CN101433526A - Non-gelatine enteric hard capsule shell material and method for producing the same - Google Patents
Non-gelatine enteric hard capsule shell material and method for producing the same Download PDFInfo
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- CN101433526A CN101433526A CNA2007100481410A CN200710048141A CN101433526A CN 101433526 A CN101433526 A CN 101433526A CN A2007100481410 A CNA2007100481410 A CN A2007100481410A CN 200710048141 A CN200710048141 A CN 200710048141A CN 101433526 A CN101433526 A CN 101433526A
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Abstract
The invention provides a composition used for preparing a non-gelatin enteric hard capsule shell material. The composition contains non-gelatin hydrophilic jellies, an enteric type material, a pH conditioning agent, water and optional coagulant aid, plasticizer and adhesive, and does not contain any organic solvent basically. The invention also discloses a method for producing the enteric hard capsule shell material. The composition does not contain the organic solvent basically, and the enteric hard capsule shell has the advantages of good mouthfeel, high clarity, fast capsule cracking and reduced requirement on storage condition of the capsule.
Description
Technical field
The present invention relates to the material field, relate more specifically to the component and the production method of non-gelatine enteric hard capsule shell.
Background technology
At present, in the preparation of the capsule shells of enteric hard wafer, need to adopt the enteric solubility material.The enteric solubility examples of material as Lac, polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, cellulose derivative (as described in the example of cellulose derivative as cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose) etc.
The enteric hard wafer of above-mentioned employing enteric solubility material all needs a large amount of organic solvents, therefore easy initiation fire and explosive incident.In addition, its break and consoluet speed also satisfactory inadequately.The weak point of this enteric hard capsule shell also is, under low moisture content or high and low temperature environment, and its yielding or embrittlement, adverse drug production.And common enteric hard capsule is that secondary dips in glue, and the technology of therefore producing the enteric hard capsule is more loaded down with trivial details.
Except the shortcoming of above-mentioned preparation aspect and aspect of performance, the enteric hard wafer of prior art also needs to improve on component.Usually, the film of existing enteric hard wafer is that the gelatin that extracts with materials such as animal bone such as cattle, pig or skins is a raw material, make stomach dissolution type hard capsule blank, the glue of the organic solvent of reuse enteric solubility material such as Lac, polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, cellulose derivative etc., outside the stomach dissolution type hard capsule blank that makes, dip in glue or spray coating, thereby make the enteric solubility hard capsule.
Although gelatin has good characteristic when the preparation hard capsule, yet gelatin has antigenicity as heterologous protein.For example, the cattle source property gelatin materials of import may contain Protein virus, uses its soft capsule that makes as raw material may cause the diffusion of bovine spongiform encephalopathy.And the gelatine enteric hard capsule has the defective of others, and for example its toleration to humiture is relatively stricter, so its application is restricted; And the gelatine enteric hard capsule can only be in cold water swelling, can not dissolve; Gelatine enteric hard capsule shell is met high humidity, hot flexible type, easy embrittlement and can not load the aldehyde medicine under low temperature, the low water content condition; Its transparency is also unsatisfactory in addition.
Along with the increase of market to non-gelatin source material demand, non-gelatine enteric hard capsule material and production technology beyond the exploitation gelatin are extremely urgent.
For overcoming the above-mentioned defective of gelatine enteric hard capsule, this area presses for the enteric hard capsule shell material and the production technology thereof of the new non-gelatin of exploitation, it has substituted gelatine enteric hard capsule shell material, and has a better physical property, and avoid adopting organic solvent in process of production, simplify production technology.
Summary of the invention
The objective of the invention is to obtain a kind of compositions that is used to prepare non-gelatine enteric hard capsule shell material, it has substituted gelatine enteric hard capsule shell material, and has better physical property, and it does not contain organic solvent substantially.
Another object of the present invention is to obtain non-gelatine enteric hard capsule shell material, it has substituted gelatine enteric hard capsule shell material, and has better physical property.
Of the present invention also have a purpose to be to obtain a kind of non-gelatine enteric hard capsule, and it has substituted gelatine enteric hard capsule shell material, and has better physical property.
Another purpose of the present invention is to obtain the production method of non-gelatine enteric hard capsule shell material, avoids adopting organic solvent in process of production, simplifies production technology.
In a first aspect of the present invention, a kind of compositions that is used to prepare non-gelatine enteric hard capsule shell material is provided, described compositions contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(D) 40～600 weight parts waters;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
Substantially do not contain organic solvent in the described compositions.
Preferably, the amount that contains organic solvent in the described compositions is not higher than 5 weight %, more preferably no higher than 1 weight %, does not most preferably contain organic solvent.
In a specific embodiment of the present invention, described compositions contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 30 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(D) 40～600 weight parts waters;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
Substantially do not contain organic solvent in the described compositions.
In a specific embodiment of the present invention, the enteric solubility material of described component (B) is selected from down the enteric solubility material of group: polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
In a specific embodiment of the present invention, the pH regulator agent of described component (C) is selected from down the pH regulator agent of group: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqua ammonia, sodium bicarbonate, potassium bicarbonate, carbonic acid ammonia, sodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate, triethanolamine or its combination.
The present invention provides a kind of non-gelatine enteric hard capsule shell material on the other hand, it is characterized in that: described material contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
The weight summation of said components (A)+(B)+(C) accounts for 85～100 weight % of described hard capsule casing material gross weight;
Described material also contains the water of 3～12 weight % that account for described hard capsule casing material gross weight.
In a specific embodiment of the present invention, described material contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 30 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
The weight summation of said components (A)+(B)+(C) accounts for 85～100 weight % of described hard capsule casing material gross weight;
Described material also contains the water of 3～12 weight % that account for described hard capsule casing material gross weight.
In a specific embodiment of the present invention, the gel of described component (A) is selected from down the hydrophilic gel of group: acetylation gellan gum, deacetylation gellan gum, κ type carrageenan, ι type carrageenan, β type carrageenan, agar, pectin, sodium alginate, xanthan gum, tragacanth, POLY-karaya, locust bean gum, Furcellaran, tamarind gum, tara gum, scleroglucan, microbial alginate, carbomer or its combination.
In a specific embodiment of the present invention, the enteric solubility material of described component (B) is selected from down the enteric solubility material of group: polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
In a specific embodiment of the present invention, the pH regulator agent of described component (C) is selected from down the pH regulator agent of group: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqua ammonia, sodium bicarbonate, potassium bicarbonate, carbonic acid ammonia, sodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate, triethanolamine or its combination.
Preferably, the flocculation aid of described component (E) is selected from down the flocculation aid of group: potassium chloride, calcium chloride, potassium phosphate, potassium citrate or its combination.
Preferably, the plasticizer of described component (F) is selected from down the plasticizer of group: glycerol, Sorbitol, Polyethylene Glycol, ethylene glycol, ethyl acetate, 1,3-butanediol, 1,4-butanediol, xylitol, Glycerine 1,3-diacetate, triacetin, monoacetin, mannitol, inositol, maltose alcohol, glucose, polypropylene glycol or its combination.
Preferably, the binding agent of described component (G) is selected from starch, dextrin, polyvinylpyrrolidone, carboxymethyl chitin, polyvinyl alcohol, sesbania gum, arabic gum, cassia gum, Pullulan, elsinan, Ficus elastica, glucosan, vinylpyrrolidone and vinyl acetate co-polymer, hydroxy alkyl cellulose, carboxyl alkyl cellulose or its combination.
In a specific embodiment of the present invention, the binding agent of described component (G) is selected from following binding agent or its combination:
High amylose starches, etherification starch, etherificate high amylose starches, etherificate high amylopectin starch, Oxytarch, oxidation high amylose starches, oxidation high amylopectin starch, esterification starch, esterification high amylose starches, esterification high amylopectin starch or its combination.
Further aspect of the present invention provides a kind of non-gelatine enteric hard capsule, and it is made by non-gelatine enteric hard capsule shell material of the present invention.
The present invention also provides a kind of production method of non-gelatine enteric hard capsule shell material, may further comprise the steps:
(a) provide non-gelatin hydrophilic gel 0.01～18 weight portion; Enteric solubility material 20～97 weight portions; PH regulator agent 0.01～25 weight portion; Flocculation aid 0～5 weight portion; Plasticizer 0～5 weight portion; Binding agent 0～80 weight portion; The water of 40～600 weight portions, described component Hybrid Heating obtains dissolved glue;
(b) glue that obtains of step (a) makes non-gelatine enteric hard capsule shell material with once dipping in glue method or pressing under 50～60 ℃ temperature;
(c) non-gelatine enteric hard capsule shell material that step (b) is obtained obtains moisture 3～12% non-gelatine enteric hard capsule shell material through 30～45 ℃ of oven dry.
The specific embodiment
The inventor is through going deep into and extensive studies for a long time, from solving existing enteric hard capsule defective, according to non-gelatin gels properties of materials, discovery with binding agent and hydrophilic gel and enteric material composite by a certain percentage after, regulate colloid pH by adding the pH regulator agent, make the present invention form the hard capsule casing material that mouthfeel is good, clarity is high, and make ideal non-gelatine enteric hard capsule shell without any need for organic solvent.Finished the present invention on this basis.
As used herein, described " alkyl " except as otherwise noted, refers to the straight or branched alkane that contains 2～20 carbon atoms.The alkane that preferably contains 1～10 carbon atom, for example, alkyl includes but not limited to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group.
Below describe in detail to various aspects of the present invention:
The invention provides a kind of compositions that is used to prepare non-gelatine enteric hard capsule shell material, described compositions contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(D) 40～600 weight parts waters;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
Substantially do not contain organic solvent in the described compositions.
Preferably, the amount that contains organic solvent in the described compositions is not higher than 5 weight % of composition total weight, more preferably no higher than 1 weight %, does not most preferably contain organic solvent.
" organic solvent " of the present invention comprises alcohols solvent, ketones solvent, ether solvent, alkane solvents or its combination.
Below each component of compositions is described in detail:
(A) non-gelatin hydrophilic gel
The composition of non-gelatin hydrophilic gel of the present invention, molecular weight or molecular weight are not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The representative example of non-gelatin hydrophilic gel of the present invention comprises (but being not limited to): acetylation gellan gum, deacetylation gellan gum, κ type carrageenan, ι type carrageenan, β type carrageenan, agar, pectin, sodium alginate, xanthan gum, tragacanth, POLY-karaya, locust bean gum, Furcellaran, tamarind gum (Tamarind Gum), tara gum, scleroglucan, microbial alginate, carbomer (Carbomer) or its combination.
Above-mentioned " acetylation gellan gum " comprises high acetylation gellan gum and low acetylation gellan gum.
" high acetylation gellan gum " of the present invention belongs to the commercially available chemical compound that gets, and its degree of acetylation is the conventional degree in this area.For example; described high acetylation gellan gum is meant that the C6 of the D-glucose residue in a kind of repetitive of gellan gum polysaccharide molecule has an appointment and 50 ± 10% is replaced by acetyl group; have the effect that hinders molecule structure of an essay net formation gel, thereby have good viscoelasticity, be referred to as high acyl gellan gum.
" low acetylation gellan gum " of the present invention belongs to the commercially available chemical compound that gets, and its degree of acetylation is the conventional degree in this area.For example, described low acetylation gellan gum is to slough low-acyl gellan gum behind most of acetyl group by the method for alkali treatment under the high temperature.Such gellan gum has good gelation.
Microorganism in the microbial alginate of the present invention is this area microorganism kind commonly used, is not specifically limited, as long as formed microbial alginate can be used as hydrophilic gel.
In non-gelatine enteric hard capsule shell compositions of the present invention, the non-gelatine enteric hard capsule shell material that makes or non-gelatine enteric hard capsule shell, the content of hydrophilic gel is generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion, this moment, the content of enteric solubility material was 20～97 weight portions.
(B) enteric solubility material
Enteric solubility material among the present invention is preferably polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
The content of enteric solubility material is generally 20～97 parts, and preferable is 30～80 parts, and more preferably 40～60 parts, this moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion.
(C) pH regulator agent
PH regulator agent among the present invention is: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqua ammonia, sodium bicarbonate, potassium bicarbonate, carbonic acid ammonia, sodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate, triethanolamine or its combination.
The content of pH regulator agent is generally 0.01～25 weight portion, preferred 0.1～8 weight portion; This moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion; The content of enteric solubility material is generally 20～97 parts, and preferable is 30～80 parts, more preferably 40～60 parts.
The inventor finds, after the quantitative pH regulator agent of adding, does not need a large amount of organic solvents also can prepare non-gelatine enteric hard capsule shell material in the enteric solubility material.In a preferred implementation, after specific enteric solubility material adds quantitative pH regulator agent, do not need organic solvent substantially, and can adopt and once dip in the glue legal system and be equipped with non-gelatine enteric hard capsule shell material, and the material breaks speed that obtains to be fast, the transparency is good; Described specific enteric solubility material is meant: polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
(D) water
Water of the present invention is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be pure water, deionized water, distilled water, mineral water or its combination.
The content of the water in the non-gelatin vegetative hard capsule casing of the present invention is generally 40～600 parts, preferred 80～400 parts, this moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion, the content of enteric solubility material is generally 20～97 parts, and preferable is 30～80 parts, more preferably 40～60 parts.
(E) flocculation aid
Hard capsule case of the present invention can optionally add flocculation aid.
Representational flocculation aid comprises (but being not limited to): potassium chloride, calcium chloride, potassium phosphate, potassium citrate and composition thereof.
The addition of flocculation aid is generally 0.01～5 weight portion, preferred 0.1～4 weight portion; This moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion.
Substantially, the consumption of flocculation aid and hydrophilic gel consumption are inversely proportional to.
(F) plasticizer
Hard capsule casing material of the present invention can optionally add plasticizer.
Representational plasticizer comprises (but being not limited to): glycerol, Sorbitol, Polyethylene Glycol and composition thereof, ethylene glycol, ethyl acetate, 1,3-butanediol, 1,4-butanediol, xylitol, Glycerine 1,3-diacetate, triacetin, monoacetin, mannitol, inositol, maltose alcohol, glucose, polypropylene glycol or its combination.
Plasticizer dosage is generally 0.01～5 weight portion, preferred 0.1～4 weight portion, and this moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion.
Usually, plasticizer dosage is relevant with capsule finished product soft or hard degree, and generally increases with the consumption of hydrophilic gel.
(G) binding agent
Hard capsule casing material of the present invention can optionally add binding agent.
Binding agent among the present invention is starch, dextrin, polyvinylpyrrolidone (also being polyvidone), carboxymethyl chitin, polyvinyl alcohol, sesbania gum, arabic gum, cassia gum, Pullulan, elsinan, Ficus elastica, glucosan, vinylpyrrolidone and vinyl acetate co-polymer, hydroxy alkyl cellulose, carboxyl alkyl cellulose or its combination.
The molecular weight or the molecular weight of described binding agent are not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
The polymerization methods of described copolymer and polymerization proportioning without limits, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Described herein " cellulose " also comprises the form of its slaine, for example is alkali metal salt, particularly as sodium salt, as sodium carboxymethyl cellulose.
Preferably, described binding agent is hydroxy alkyl cellulose, carboxyl alkyl cellulose, starch or its combination.Specifically for example, hydroxy alkyl cellulose and starch composites.
More preferably, described binding agent is a starch.
Most preferably, described starch is selected from high amylose starches, etherification starch, etherificate high amylose starches, etherificate high amylopectin starch, Oxytarch, oxidation high amylose starches, oxidation high amylopectin starch, esterification starch, esterification high amylose starches, esterification high amylopectin starch.
The content of binding agent is generally 0～80 part, and preferable is 0～60 part, more preferably 0～50 part, this moment, the content of hydrophilic gel was generally 0.01～18 weight portion, preferred 0.1～18 weight portion, more preferably 0.1～8.5 weight portion, the enteric solubility material is 20～97 weight portions.
The inventor finds, add the starch of particular types to hard capsule casing material that compositions makes as binding agent and increase significantly on the transparency, the starch of described particular types is selected from high amylose starches, etherification starch, etherificate high amylose starches, etherificate high amylopectin starch, Oxytarch, oxidation high amylose starches, oxidation high amylopectin starch, esterification starch, esterification high amylose starches, esterification high amylopectin starch.
Except said components, hard capsule casing material compositions of the present invention can also optionally be added other additives.For example antiseptic, antioxidant, pigment, flavoring agent, flavouring agent etc.Described other components of additives is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Representational antiseptic comprises (but being not limited to): sodium benzoate, methyl parahydroxybenzoate, propyl p-hydroxybenzoate and composition thereof.The weight content of antiseptic is generally 0.001～0.2%, preferably is about 0.01～0.19%, in the hard capsule casing material gross weight that makes at last.The antiseptic consumption is directly proportional substantially with binder dosage.
Representational antioxidant comprises (but being not limited to): propyl gallate, tea polyphenols, phytic acid, phospholipid, L～ascorbic acid and composition thereof.The weight content of antioxidant is generally 0.001～0.2%, preferably is about 0.01～0.19%, in the hard capsule casing material gross weight that makes at last.
The present invention also provides a kind of non-gelatine enteric hard capsule shell material, and described material contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
The weight summation of said components (A)+(B)+(C) accounts for 85～100 weight % of described hard capsule casing material gross weight;
Described material also contains the water of 3～12 weight % that account for described hard capsule casing material gross weight.
In the component of hard capsule casing material of the present invention, (A) non-gelatin hydrophilic gel, (B) enteric solubility material; (C) pH regulator agent; (E) flocculation aid; (F) plasticizer; (G) each component such as binding agent as mentioned above, identical with the description in the compositions about each component.
In the component of hard capsule casing material of the present invention, the kind of water is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.For example be pure water, deionized water, distilled water, mineral water or its combination.
The content of water is generally 3～12 weight % that account for described hard capsule casing material gross weight in the non-gelatin vegetative hard capsule casing material of the present invention.
Hard capsule casing material of the present invention can also optionally add other additives, and described other content of additive is not more than 15 weight % of hard capsule casing material gross weight usually.For example antiseptic, antioxidant, pigment, flavoring agent, flavouring agent etc.Described other components of additives is not particularly limited, only otherwise goal of the invention of the present invention is produced restriction to get final product.
Representational antiseptic comprises (but being not limited to): sodium benzoate, methyl parahydroxybenzoate, propyl p-hydroxybenzoate and composition thereof.The weight content of antiseptic is generally 0.001～0.2%, preferably is about 0.01～0.19%, in the hard capsule casing material gross weight.The antiseptic consumption is directly proportional substantially with binder dosage.
Representational antioxidant comprises (but being not limited to): propyl gallate, tea polyphenols, phytic acid, phospholipid, L～ascorbic acid and composition thereof.The weight content of antioxidant is generally 0.001～0.2%, preferably is about 0.01～0.19%, in the hard capsule casing material gross weight.
The production method of non-gelatine enteric hard capsule shell of the present invention comprises step:
(a) provide non-gelatin hydrophilic gel 0.01～18; Described pH regulator agent 0.01～20 weight portion of weight portion; The enteric solubility material is 20～97 weight portions, optional flocculation aid 0～5 weight portion; Optional plasticizer 0～5 weight portion; Binding agent 0～80 weight portion; The heating of described component and water mixes and obtains dissolved glue;
(b) glue that obtains of step (a) makes non-gelatine enteric hard capsule shell material with dipping in glue method or pressing under 50～60 ℃ temperature;
(c) non-gelatine enteric hard capsule shell that step (b) is obtained is through 30～45 ℃ of oven dry, and obtaining moisture is the non-gelatine enteric hard capsule shell material of 3～12 weight %.
Heating-up temperature is not specifically limited in the step (a), as long as obtain dissolved glue.
In a specific embodiment of the present invention, the present invention adopts elder generation with hydrophilic gel, binding agent and enteric solubility material mixing, adds water again and adds pH regulator agent, flocculation aid, plasticizer, makes non-gelatine enteric hard capsule shell material after the heating and melting.
In another preference, can mix the hydrophilic gel of 1～6 parts by weight earlier, the binding agent of 5～10 parts by weight, the enteric solubility material of 10～70 weight portions, the pH regulator agent of 1～15 weight portion, the plasticizer of 3～15 parts by weight forms mixture; Water with 28.8～94 parts by weight is heated to 75～95 ℃ again, mixture is dissolved in to make the colloid uniform dissolution then, obtains the liquid material; After insulation, the glue legal system is dipped in the feed liquid employing and get enteric hard capsule shell.After drying, softgel shell still contains a certain amount of water, general finished product water content about 3～12%.
The preparation method of non-gelatine enteric hard capsule shell of the present invention can be carried out on the equipment of existing preparation gelatin hard softgel shell.Need not set in addition under the condition that is equipped with, as long as can make required non-gelatine enteric hard capsule shell according to parameters such as the corresponding adjustment baking temperature of prescription, humidity, coating thickness, running speed, die sizes.
Compared with prior art, major advantage of the present invention is:
(1) preparation enteric capsule shell used colloidal materials does not contain animal protein and fat based on the non-gelatin gels of hydrophilic, thereby has avoided the pollution that may be caused by the animal proteinum protein.
(2) can add the plasticizer of enumerating among the present invention according to circumstances.
(3) the non-gelatin gel agent of hydrophilic is easy to dissolving, can save the imbibition stage necessary when making gelatine enteric capsule, saves the production time.
(4) tolerance to humiture makes it very convenient in use, storage and transportation.And gelatine enteric hard capsule shell is relatively stricter to the toleration of humiture, so its application is restricted.
(5) when keeping the advantage of gelatine enteric hard capsule shell, overcome gelatine enteric hard capsule shell and met high humidity, hot flexible type, under low temperature, the low water content condition easily embrittlement and can not load the aldehyde medicine etc. shortcoming.
(6) the non-gelatine enteric hard capsule also can dissolve in cold water, and the gelatine enteric hard capsule can only be in cold water swelling, can not dissolve
(7) the present invention once dips in gum forming and prepares the non-gelatine enteric hard capsule, has overcome gelatine enteric hard capsule secondary and has dipped in the gum forming preparation.
(8) the present invention's enteric solubility material of having overcome preparation gelatine enteric hard capsule also need use a large amount of organic solvents and easily initiation fire and explosive incident.
Chemical compound provided by the present invention can be synthetic by marketable material and traditional chemical transform mode.
Other aspects of the present invention are because the disclosure of this paper is conspicuous to those skilled in the art.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and percentage ratio are based on weight, unless stated otherwise.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any in addition method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Non-gelatine enteric hard capsule shell material 1
| Prescription | Consumption |
| The acetylation gellan gum | 1.25 gram |
| Hypromellose | 25 grams |
| The phthalic acid hypromellose | 30 grams |
| Calcium chloride | 1 gram |
| Ammonia | 25ml (25 gram) |
| Deionized water | 192.8 gram |
Manufacture method is: get acetylation gellan gum 1.25 grams, and phthalic acid hypromellose 30 grams, ammonia 25ml, calcium chloride 1 gram is poured in the 192.8 gram deionized waters, is heated to 100 ℃.Dissolving evenly stirs hypromellose 25 gram addings, behind insulation, froth breaking again, employing is once dipped in glue and is obtained hard capsule case, 40 ℃ of oven dry, the capsule shells water content is at 2 grams (3%), and the non-gelatine enteric hard capsule shell that makes is bright, flexible, mouthfeel is good.
Enteric hard capsule disintegrate standard according to Chinese Pharmacopoeia 2005 editions is measured, 45 minutes capsules break time.
Embodiment 2
Non-gelatine enteric hard capsule shell material 2
| Prescription | Consumption |
| ι type carrageenan | 4 grams |
| Hydroxypropyl starch | 16 grams |
| 1,2,4-benzenetricarboxylic acid cellulose acetate | 30 grams |
| Calcium chloride | 2 grams |
| Deionized water | 138 grams |
| Sodium carbonate | 10 grams |
Manufacture method is: get ι type carrageenan 4 grams, and hydroxypropyl starch 16 grams, calcium chloride 2 grams, 1,2,4-benzenetricarboxylic acid cellulose acetate 30 grams, sodium carbonate 10 grams are poured in the 138 gram deionized waters, are heated to 100 ℃.Dissolving is even, and behind insulation, froth breaking, employing is once dipped in glue and obtained enteric hard capsule shell, and 40 ℃ of oven dry, the capsule shells water content is at 4.8 grams (8%), and the non-gelatine enteric hard capsule shell that makes is bright, flexible, mouthfeel is good.
Enteric hard capsule disintegrate standard according to Chinese Pharmacopoeia 2005 editions is measured, 35 minutes capsules break time.
Embodiment 3
Non-gelatine enteric hard capsule shell material 3
| Composition of raw materials | Consumption |
| Hypromellose | 18 grams |
| κ type carrageenan | 1.6 gram |
| The enteric acrylic resin | 30 grams |
| Sodium hydroxide | 0.6 gram |
| Potassium chloride | 0.24 gram |
| L～ascorbic acid | 0.12 gram |
| Deionized water | 67.5 gram |
| Glycerol | 2.4 gram |
Manufacture method is: take by weighing κ type carrageenan 1.6 gram, enteric acrylic resin 30 grams, glycerol 2.4 grams, potassium chloride 0.24 gram, L～ascorbic acid 0.12 gram, sodium hydroxide 0.6 gram and pour 67.5 gram deionized waters into, be heated to 90 ℃, dissolving evenly, again hypromellose 18 grams are poured into, stir, cooling down is cooled to 55 ℃ with feed liquid behind the bubble, adopts once to dip in the glue legal system and get capsule shells.In about 35 ℃ of oven dry, the capsule water content of membrane is controlled in 1.1 grams (3%) transparent, the good springiness of the non-gelatine enteric hard capsule shell that finally obtains.
Enteric hard capsule standard according to Chinese Pharmacopoeia 2000 editions is measured, 50 minutes capsules break time.
Comparative Examples 1
Method according to embodiment 1 makes gelatine capsule, and difference is vegetalitas hydrophilic gel and binding agent equivalent are replaced with gelatin, and the product that obtains (snap fit capsule) compares with the product of embodiment 1 and 2, and the gained result is as follows:
(1) result of capsule shelf characteric such as following table 1:
Table 1 capsule shelf characteric relatively
| Project | The non-snap fit capsule that embodiment 1 and 2 makes | Snap fit capsule |
| Temperature: zero degree, humidity: 50% | Capsule is embrittlement not | The capsule embrittlement |
| Temperature: 40 degree, humidity: 50% | Capsule is indeformable | Capsule deformation |
The period of storage of above-mentioned storage requirement is a week.
(2) result of capsule transparency such as following table 2:
| Project | The non-snap fit capsule that embodiment 1 makes | The non-snap fit capsule that embodiment 2 makes | Snap fit capsule |
| Transparency relatively | More transparent | More transparent | Faint yellow |
The transparency assay method is as follows:
Sample thief 5.0g, after adding water 90ml and making expansion, heating for dissolving in 65～70 ℃ of water-baths is taken out, and adds water and makes into 100ml; Divide and get 5ml, put in the 25ml nessler colorimetric tube, (precision is measured standard sodium chloride solution 30ml with contrast liquid with volume immediately, put in the 50ml measuring bottle, add nitric acid and each 1ml of silver nitrate test solution, be diluted with water to scale, in the dark placed 5 minutes, available in case of necessity liquor sacchari usti toning) more muddy degree.
For the purpose of accurately, measure three times.If the turbidity of sample all less than contrast liquid, is considered as " more transparent " in measuring for three times.
The muddy degree that compares three samples simultaneously, three's transparency order is as follows:
The sample of embodiment 2〉sample of embodiment 1〉sample of Comparative Examples 1.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (12)
1. compositions that is used to prepare non-gelatine enteric hard capsule shell material, it is characterized in that: described compositions contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(D) 40～600 weight parts waters;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
Substantially do not contain organic solvent in the described compositions.
2. compositions as claimed in claim 1 is characterized in that,
The enteric solubility material of described component (B) is selected from down the enteric solubility material of group: polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
3. compositions as claimed in claim 1 is characterized in that,
The pH regulator agent of described component (C) is selected from down the pH regulator agent of group: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqua ammonia, sodium bicarbonate, potassium bicarbonate, carbonic acid ammonia, sodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate, triethanolamine or its combination.
4. non-gelatine enteric hard capsule shell material, it is characterized in that: described material contains following components by weight percent:
(A) the non-gelatin hydrophilic gel of 0.01～18 weight portion;
(B) 20～97 weight portion enteric solubility materials;
(C) 0.01～25 weight portion pH regulator agent;
(E) 0～5 weight portion flocculation aid;
(F) 0～5 weight portion plasticizer;
(G) 0～80 weight portion binding agent;
The weight summation of said components (A)+(B)+(C) accounts for 85～100 weight % of described hard capsule casing material gross weight;
Described material also contains the water of 3～12 weight % that account for described hard capsule casing material gross weight.
5. material as claimed in claim 4 is characterized in that,
The gel of described component (A) is selected from down the hydrophilic gel of group: acetylation gellan gum, deacetylation gellan gum, κ type carrageenan, ι type carrageenan, β type carrageenan, agar, pectin, sodium alginate, xanthan gum, tragacanth, POLY-karaya, locust bean gum, Furcellaran, tamarind gum, tara gum, scleroglucan, microbial alginate, carbomer or its combination.
6. material as claimed in claim 4 is characterized in that,
The enteric solubility material of described component (B) is selected from down the enteric solubility material of group: polyvinyl alcohol acetic acid phthalic acid ester, crylic acid resin, acetyl pullulan, cellulose acetate phthalate, 1,2,4-benzenetricarboxylic acid cellulose acetate, Hydroxypropyl Methylcellulose Phathalate, 1,2,4-benzenetricarboxylic acid hydroxypropyl emthylcellulose, succinic acid cellulose acetate and succinic acid acetic acid hydroxypropyl emthylcellulose or its combination.
7. material as claimed in claim 4 is characterized in that,
The pH regulator agent of described component (C) is selected from down the pH regulator agent of group: sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, aqua ammonia, sodium bicarbonate, potassium bicarbonate, carbonic acid ammonia, sodium hydrogen phosphate, dipotassium hydrogen phosphate, diammonium phosphate, triethanolamine or its combination.
8. material as claimed in claim 4 is characterized in that,
The binding agent of described component (G) is selected from following binding agent or its combination:
High amylose starches, etherification starch, etherificate high amylose starches, etherificate high amylopectin starch, Oxytarch, oxidation high amylose starches, oxidation high amylopectin starch, esterification starch, esterification high amylose starches, esterification high amylopectin starch or its combination.
9. a non-gelatine enteric hard capsule is characterized in that, it is made with the described non-gelatine enteric hard capsule shell material of claim 2.
10. the production method of a non-gelatine enteric hard capsule shell material is characterized in that, may further comprise the steps:
(a) provide non-gelatin hydrophilic gel 0.01～18 weight portion; Enteric solubility material 20～97 weight portions; PH regulator agent 0.01～25 weight portion; Flocculation aid 0～5 weight portion; Plasticizer 0～5 weight portion; Binding agent 0～80 weight portion; The water of 40～600 weight portions, described component Hybrid Heating obtains dissolved glue;
(b) glue that obtains of step (a) makes non-gelatine enteric hard capsule shell material with once dipping in glue method or pressing under 50～60 ℃ temperature;
(c) non-gelatine enteric hard capsule shell material that step (b) is obtained obtains moisture 3～12% non-gelatine enteric hard capsule shell material through 30～45 ℃ of oven dry.
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