substance, and having at least carrageenan and alginates in the composition of the capsule film. A soft capsule characterized by the above is disclosed. Then, this document describes that the diameter of the capsule is 0.5 to 15 mm, preferably 1 to 8 mm, and in the examples, a capsule having a diameter of 4 mm is manufactured.

Patent Document 2 discloses a method for producing a seamless capsule, which comprises a coating step of coating the seamless capsule separated from the curing liquid with an adsorbent powder during or after drying. It is described that the diameter of the capsule is 1 mm to 7 mm, and in the example, a capsule having a diameter of 3.5 mm was obtained.

Japanese Patent No. 4822299 (Claims, Examples, Paragraph 0068) JP-A-2015-81249 (Claims, Examples, Paragraph 0051)

An object of the present invention is to provide a seamless capsule having a relatively large particle size (diameter).

Although the diameter of the seamless capsule is widely described as in Patent Documents 1 and 2, the diameter of the seamless capsule is actually 3.5 mm or 4 mm at most, and a large particle size (for example, 9 mm or more and 10 mm or more). ) Seamless capsules have not been manufactured.

On the other hand, according to the study by the present inventors, when an attempt is made to produce a seamless capsule having a large diameter by a general method, the capsule itself is not formed because it actually breaks during the production. However, capsule formation is hindered not only when the film ratio or film thickness is small, but also when the film ratio or film thickness is large, the effect of surface tension is large, which causes the capsule to crack during drying or due to a small impact. It was found that there are cases where it is not possible to form seamless capsules that can guarantee practicality. Capsules with a diameter of at most 3.5 mm or 4 mm and capsules with a large particle size may differ greatly in the form of the capsule itself, and this has been realistically assumed by seamless capsules with a large particle size. It was not done and was considered to be one of the factors that were not actually manufactured.

Under these circumstances, as a result of diligent studies, the present inventors have controlled the manufacturing conditions of seamless capsules (furthermore, select a film or inclusions), so that even if the particle size is relatively large, Seamless capsules that have characteristics such as the ability to obtain seamless capsules and small variations in film thickness (uneven thickness) are capsules that can withstand practical use despite their large particle size. Capsules with a desired film can be obtained regardless of the film ratio or thickness, and seamless capsules (particularly large particle size seamless capsules) having gel-like inclusions that have not been known at all can be obtained. I found that.
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 present invention relates to the following inventions and the like.
[1] A seamless capsule having a diameter of 5 mm or more and a ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 being 3.5 or less.
[2] The seamless capsule according to [1], which has a diameter of 7 mm or more.
[3] The seamless capsule according to [1] or [2], wherein the diameter is 10 mm or more, and the ratio T2 / T1 of the maximum thickness T2 to the minimum thickness T1 of the film is 3 or less.
[4] The seamless capsule according to any one of [1] to [3], wherein the ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 is 2.3 or less.
[5] The seamless capsule according to any one of [1] to [4], which has a sphericity of 80% or more.
[6] Any of [1] to [5] having a diameter of 10 mm or more, a ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 of 2.1 or less, and a sphericity of 85% or more. Seamless capsule described in Crab.
[7] The seamless capsule according to any one of [1] to [6], which has a film ratio of 3 to 60% by mass.
[8] The seamless capsule according to any one of [1] to [7], wherein the film ratio is 10% by mass or less.
[9] The seamless capsule according to any one of [1] to [8], wherein the film ratio is 15% by mass or more.
[10] The seamless capsule according to any one of [1] to [9], which has a diameter of 13 mm or more.
[11] The seamless capsule according to any one of [1] to [10], which has a diameter of 15 mm or more.
[12] The seamless capsule according to any one of [1] to [11], wherein the inclusion is in the form of a gel.
[13] The seamless capsule according to any one of [1] to [12], wherein the value SD / T is 0.2 or less, where SD is the standard deviation of the film thickness and T is the film thickness.
[14] An apparatus including a concentric multiple nozzle having concentric circles of an outer nozzle for passing a film liquid containing a component of a film and an inner nozzle for supplying a content liquid containing a component of an inclusion, and a forming tube. It is a method for manufacturing a seamless capsule including a capsule forming step of forming a capsule in the forming tube by discharging the content liquid from the discharge port of the inner nozzle and the coating liquid from the discharge port of the outer nozzle into the forming tube. hand,
When the distance between the axis of the concentric multiple nozzle and the axis of the forming tube is X and the diameter of the capsule is D, the value X / D is adjusted to be 3 or less, and
A method for manufacturing a seamless capsule, in which the value Y / D is adjusted to 0.4 or less when the width of the discharge port of the inner nozzle is Y and the diameter of the capsule is D.
[15] The production method according to [14], wherein the value X / D is adjusted to 2 or less and the value Y / D is adjusted to 0.28 or less to obtain a seamless capsule with a yield rate of 80% or more.
[16] The production method according to [14] or [15], wherein the seamless capsule is the seamless capsule according to any one of [1] to [13].

The present invention can provide a seamless capsule having a relatively large particle size (diameter).

The seamless capsule of the present invention usually does not break during drying or due to a small impact. Therefore, the present invention can provide a seamless capsule that is not only large in diameter but also practical.

In another aspect of the present invention, it is possible to obtain a seamless capsule having a clean shape with few dents and the like even if the particle size is large.

In another aspect of the present invention, a seamless capsule having excellent stability can be obtained without deformation / breakage of the capsule, leakage of inclusions, etc. even after long-term storage.

In another aspect of the invention, seamless capsules can be obtained that have the desired properties required (eg, feel, disintegration, etc.) despite their relatively large particle size.

In another aspect of the present invention, a seamless capsule having a large particle size can be obtained regardless of the film ratio and the film thickness.

In another aspect of the invention, seamless capsules with solid (particularly gel-like) inclusions can be obtained.

FIG. 1 is a schematic view showing a manufacturing process (manufacturing apparatus) of a seamless capsule by a dropping method.

[capsule]
Capsules usually have a film (capsule, capsule film) and inclusions (inclusions contained within the film). In other words, the capsule has an inclusion and a coating covering the inclusion.

(Film)
The film may usually contain a film-forming component (film-forming base, film-forming agent). The film-forming component is not particularly limited and may be appropriately selected depending on the intended use of the capsule and the like. For example, a polysaccharide (or a derivative thereof) {for example, a seaweed-derived polysaccharide [for example, agar, carrageenan, alginic acid or a salt thereof (eg For example, alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), iron salt, tin salt, etc.), dextrin, dextrin, etc.], resin-derived polysaccharides (Eg, gati gum, arabic gum, etc.), microbial-derived polysaccharides (eg, purulan, welan gum, xanthan gum, gellan gum, etc.), plant-derived polysaccharides (eg, tragant gum, pectin, glucomannan, starch, polydextrose, dextrin, maltodextrin) , Cyclodextrin, refractory dextrin, etc.), seed-derived polysaccharides [eg, guar gum or derivatives thereof (eg, hydroxypropyl guar gum, cationized guar gum, guar gum degradation products (such as guar gum enzymatic degradation products)), tara gum, tamarind seeds Gum, Locust Bean Gum, Psyllium Seed Gum, Amaseed Gum, etc.], Fermented Polysaccharides (eg, Daiyutan Gum, etc.), Cellulose Derivatives (eg, Hydroxypropyl Cellulose, Hydroxypropyl Methyl Cellulose, Methyl Cellulose, Carboxymethyl Cellulose, etc.), Chitosan, etc.}, Examples include synthetic resins (such as polyvinyl alcohol), proteins (eg, gelatin, casein, zein, etc.), polysaccharide alcohols (eg, sorbitol, martitol, lactitol, palatinit, xylitol, mannitol, galactitol, erythritol) and the like. Depending on the type of the film-forming component, the film-forming component may function as a plasticizer, a sweetener, a dietary fiber, a bulking agent, or the like.

The film-forming component may be used alone or in combination of two or more.

Among these, agar, carrageenan, gelatin and the like are typical. Therefore, the film-forming component may be composed of at least one film-forming component (A) selected from agar, carrageenan and gelatin. In particular, the film-forming component may be composed of non-gelatin-based components such as agar and / or carrageenan.

The agar is not particularly limited, and examples thereof include powdered agar, solid agar, and flake agar. Examples of the raw material for agar include red algae (for example, gelidiaceae, Gracilaria, etc.).

The strength of the agar can be appropriately selected according to the use of the capsule, the texture, and the like. For example, in the viewpoint of cracking feeling and touch, jelly strength of agar, 500 g / cm ² or more (e.g., 550~3000g / ^cm 2), preferably 600 g / cm ² or more (e.g., 650~2000g / ^cm 2) , more preferably 700 g / cm ² or more (e.g., 750~1500g / cm ²⁾ it may be, may be 800 g / cm ² or more.
Further, in a case such as that desired soft capsule shell, jelly strength of agar, 500 g / cm ² or less (e.g., 100 to 500 g / ^cm 2), preferably 300 g / cm ² or less (e.g., 100 to 300 g / cm ² ), More preferably 250 g / cm ² or less (for example, 150 to ^{250 g / cm 2} ).
The jelly strength can be measured by the cold water method.

Examples of carrageenan include κ (kappa) carrageenan, ι (iota) carrageenan, λ (lambda) carrageenan, μ (mu) carrageenan, ν (new) carrageenan, θ carrageenan, ζ (zeta) carrageenan, and π carrageenan. Be done.
Carrageenan may be derived from all algae such as red algae such as Suginori, Mirin, and Ibaranori.
The viscosity of carrageenan can be appropriately selected depending on the use of the capsule, texture and the like. For example, in the case of agar such as cracking feeling and feeling, it may be 5 mPa · s or more. The upper limit of the viscosity is not particularly limited, but is preferably 500 mPa · s or less. The viscosity can be measured using, for example, a B-type viscometer.

The gelatin is not particularly limited, and examples thereof include pig gelatin, bovine gelatin, chicken gelatin, and fish gelatin.
Further, as the gelatin, gelatin derivatives such as succinate gelatin, gelatin hydrolyzate, hydrolyzed gelatin, and crosslinked gelatin may be used.
If the purpose is not to use ingredients derived from mammals (for example, cows, pigs, etc.) due to religious restrictions, allergy problems, etc., gelatin derived from mammals is not used to make non-mammalian capsules. be able to.
The strength of gelatin can be appropriately selected depending on the use of the capsule, texture and the like. For example, from the viewpoint of cracking feeling and feel, gelatin has a bloom strength of 150 or more (for example, 160 to 500), preferably 170 or more (for example, 175 to 450), and more preferably 200 or more (for example, 200 to 400). ) May be.
Further, when a soft capsule film is desired, the bloom strength of gelatin may be 150 or less, preferably 130 or less, and more preferably 100 or less.
Bloom strength is defined, for example, by the mass required for a cylindrical piston with a diameter of 12.7 mm to be pushed into a 4 mm gel.

When the film contains the film-forming component (A), the ratio (solid content ratio) of the film-forming component (A) in the film (or film-forming component) is, for example, 10% by mass or more (for example, 10 to 100% by mass). It may be preferably 15% by mass or more (for example, 15 to 95% by mass), more preferably 20% by mass or more (for example, 20 to 90% by mass), and 30% by mass or more (for example, 40% by mass or more). , Preferably 50% by mass or more).

Further, the film may contain a combination of the film-forming component (A) and another film-forming component. The other film-forming component (film-forming component (B)) may be a component other than the film-forming component (A) and can be selected according to the function required for the capsule, for example, alginic acid or a salt thereof, or a microorganism. Derived polysaccharides (eg, gellan gum, etc.), plant-derived polysaccharides (eg, pectin, starch, dextrin, maltodextrin, cyclodextrin, refractory dextrin, etc.), seed-derived polysaccharides [eg, guar gum or derivatives thereof (eg, guar gum or derivatives thereof, etc.) (Gurgam decomposition products, etc.)], polysaccharide alcohols (eg, sorbitol, xylitol, etc.) and the like. The film-forming component (B) may be composed of at least one of these components.

The film-forming component (B) may be used alone or in combination of two or more.

When the film contains the film-forming component (B), the ratio (solid content ratio) of the film-forming component (B) in the film (or film-forming component) is, for example, 70% by mass or less (for example, 0.1 to 65% by mass). %), preferably 60% by mass or less (for example, 0.5 to 55% by mass), more preferably 50% by mass or less (for example, 1 to 45% by mass), and 2% by mass or more (for example, 1 to 45% by mass). It may be 2 to 40% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass).

When the film contains a film-forming component (A) and a film-forming component (B), the ratio of these is, for example, the former / the latter (mass ratio) = 99.5 / 0.5 to 10/90 (for example, 99/1 to 15/85), more preferably 98/2 to 20/80 (eg, 95/5 to 25/75), 99/1 to 30/70 (eg, 95/5 to 5). It may be about 40/60, preferably about 90/10 to 50/50).

The film-forming component may be either water-soluble or water-insoluble, depending on the intended use, and a water-soluble component and a water-insoluble (hydrophobic) component may be used in combination.

The film may contain a plasticizer for adjusting the film strength and the like. Examples of the plasticizer include polyhydric alcohols (for example, (poly) alkylene glycols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; polyols having three or more hydroxyl groups such as glycerin), sugars [for example, simple substances. Sugars (eg glucose, fructose, glucose, galactose, etc.), disaccharides (eg, sucrose, malt sugar, trehalose, coupling sugar, etc.), oligosaccharides (eg, maltooligosaccharide, etc.)], sugar alcohols (eg, sorbitol, etc.) , Martinol, lactitol, palatinit, xylitol, mannitol, galactitol, erythritol and other above-exemplified sugar alcohols), polysaccharides or derivatives thereof [eg, starch, starch derivatives (eg, polydextrose, dextrin, maltodextrin, indigestible). Sex dextrins, cyclodextrins (α, β, or γ, etc.), cellulose derivatives (eg, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, carboxymethyl cellulose, etc.)], polyvinyl alcohols, triacetin, and the like can be mentioned.
The DE (starch decomposition degree) of the starch derivative may be, for example, about 10 to 90.

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

In addition, sugar alcohol, starch, starch derivative and the like can also be used as a film-forming component as described above.

Of these, polyhydric alcohols, sugars, starches, starch derivatives and the like may be preferably used as the plasticizer. Therefore, the plasticizer may be composed of at least one of these. On the other hand, in the present invention, capsules can be obtained without using sugars (for example, sucrose, trehalose, etc.).

When the film contains a plasticizing agent, the proportion of the plasticizing agent (solid content ratio) in the film is, for example, 70% by mass or less (for example, 0.1 to 65% by mass), preferably 60% by mass or less (for example, 0. 5 to 55% by mass), more preferably 50% by mass or less (for example, 1 to 45% by mass), 2% by mass or more (for example, 2 to 60% by mass, preferably 3 to 50% by mass). More preferably, it may be 5 to 40% by mass).

In particular, the coating may contain at least glycerin. When the film contains glycerin, the proportion of glycerin in the film is, for example, 70% by mass or less (for example, 0.1 to 65% by mass), preferably 60% by mass or less (for example, 2 to 55% by mass), more preferably. May be 50% by mass or less (for example, 3 to 45% by mass), or 5% by mass or more (for example, 7 to 50% by mass).

The film may contain other components depending on the intended use and the like. Other ingredients include, for example, colorants (pigments, pigments), flavoring agents, sweeteners, antioxidants, preservatives, seasonings, spices, acidulants (eg, citric acid or salts thereof), bitterness agents. , Salt content, umami component, and other components described in the section of inclusions described later (for example, physiologically active substance, biologically active substance, etc.) and the like. Depending on the type of sweetener, the sweetener can also be used as a film-forming component or a plasticizer as described above.

Other components may be used alone or in combination of two or more.

When the film contains other components, the proportion of the other components in the film is, for example, 30% by mass or less (for example, 0.01 to 25% by mass), preferably 20% by mass or less (for example, 0.05 to 15%). It may be 10% by mass or less (for example, 0.1 to 8% by mass), more preferably 10% by mass or less.

The film may contain a solvent component (eg, water). The proportion of the solvent component in the film is, for example, 30% by mass or less (for example, 0.1 to 25% by mass), preferably 20% by mass or less (for example, 1 to 18% by mass), and more preferably 15% by mass or less (for example, 15% by mass or less). For example, it may be about 3 to 12% by mass).

(Intensions)
The inclusions of the capsule can be appropriately selected depending on the intended use and the like, and are not particularly limited.
The inclusion may be an oil-based component (oil-soluble component, lipophilic component) or a water-soluble component (hydrophilic component), depending on the type and use of the film, and contains both of them. May be good. Further, the inclusion may be in the form of a liquid or a solid, and may contain a combination thereof. Usually, the inclusions often contain at least a liquid.

The inclusions may typically be liquid. Such a liquid inclusion may be liquid as a whole, may be composed of only a liquid component (one or two or more liquid components), or may be a liquid component (or a liquid component as a solvent or a dispersion medium). ), Other components (another liquid component, gaseous component, and / or solid component) may be dissolved or dispersed (forming a liquid inclusion as a whole).

The liquid also includes a colloidal form, an emulsion form, and a jelly form.

In another aspect of the present invention, the inclusions in the capsule may be solid. The solid state includes a state in which there is substantially no fluidity, for example, a gel [gel-like (gummy-like)]. The solid inclusion may be solid as a whole, may be composed of only a solid component (one or two or more solid components), or may be a solid component (or a solid component). Other components (liquid component, gaseous component, and / or another solid component) may be mixed or dispersed (forming solid inclusions as a whole) as a dispersion medium.

The inclusions are not particularly limited, and are, for example, fragrances, cosmetics, surfactants, detergents, bathing agents, surfactants, refreshing agents, physiologically active substances (for example, vitamins, amino acids, collagen, collagen peptides, lipids). , Isoflavones, minerals, enzymes, hormones, etc.), bioactive substances (medicines, etc.), microorganisms (for example, bacteria such as lactic acid bacteria, bifidus bacteria, natto bacteria, yeast; fungi such as yeast; It may be classified into (or an extract thereof), a plant (or an extract thereof), a sweetener, an acidulant, a seasoning, a tonic, and the like. These components may be in a solid state or a liquid state, and may be used alone or in combination of two or more.

As mentioned above, in one aspect of the invention, the inclusions are liquid. The liquid component (or liquid inclusion) constituting the liquid inclusion may be either hydrophilic or lipophilic, but as described later, it is usually with respect to the film (or the portion in contact with the film). It may be insoluble (non-erosive).

Specific liquid components (lipophilic liquid components) include, for example, fatty acids (eg, capric acid, capric acid, eicosapentaenoic acid, docosahexaenoic acid, oleic acid, linoleic acid, etc.), fatty acid esters [eg, triglycerides (medium). Glycerin esters (fats) such as chain fatty acid triglycerides (MCT, etc.); non-glycerin-based fatty acid esters such as isopropyl myristate), etc.], vegetable oils (eg, olive oil, sunflower oil, corn oil, lacquer oil, grape seed oil, wheat Germ oil, rapeseed oil, jojoba oil, safflower oil), hardened oil, mineral oil, silicone oil, sucrose fatty acid ester, liquid paraffin, squalane, fragrance (eg, esters, alcohols, aldehydes, ketones, phenols) , Ethers, lactones, hydrocarbons, nitrogen-containing compounds, sulfur-containing compounds, acids, etc.) and the like.

The liquid inclusion may be composed of only the liquid component as described above, and another component (for example, another liquid component and / or a solid component) is dissolved in the liquid component (liquid component as a dispersion medium). Alternatively, it may be dispersed.

In another aspect of the invention, the inclusions may be solid (such as gel). The solid component constituting the solid inclusion may be either hydrophilic or lipophilic. Further, the solid component may be soluble (erosive) or insoluble (non-erosive) with respect to the film (or a portion in contact with the film), and may be particularly insoluble.

Conventionally, seamless capsules having solid inclusions (such as gummy candies) (and having a large particle size) have not been known. Since seamless capsules can usually be produced only in a liquid state, this is considered to be one of the reasons why seamless capsules having solid inclusions have not been known in the past.

The solid component (or the solid component constituting the solid inclusion) is not particularly limited, and for example, the component exemplified in the above-mentioned film section [for example, a film-forming component (gelatin, agar, carrageenan, etc.), etc. Plasticizers, etc.] and the like.

The solid inclusion may be composed of only such a solid component, in addition to the solid component (solid component as a dispersion medium or matrix) and other components (eg, another solid component and / or). Liquid components) may be mixed or dispersed.

These components may be used alone or in combination of two or more.

When the inclusion contains a liquid component and a solid component, the ratio thereof is not particularly limited and can be appropriately selected depending on whether the form of the inclusion is liquid or solid. For example, the former. / The latter (mass ratio) = 99.99 / 0.01 to 0.01 / 99.99, preferably 99.9 / 0.1 to 0.1 / 99.9, more preferably 99.5 / 0. It may be about 5 to 0.5 / 95.5, and may be about 99.99 / 0.01 to 10/90 (for example, 99.9 / 0.1 to 20/80, preferably 99.5 / 0. 5 to 30/70, more preferably 99/1 to 50/50), 0.01 / 99.99 to 90/10 (eg, 0.01 / 99.9 to 80/20, preferably 0.5 / It may be 99.5 to 70/30, more preferably 1/99 to 50/50).

(Capsule form)
The capsule has a film (shell) as the outermost layer, and contains inclusions in the film (inside). Such capsules may usually be seamless capsules (seamless capsules).

The film may be a single layer or may be formed of a plurality of layers. When formed of a plurality of layers, the thickness ratio of one layer to the other layer is not particularly limited, and is, for example, 100/1 to 0.01/1 (for example, 50/1 to 0. 02/1), preferably 20/1 to 0.05 / 1 (for example, 10/1 to 0.1 / 1), and more preferably 5/1 to 0.2 / 1.

The diameter (diameter, average diameter) of the capsule (or film) is relatively large, for example, 5 mm or more (for example, 6 to 50 mm), preferably 7 mm or more (for example, 7.5 to 40 mm), and more preferably 8 mm or more. (For example, 9 to 35 mm), particularly 10 mm or more (for example, 10 to 30 mm) may be used, more than 10 mm (for example, 10.5 mm or more), 11 mm or more (for example, 11.5 mm or more, 12 mm or more, 13 mm or more). , 15 mm or more, 16 mm or more, 17 mm or more, 18 mm or more, 19 mm or more).

The capsule of the present invention usually has a small deviation in the thickness of the film. For example, the ratio T2 / T1 of the maximum thickness T2 to the minimum thickness T1 of the capsule (or film) can be selected from the range of 3.5 or less (for example, 3.2 or less), and preferably 3 or less (for example, 2.8). Below), more preferably 2.5 or less (for example, 2.3 or less), particularly preferably 2.1 or less (for example, 2.0 or less), most preferably 1.8 or less (for example, 1.6 or less). It may be 1.2 or less.

The thickness of the film (average thickness, total thickness when formed of a plurality of layers, the same applies hereinafter) is not particularly limited and may be appropriately selected depending on the intended use, for example, 20 μm to 5 mm, preferably 30 μm. It may be about 3 mm, more preferably about 40 μm to 1 mm, and can be made relatively small [for example, 1 mm or less (for example, 800 μm or less, 500 μm or less, 300 μm or less, etc.)] or relatively large. [For example, it may be 1 mm or more (for example, 1.5 mm or more, 2 mm or more, 3 mm or more, 4 mm or more, 5 mm or more, 7 mm or more, etc.)].

When the diameter of the film (average diameter) is D and the thickness of the film (average thickness) is T, the value [T / D] × 100 (%) is, for example, 0.1 to 95%, preferably 0.2. It may be about 90%, more preferably about 0.3 to 80%, and is relatively large (for example, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, It can be 35% or more, 40% or more, etc., or relatively small (for example, 5% or less, 4% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, It can also be 1% or less).

In the present invention, it is possible to provide capsules having a relatively small variation. For example, when the standard deviation of the film thickness is SD and the film thickness (average thickness) is T, the value SD / T is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less. In particular, it may be 0.2 or less (for example, 0.16 or less), 0.15 or less (for example, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less, 0.10 or less. , 0.090 or less, 0.080 or less).

If the thickness of the film or its ratio to the film thickness is small, it is due to the thinness of the film, and if the thickness of the film or its ratio to the film thickness is large, it is due to the influence of surface tension in the capsule manufacturing process. Therefore, it is difficult to obtain good capsules, but the present invention can provide capsules in any case.

In the capsule of the present invention, the film ratio (ratio of the film to the entire capsule (total amount of film and inclusions)) is, for example, 0.1 to 99% by mass (for example, 0.5 to 95% by mass), preferably 1. It may be about 90% by mass, more preferably 2 to 80% by mass (for example, 2.5 to 70% by mass), usually about 3 to 60% by mass (for example, 3 to 50% by mass), and is relatively large. [For example, 10% by mass or more (for example, 12 to 90% by mass), preferably 15% by mass or more (for example, 18 to 80% by mass), more preferably 20% by mass or more (for example, 22 to 70% by mass). It can be usually 10 to 50% by mass (for example, 15 to 45% by mass), or relatively small [for example, 20% by mass or less (for example, 0.1 to 18% by mass), preferably 15% by mass]. The following (for example, 0.5 to 12% by mass), more preferably 10% by mass or less (for example, 1 to 8% by mass), particularly 8% by mass or less (for example, 2 to 7% by mass or less)]. it can.

Similar to the above-mentioned thickness, it is usually difficult to obtain a capsule with a large diameter regardless of whether the film ratio is large or small, but in the present invention, it is possible to obtain a capsule with such a large or small film ratio. , Good capsules can be obtained.

In the capsule of the present invention, the water content of the film can be selected according to the intended use of the capsule, and is, for example, 50% by mass or less (for example, 0.1 to 40% by mass), preferably 30% by mass or less (for example, for example. 0.5 to 25% by mass), more preferably 20% by mass or less (for example, 1 to 15% by mass).

The strength (average strength) of the capsule (coating) of the present invention is not particularly limited, but for example, the maximum load value when the capsule is pushed in by 5 mm is 0.1 N or more, preferably 0.2 N to 50 N, more preferably 0.2 N to 50 N. It may be about 0.3N to 30N. Although the capsule of the present invention has a relatively large particle size, it is not broken by a small impact and has practicality.

The shape of the capsule (or film) of the present invention may be non-spherical (elliptical, flat, etc.), but may be usually spherical.

In a spherical capsule, the sphericity (average sphericity) may be, for example, 50% or more, preferably 60% or more, more preferably 70% or more, particularly 80% or more, and 85% or more (for example). , 90% or more).

In the present invention, in particular, when the particle size is relatively large, the film ratio is small or large, the film thickness is small or large, or the film thickness is small or large relative to the film diameter, the inclusions are gel. Capsules with high sphericity can be obtained even in the case of a shape (gummy shape).

The capsules of the present invention are usually stable and can retain their shape over a long period of time. For example, the capsule of the present invention has a value of D1 / D2 (average) when the diameter (average diameter) before storage is D1 and the diameter (average diameter) after storage at 35 ° C. (sealed state) for 6 months is D2. The value) is 0.5 to 2 (for example, 0.6 to 1.7), preferably 0.65 to 1.5 (for example, 0.7 to 1.4), and more preferably 0.8 to 1. It may be .3 (eg, 0.85 to 1.2), especially 0.9 to 1.1 (eg, 0.95 to 1.05), substantially 1 (change in diameter before and after storage). None) may be.

As described above, the capsule of the present invention has a film (shell) and an inclusion (core) in the film (inside).
The inclusion may form a plurality of layers (multilayers). That is, such a capsule may have a film and an inclusion (core) composed of a plurality of layers. The plurality of layers may be two or more layers, for example, 2 to 5 layers, preferably 2 to 4 layers, and more preferably 2 to 3 layers.

The inclusions (inside the capsule, inside the coating) may include a capsule (second capsule). Examples of the embodiment of the capsule containing the second capsule in the inclusion include a capsule having a film (the film of the first capsule) and an inclusion containing a liquid component and capsules dispersed in the liquid component. Be done. In such inclusions, the number of second capsules may be one or more and may be plural (eg, 2-10). The second capsule may have a coating and inclusions within the coating, similar to the first capsule. In such a second capsule, the same components as described above can be used as the film and inclusions.

As described above, the capsule of the present invention (first capsule) is usually a seamless capsule, but the second capsule does not necessarily have to be a seamless capsule, and like the first capsule, it is a seamless capsule. There may be.

In the capsule (first capsule, second capsule), the film and the inclusions may be insoluble (non-erosive) with each other. For example, when the film is water-soluble, the inclusions (or the portion of the inclusions that comes into contact with the film) may be water-insoluble (hydrophobic).

Further, when the inclusion is a plurality of layers, the contacting or adjacent layers may be insoluble in each other (for example, a water-soluble layer and a water-insoluble layer in contact with the water-soluble layer). May be configured). Further, when the inclusion contains a liquid component (for example, a hydrophobic or oil-soluble liquid component) and a capsule (second capsule), at least the surface (film) of the second capsule is relative to the liquid component. It may be insoluble (eg, water soluble).

The capsule of the present invention may have a coating layer (a layer for coating or coating a film), if necessary. The coating agent constituting the coating layer is not particularly limited and may be appropriately selected depending on the intended use. For example, cellulose derivatives (hydroxypropyl methylcellulose, methylcellulose, ethylcellulose, etc.), methacrylic acid copolymers, shellac, water-soluble shellac, silicones, etc. Examples include oil, carnauba wax and zein. These may be used individually by 1 type, and may be used in combination of 2 or more type as needed.

[Capsule manufacturing method]
The present invention includes a method for producing capsules.

Capsules can usually be produced by a dropping method (seamless capsule method) using multiple nozzles. That is, by the dropping method (dropping method), the inclusions can be filled in the film (or the inside of the film) to obtain capsules.

In the dropping method, for example, as shown in FIG. 1, a composite nozzle device arranged substantially concentrically is used. The composite nozzle device includes, for example, an inner nozzle 4 for passing the content liquid (a liquid containing constituent components of inclusions, an inclusion liquid) supplied from the charging port A, and a coating liquid (film composition) supplied from the charging port B. It has an outer nozzle 5 through which a liquid containing a component is passed, and the inner nozzle 4 and the outer nozzle 5 are arranged substantially concentrically and include a composite nozzle (concentric multiple nozzle). Then, using this composite nozzle device, the inner solution 1 supplied to the inner nozzle 4 is discharged from the discharge port of the inner nozzle 4 to the forming pipe 7, and the coating liquid 2 supplied to the outer nozzle 5 is discharged from the outer nozzle 5. It is discharged from the discharge port (width Y) to the forming pipe 7. The inner solution 1 and the coating liquid 2 are simultaneously discharged from the inner nozzle 4 and the outer nozzle 5 into an oil liquid or a gas to form a coaxial flow in the carrier flow 6 flowing downstream, and physical such as vibration. A force is applied to cut the discharged liquid at regular intervals, the cut portion is made spherical by the interface between the oil liquid or gas and the coating liquid or the surface tension, and the membrane layer is gelled by cooling to form a capsule (wet capsule). ) Is manufactured. The film layer 2 surrounds the extruded inclusions 1 to form the capsule 3. The obtained capsule 3 may be collected and then dried to obtain a seamless capsule (dried capsule) in the final form.

Seamless capsules typically include a nozzle unit (concentric multiple nozzles) that is concentrically provided with an outer nozzle that allows the coating liquid to pass through and an inner nozzle that supplies the content liquid, and a forming tube (downstream side or on the axis of the nozzle unit). Capsules are formed in the forming tube by discharging the content liquid from the discharge port of the inner nozzle and the coating liquid from the discharge port of the outer nozzle into the forming tube, respectively. It is manufactured through the process of making it.

Here, in the present invention, it is preferable to adjust the conditions in this series of manufacturing steps.
For example, the distance between the axis (center line) of the concentric multiple nozzle and the axis (center line) of the forming tube (that is, the deviation from the center of the forming tube of the concentric multiple nozzle) is X, and the capsule (coating). ) Is D, and the value X / D is 3.5 or less (for example, 3.2 or less), preferably 3 or less (for example, 2.5 or less), and more preferably 2.4 or less (for example). 2.35 or less), particularly preferably 2.3 or less (for example, 2.2 or less), usually 2 or less (for example, 1.9 or less) may be adjusted to 1.8 or less (for example, 1.9 or less). It may be adjusted to be 1.7 or less), 1.5 or less, 1 or less, 0.7 or less, 0.5 or less, and the like.

Further, when the width of the discharge port of the inner nozzle (that is, the nozzle interval) is Y and the diameter of the capsule (coating) is D, the value Y / D is 0.4 or less (for example, 0.001 to 0. 37), preferably 0.35 or less (for example, 0.005 to 0.34), more preferably 0.3 or less (for example, 0.01 to 0.29), and particularly preferably 0.28 or less (for example, for example). It may be adjusted to 0.03 to 0.26), most preferably 0.25 or less (for example, 0.05 to 0.25).

By adjusting (selecting) such conditions, seamless capsules, particularly seamless capsules having a relatively large particle size as described above can be efficiently obtained. Further, by adjusting such conditions, it is easy to obtain a seamless capsule having a small unevenness in the film thickness and a seamless capsule having a small variation among a plurality of capsules.
Moreover, the moldability of the capsule itself is high, and the raw materials can be encapsulated relatively completely.
For example, in the method of the present invention, the yield rate (mass ratio of the encapsulated raw material among the raw materials) is 20% or more (for example, 30% or more), preferably 40% or more (for example, 50% or more), more preferably. May be 60% or more (for example, 70% or more), particularly 80% or more (for example, 85% or more).

The film liquid and the content liquid are liquids (liquid components) containing the constituent components of the film and the inclusions, respectively. Such a liquid may be liquefied by heating (heating) melting, or may contain a solvent.
For example, the film solution may be a solution in which a film-forming component (such as agar) is dissolved in a solvent (for example, water, alcohol such as ethanol, particularly water). Further, as the content liquid, when the inclusion is a liquid component, the inclusion itself may be used as the content liquid, and when the inclusion is a solid state (gel form or the like), the inclusion is liquefied with a solvent. Alternatively, the inclusions melted by heating may be used as the content liquid.

The viscosity of the coating liquid and the content liquid can be appropriately selected. For example, the viscosity of the coating liquid may be, for example, 50 mPa · s or more (for example, 70 to 500 mPa · s, preferably 80 to 300 mPa · s). Further, the viscosity of the content liquid may be as long as it can guarantee the fluidity, and can be appropriately selected depending on the type of inclusions and the like.

Other manufacturing conditions (temperature of film liquid, temperature of content liquid, cooling temperature, cooling time, drying temperature, drying time, etc.) depend on the type of film liquid and inclusions, film thickness, film ratio, etc. , Can be selected as appropriate.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples, and many modifications are made in the art within the technical idea of the present invention. It is possible by a person with ordinary knowledge.

Various physical properties were measured or evaluated as follows.

[Diameter of film (outer diameter of capsule), thickness, SD value, sphericity]
The major axis and the minor axis of the capsule were measured using a caliper (Digital caliper CD-10CX manufactured by Mitutoyo).
Then, the diameter (average diameter) was obtained as the arithmetic mean of the major axis and the minor axis.
The sphericity was [minor diameter / diameter] × 100 (%).
In addition, the capsule was cut vertically and horizontally, and the maximum thickness and the minimum thickness were measured using the same caliper. The thickness (average thickness) of the capsule was the arithmetic mean of these, and the ratio T2 / T1 of the maximum thickness T2 to the minimum thickness T1 of the film was calculated based on these thicknesses.
The number of measurements was 10 (n = 10), and the arithmetic mean of these was taken as each value.
The SD value is the standard deviation.

[Yield rate]
The yield rate was defined as the mass ratio of the amount that could be encapsulated (the amount that withstood drying and retained the shape of the capsule) with respect to the amount of the raw material used. The raw materials that did not reach encapsulation include those that did not form capsules at all and those that cracked during drying.

[Moldability]
The moldability of the seamless capsule was evaluated as follows.
⊚: Encapsulation was possible with a yield rate of 80% or more.
〇: Encapsulation was possible with a yield rate of 50% or more and less than 80%.
Δ: Encapsulation was possible with a yield rate of less than 50%.
X: Could not be encapsulated.

[Stability test]
The capsule was placed in a No. 6 bottle, capped, and stored at 35 ° C. for 6 months with the lid closed.
The capsules after storage were evaluated according to the following criteria.
(Capsule deformation)
〇: When the diameter of the film before storage is D2 and the diameter of the film after storage is D1, the value of D1 / D2 is 0.9 to 1.1 (1 or almost 1).
X: The value of D1 / D2 is much smaller than 0.9 or much larger than 1.1.
(Capsule damage / leakage)
Visually, the capsule was checked for damage or leakage.

In each specification (formulation) shown below, the in-liquid dripping method as described in the above figure (a fluid liquid is extruded from a concentric nozzle while applying vibration at regular intervals, and the capsule is cooled in the liquid. We tried to manufacture seamless capsules by the method of molding capsules with.
The in-liquid dropping method was carried out under the conditions shown in the table below, and the coating liquid and the content liquid were prepared as follows.
(Film liquid)
It was prepared by mixing the raw material and an appropriate amount of water, and then heating at a predetermined temperature (about 65 to 90 ° C.) for 2 hours or more with appropriate stirring to confirm that all the raw materials were dissolved. .. If necessary, suction-type defoaming using a vacuum pump or defoaming by centrifugation was performed.
(Content liquid)
If necessary, the ingredients were heated and mixed so that the raw materials were uniform. Since it is necessary to be liquid at the time of filling, if the gel or fluidity is poor, it is appropriately heated to make it fluid. In mixing, a high speed stirrer and / or a fine grinder was used as needed.

結果を下記表に示す。

The results are shown in the table below.

In the present invention, seamless capsules having a relatively large particle size can be obtained.

1 Inclusion 2 Film layer (film)
3 Seamless capsule 4 Inner nozzle 5 Outer nozzle 6 Carrier flow 7 Forming tube A Encapsulating liquid inlet B Coating liquid inlet

Claims (16)

A seamless capsule having a diameter of 5 mm or more and a ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 being 2.3 or less. The seamless capsule according to claim 1, which has a diameter of 7 mm or more. The seamless capsule of claim 1 or 2, wherein a diameter of the 10mm or more. The seamless capsule according to any one of claims 1 to 3, wherein the ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 is 2.1 or less. The seamless capsule according to any one of claims 1 to 4, wherein the sphericity is 80% or more. The seamless according to any one of claims 1 to 5, wherein the diameter is 10 mm or more, the ratio of the maximum thickness T2 to the minimum thickness T1 of the film T2 / T1 is 2.1 or less, and the sphericity is 85% or more. capsule. The seamless capsule according to any one of claims 1 to 6, wherein the film ratio is 3 to 60% by mass. The seamless capsule according to any one of claims 1 to 7, wherein the film ratio is 10% by mass or less. The seamless capsule according to any one of claims 1 to 7 , wherein the film ratio is 15% by mass or more. The seamless capsule according to any one of claims 1 to 9, which has a diameter of 13 mm or more. The seamless capsule according to any one of claims 1 to 10, which has a diameter of 15 mm or more. The seamless capsule according to any one of claims 1 to 11, wherein the inclusion is in the form of a gel. The seamless capsule according to any one of claims 1 to 12, wherein the value [SD / T] is 0.2 or less, where SD is the standard deviation of the film thickness and T is the film thickness. Using a device equipped with a concentric multiple nozzle and a forming tube, which are concentrically provided with an outer nozzle through which the coating liquid containing the constituents of the coating is passed and an inner nozzle for supplying the content liquid containing the constituents of the inclusions, the inner side is used. One of claims 1 to 13, further comprising a capsule forming step of forming a capsule in the forming tube by discharging the content liquid from the discharge port of the nozzle and the coating liquid from the discharge port of the outer nozzle into the forming tube. The method for manufacturing a seamless capsule described above.
When the distance between the axis of the concentric multiple nozzle and the axis of the forming tube is X and the diameter of the capsule is D, the value X / D is adjusted to be 3 or less, and
A method for manufacturing a seamless capsule, in which the value Y / D is adjusted to 0.4 or less when the width of the discharge port of the inner nozzle is Y and the diameter of the capsule is D. The manufacturing method according to claim 14, wherein the value X / D is adjusted to 2 or less and the value Y / D is adjusted to 0.28 or less. The manufacturing method according to claim 14 or 15, wherein the value X / D is adjusted to 2 or less and the value Y / D is adjusted to 0.28 or less to obtain a seamless capsule with a yield rate of 80% or more.

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