JP4948835B2 - Hard coating layer, hard coating product and manufacturing method thereof - Google Patents

Description

  The present invention relates to a hard coating layer mainly composed of saccharides and sugar alcohols, a hard coating product in which a core material is coated with the hard coating layer, and a method for producing the same.

  Coating products are mainly formed by forming a film on the surface of the core material containing foods and pharmaceuticals, reducing the quality deterioration due to moisture absorption, oxidation and photolysis of the core material, and bitterness, odor and irritation of the core material. As a typical example, a coating technique for forming a saccharide film is well known. In addition to the viewpoint of whether or not the core material can be coated, the applicability of many materials to the coating field is being studied in accordance with various modern preferences.

  Among them, sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α-D- The applicability of coating products using sugars and sugar alcohols such as a mixture of glucopyranosyl-1,1-D-mannitol) has been studied.

  As a coating technique using sugar, Patent Document 1 discloses the production of a sugar-coated tablet characterized by applying sugar coating using a syrup containing at least one selected from hydroxypropylcellulose, hydroxypropylmethylcellulose and methylcellulose as a binder. The law is introduced. Further, in the specification, as an explanation of the prior art, it is described that a binder such as gelatin or gum arabic is added and used in order to increase the strength of the sugar-coating layer or to increase the bonding strength between the core tablet and the sugar-coating layer. ing.

  As a coating technique using sugar, Patent Document 2 discloses a solid preparation characterized by applying sugar coating to a solid preparation using a sugar coating solution containing pullulan and / or a water-soluble pullulan derivative in an aqueous sucrose solution. The sugar coating method is introduced. Further, in the specification, as an explanation of the prior art, it is described that a binder such as gelatin or gum arabic is added and used in order to increase the strength of the sugar-coating layer or to increase the bonding strength between the core tablet and the sugar-coating layer. ing.

  As a coating technique using trehalose, Patent Document 3 discloses a sugar-coated solid material in which the sugar-coated portion contains trehalose having a purity of 95% by weight or more and the surface is smooth and crystalline, and trehalose in the solid material. A sugar coating characterized by contacting trehalose syrup having a purity of 98% by weight or more, a concentration of 45 to 60% by weight and a temperature of 30 to 60 ° C. with a core material adjusted to a temperature of 20 to 50 ° C. A method for producing a sugar-coating solid that contains trehalose with a purity of 95% by weight or more and has a smooth surface is introduced.

  As a coating technique using lactitol, Patent Document 4 discloses a sugar-coated product in which a core material is coated with a sugar-coating layer containing lactitol and crystalline cellulose, 40 to 65% by weight of dry matter weight of lactitol, and 0% of crystalline cellulose. A process for producing a sugar-coated product characterized in that a sugar-coated syrup containing 5 to 3% by weight is supplied to a core material placed in a sugar-coated bread is introduced. Binders such as gum, pullulan, karaya gum, and xanthan gum are exemplified as substances that may be added to the sugar-coated syrup.

  Palatinite (registered trademark), which is a mixture of 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α-D-glucopyranosyl-1,1-D-mannitol) Patent Document 5 discloses a coated product comprising a core and a coating as a coating technique using the coating, wherein the coating is 57% by weight: 43% by weight to 99% by weight: 1% by weight of 1,6. At least a 1,6-GPS concentrated mixture consisting of GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α-D-glucopyranosyl-1,1-D-mannitol) A coated product comprising a single layer is disclosed, and further in the specification, as a film former, methylcellulose, gelatin, hydroxypropylcellulose, ethylcellulose , Hydroxyethyl cellulose, carboxymethyl cellulose and mixtures thereof.

  As a coating technique using maltitol, Patent Document 6 discloses that in the production of a sugar-coated solid preparation, the core material is coated with an aqueous solution containing a sugar-coating reinforcement together with high-purity maltitol having a purity of 90 w / w% or more. A method for producing a sugar-coating solid preparation characterized by drying maltitol to crystallize maltitol is disclosed, and the use of pullulan as the sugar-coating reinforcement is disclosed.

  Furthermore, as a coating technique using various saccharides and sugar alcohols, Patent Document 7 discloses any one sugar / sugar selected from the group consisting of maltitol, xylitol, erythritol, mannitol, lactitol, palatinit, trehalose, and sucrose. A hard sugar-coated preparation having a hard sugar-coated layer containing alcohol and oxidized starch and / or acid-treated starch is disclosed.

  As introduced in the above-mentioned Patent Documents 1 to 7, as a method for obtaining a hard coating layer with various saccharides or sugar alcohols, use of saccharides or sugar alcohols forming the coating layer with high purity, In addition to sugars or sugar alcohols, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, pullulan, water-soluble pullulan derivatives, gelatin, gum arabic, starch, karaya gum, xanthan gum, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, oxidized starch, acid-treated starch A method of adding various components as reinforcing agents has been proposed.

  However, many of the conventional reinforcing agents do not necessarily have good solubility in water, and it takes time to prepare a coating solution because the viscosity tends to increase when dissolved in water. There was a case. In addition, when a raw material solution for forming a hard coating layer (hereinafter referred to as a coating solution) is used, it often becomes an aqueous solution having a high viscosity, and further, a natural product is used as it is as a reinforcing agent. Since dust and impurities may be included, even if a coating solution is applied to the surface of the core material when forming the hard coating layer, the coating layer does not stretch sufficiently and the coating layer is uneven. It has been pointed out that there are problems in operability at the time of forming a coating layer, such that the core material is easily solidified because the coating solution is highly viscous and sticky. In addition, the quality of coating products using conventional reinforcing agents can be attributed to the physical properties of the reinforcing agent itself and the above-mentioned problems in the manufacturing process, but the strength of the hard coating layer is low, the core It is difficult to form a uniform and smooth hard coating layer on the material, coating products prepared with the addition of a reinforcing agent are less disintegrating, cracks occur on the surface of the hard coating product over time, reinforcement Depending on the agent, the physical properties of the hard coating product itself have many points to be improved, such as the hard coating layer formed easily browning over time. In addition, it can be said that the reinforcing agents introduced in the prior art are expensive, the production volume is unstable, and it is difficult to ensure the stability of raw materials, which is a concern for manufacturing on an industrial scale.

JP-A 49-108225 JP 59-219220 A JP-A-9-154493 JP-A-6-70688 JP 2000-342185 A JP-A 61-263915 JP 2003-292436 A

  The problem to be solved by the present invention is to provide a hard coating layer, a hard coating product mainly comprising a specific saccharide or sugar alcohol, and a method for producing the same, by using hydroxyalkylated dextrin as a reinforcing agent. Improved and satisfactory with respect to strength, smoothness of hard coating layer surface, disintegration of hard coating products, crunchiness when chewing hard coating products, hard coating products are difficult to crack, etc. It is to provide what can be done.

  The inventor has made sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α- D-glucopyranosyl-1,1-D-mannitol), a hard coating layer mainly composed of any one selected from the group of the above saccharides and sugar alcohols, or quality and physical properties of a hard coating product As a result of intensive studies on the above, as a result of using the hydroxyalkylated dextrin as a reinforcing agent for the coating layer, the problem is improved or solved by using any one of the saccharides and sugar alcohols as a main component and the present invention. It came to complete. The mixture of 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α-D-glucopyranosyl-1,1-D-mannitol) is hereinafter referred to as 1 , 6-GPS and 1,1-GPM, or Paratinit, the registered trademark of the product.

  That is, the means for solving the problems of the present invention are as follows.

  First, as main components, sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM A mixture of (α-D-glucopyranosyl-1,1-D-mannitol), any one selected from the group of the above saccharides and sugar alcohols, and a hydroxyalkylated dextrin as a reinforcing agent in the solid state of the hard coating layer It is a hard coating layer containing 0.1 to 10.0% by weight in terms of product.

  Second, the hard coating layer according to the first, wherein the hydroxyalkylated dextrin is hydroxypropylated dextrin.

  Third, the hard coating layer according to the first or second aspect, wherein the dextrose equivalent (DE) of the hydroxyalkylated dextrin is 0.1 or more and less than 5.0.

  Fourth, the hard coating layer according to any one of the first to third, wherein the hydroxyalkylated dextrin is crosslinked with a crosslinking agent.

  Fifth, the hard coating layer according to any one of the first to fourth, wherein the hydroxyalkylated dextrin has a viscosity of 50 to 350 cp when it is an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C. It is.

  Sixth, it is a hard coating product in which a core material is coated with the hard coating layer described in any one of the first to fifth.

  Seventh, sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) as a main component in the solid component of the coating solution ) And 1,1-GPM (α-D-glucopyranosyl-1,1-D-mannitol), any one selected from the group of saccharides and sugar alcohols, and hydroxyalkylated as a reinforcing agent This is a method for producing a hard coating product, in which a coating solution containing dextrin is applied to a core material, dried to crystallize solids from the coating solution, and the coating solution is applied and dried repeatedly.

  The hard coating layer is a coating solution containing the components that form the coating layer is applied around the core material, then solids are crystallized from the coating solution by a drying process, and further solidified, and the coating solution is applied and dried. This refers to a crystallized solidified product obtained by repeating the above step until a crystallized product having a desired thickness or weight is formed around the core material. Hard coating products refer to core coating surfaces and surroundings that are coated with a hard coating layer. This hard coating layer provides protection to the core material against impacts and moisture, and has an excellent appearance. It becomes possible to make it. Also, the hard coating product can be chewed with a crunchy and favorable crunchy texture when eaten.

  In the hard coating layer according to the present invention, hydroxyalkylated dextrin is employed as a reinforcing agent. By using this hydroxyalkylated dextrin as a reinforcing agent, the strength of the hard coating layer is high, the surface of the hard coating layer has excellent smoothness, and the disintegration property of the hard coating product is good. The present invention has satisfactory crunch properties when chewed with a hard coating product and satisfies the problems of the present invention, such as being hard to crack on the surface of the coating layer even if the hard coating product is stored under dry conditions. It is possible to bring about a favorable effect.

  In preparing the hydroxyalkylated dextrin, the starch is hydroxyalkylated and then hydrolyzed by a known method until it has a desired dextrose equivallent (DE); Any method of preparing a dextrin having DE and then performing a hydroxyalkylation treatment on the obtained dextrin may be adopted. However, considering the ease of preparation and the stability of quality after preparation, it can be said that the former preparation method in which starch is hydroxyalkylated first is preferable.

  The starch hydrolysis treatment performed in the preparation of the hydroxyalkylated dextrin is not particularly limited as long as the starch is hydrolyzed to a desired DE value, such as acid, alkali, heating, and enzyme treatment. Hydrolysis treatment by enzyme treatment, typified by α-amylase, is preferable because it is easy to prepare dextrins having a. The DE of the hydroxyalkylated dextrin that can be employed as a reinforcing agent varies depending on the degree of substitution of hydroxyalkylation and the presence or absence of crosslinking, but the approximate DE is 0.1 or more and less than 5.0, preferably 0. 0.5 or more and 3.5 or less, particularly preferably 1.2 or more and 2.5 or less.

  In the preparation of the hydroxyalkylated dextrin, as described above, dextrin can be prepared by hydrolyzing starch until it has the desired DE with acid. On the other hand, there is a substance called acid-treated starch by those skilled in the art in Japan. This is a substance sometimes translated as Thinboiling Starch and Modified Starch, and it is listed as a kind of modified starch as a classification, but as the name suggests, it is one of the substances obtained by treating starch with mineral acid solution. Therefore, confusion with dextrin that can be prepared by acid hydrolysis may occur. However, acid-treated starch and dextrin have differences not only in classification but also in terms of substances and physical properties. For example, the former acid-treated starch is a part of the amorphous part of starch particles. Is decomposed, but the starch particle structure itself remains, and a color reaction that turns purple with respect to the iodine starch reaction is observed. Moreover, since the starch structure substantially remains in the acid-treated starch, it is very difficult to define the degree of decomposition by DE. On the other hand, the latter dextrin does not retain the starch particle structure and has a degree of decomposition that can be defined by DE. Therefore, in this invention, the hydroxyalkylated dextrin which is a reinforcing agent which concerns on this invention, and an acid process hydroxyalkylated starch or a hydroxyalkylated acid process starch are handled as a completely different substance. Further, when used as a reinforcing agent for the hard coating layer, the difference between the two is clearly shown.

  As raw materials used for the preparation of hydroxyalkylated dextrin, various starches such as corn starch (corn starch), waxy corn starch, high amylose corn starch, wheat starch, rice starch, sago starch, sorghum starch, potato starch, sweet potato starch, Various underground starches such as tapioca starch, dextrins prepared using these various starches as a raw material, and mixtures of these various starches and various dextrins can be employed, and there are no particular restrictions on the types and origins thereof. Among these, waxy corn starch, potato starch, tapioca starch, or the like in terms of difficulty in aging of the reinforcing agent after processing preparation, ease of preparation of the coating solution, excellent operability when forming the coating layer, or the like Dextrins prepared from these are preferred. Also, dextrin prepared from waxy corn starch or waxy corn starch is particularly preferred because it has a high amylopectin content, is less likely to cause aging after processing, and is particularly excellent in terms of quality stability.

  The hydroxyalkylated dextrin is obtained by subjecting starch or dextrin as a raw material to hydroxyalkylation by allowing various alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and the like to act. Among these, hydroxypropylated dextrin is preferable because of the quality of the hard coating layer. The degree of substitution representing the degree of hydroxyalkylation may be slightly varied depending on the type of starch, the presence or absence of crosslinking treatment, the DE value of hydroxyalkylated dextrin, etc., but is not particularly limited as long as it does not impede the practice of the present invention. . The degree of substitution is a value obtained from the average value of substituents per glucose residue of starch, and the degree of substitution may be expressed as DS (degree of substitution). Illustrative examples of the degree of substitution preferred in the present invention are DS of about 0.01 to 0.36, and a more preferred range is DS of 0.03 to 0.20, and among them, particularly preferred is DS of about 0.06 to 0.18. . In the present invention, there is no need to increase the degree of substitution more than necessary, but there is no particular problem even if the degree of substitution is increased beyond the numerical values shown above.

  In the hard coating layer according to the present invention, the hydroxyalkylated dextrin employed as a reinforcing agent is allowed to react with a crosslinking agent to give a crosslinked structure, thereby suppressing dextrin aging. The quality of the coating solution can be stabilized, the increase in viscosity of the coating solution over time can be suppressed, and favorable properties can be provided as a reinforcing agent. Cross-linking agents include epichlorohydrin, sodium trimetaphosphate, sodium trimetaphosphate / sodium tripolyphosphate, acrolein, cyanuric chloride, adipic acid / acetic acid mixed anhydride, phosphorus oxychloride, formalin, diepoxide compound, dialdehyde Any reagent that can react with the hydroxyl group of starch to form a crosslinked structure, such as a compound, can be used. Among the cross-linked structures obtained by the cross-linking agent, phosphoric acid cross-linked hydroxyalkylated phosphoric acid cross-linked dextrin can be said to be a particularly preferable form as a reinforcing agent for the hard coating layer according to the present invention.

  When preparing a hydroxyalkylated cross-linked dextrin as a reinforcing agent for the hard coating layer according to the present invention, the timing for carrying out the cross-linking reaction is not particularly limited. For example, the starch or dextrin before the hydroxyalkylation reaction is subjected to a crosslinking reaction, and once the crosslinked starch or crosslinked dextrin is formed, the hydroxyalkylation is performed, and finally the desired DE is obtained as necessary. You may employ | adopt the preparation method which performs a hydrolysis process until it has. As another method, it is also possible to employ a preparation method in which a starch or dextrin is subjected to a hydroxyalkylation reaction to obtain a hydroxyalkylated starch or a hydroxyalkylated dextrin, and then a crosslinking reaction is performed. And finally, you may employ | adopt the preparation method which performs a hydrolysis process until it has desired DE as needed. Moreover, when performing these reactions, there is no restriction | limiting in particular about the grade of a crosslinking reaction, if it is a range which does not prevent implementation of this invention. In the present invention, starch is used as a starting material, hydroxyalkylated starch is then prepared by a hydroxyalkylation treatment, then a hydroxyalkylated crosslinked starch having a crosslinked structure is prepared by a crosslinking agent, and finally a desired DE is obtained. A method for preparing a hydroxyalkylated crosslinked dextrin by carrying out a hydrolysis reaction until it is contained is preferable in terms of ease of controlling the preparation reaction of the reinforcing agent and the quality and stability of the obtained reinforcing agent.

  DE of hydroxyalkylated dextrin, which is a reinforcing agent for hard coating layers according to the present invention, is the type of starch, the type and substitution degree of hydroxyalkylation, the presence or absence of a crosslinked structure, the quality and stability when used as a reinforcing agent, etc. Judgment should be made comprehensively. For example, when the approximate degree of decomposition of a hydroxyalkylated crosslinked dextrin having a crosslinked structure is represented by DE, DE is 0.1 or more and less than 5.0, more preferably DE 0.5 or more and 3.5 or less, and particularly preferably among them. Is DE 1.0 to 2.5, most preferably DE 1.2 to 2.0. Further, when the approximate degree of decomposition of a hydroxyalkylated dextrin having no cross-linked structure is represented by DE, DE is 0.1 or more and less than 5.0, more preferably DE 0.5 or more and 3.5 or less. Preferably, DE is 1.5 or more and 3.0 or less, and most preferably DE is 2.0 or more and 2.5 or less. Further, if DE is less than 0.1, the viscosity when used as a coating solution is high, the hydrolysis reaction is difficult to control and the preparation is difficult, and the preferable effects according to the present invention are not sufficiently exhibited. There is a fear. Moreover, when DE is 5.0 or more, the formation of the coating layer is delayed, the smoothness of the surface of the coating layer is lowered, or the crunch property of the coating product is inferior. There is.

  As a preferable form of the reinforcing agent for the hard coating layer according to the present invention, for example, hydroxypropylated starch having a substitution degree of about 0.06 to 0.18 by hydroxypropylation using waxy corn starch and / or tapioca starch as a starting material. Then, the hydroxypropylated phosphate-crosslinked dextrin derived from waxy corn starch and / or tapioca starch prepared by phosphoric acid crosslinking and finally having a DE of about 1.2 to about 2.0 by enzymatic hydrolysis treatment Can be illustrated. As another form, starch, which is selected from the group consisting of waxy corn starch, tapioca starch, and potato starch, is used as a starting material, and the degree of substitution is about 0.06 to 0.12 by hydroxypropylation. Hydroxypropylated dextrin derived from waxy corn starch and / or tapioca starch and / or potato starch, which was prepared by hydrolyzing the starch and then having a DE of 2.0 to DE of about 2.5 by enzymatic hydrolysis. It can be illustrated.

  The hydroxyalkylated dextrin, which is a reinforcing agent for the hard coating layer according to the present invention, is prepared to have various physical properties depending on various factors such as starch type, hydroxyalkyl group type and substitution degree, presence / absence of crosslinking agent, DE value, etc. However, as one guideline that the effect according to the present invention is suitably expressed, an aqueous solution of hydroxyalkylated dextrin can be prepared and evaluated by the viscosity of the aqueous solution at that time. Specifically, an aqueous hydroxyalkylated dextrin solution having a solid content of 30% by weight and a temperature of 30 ° C. is prepared, and the standard of the lower limit when the viscosity at that time is measured with a B-type viscometer is preferably 50 cp or more, More preferably, it is 100 cp or more, Especially preferably, it is 140 cp or more, Most preferably, it is 150 cp or more. The upper limit of the viscosity range is preferably 350 cp or less, more preferably 320 cp or less, particularly preferably 300 cp or less, and most preferably 270 cp or less. By using a hydroxyalkylated dextrin having the above-mentioned viscosity as an aqueous solution as a reinforcing agent, it is relatively easy to prepare a coating solution, and the coating solution can be stretched with respect to the core material. The prepared hard coating layer and hard coating product also have high strength with respect to the strength of the hard coating layer, and the surface of the hard coating layer has excellent smoothness. Good disintegration, good crunch properties when chewing hard coating products, and brings about favorable effects such as hard cracking of hard coating layer surface even when hard coating products are stored under dry conditions be able to.

  In the present invention, sugars and sugar alcohols used as the main component of the hard coating layer are sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS and 1,1-GPM. Mixture, refers to a substance described in the above group.

  Examples of the mixture of 1,6-GPS and 1,1-GPM include sugar alcohol products sold under the trade name of Palatinite (registered trademark) by Mitsui Sugar Co., Ltd.

  The above saccharides and sugar alcohols only need to be of a quality that is commercially available for various uses such as foods, food additives, and pharmaceuticals, and are particularly affected by their raw materials, manufacturing methods, or shapes such as liquids and solids. I will not receive it. Further, as long as the implementation of the present invention is not hindered, the above saccharides and sugar alcohols may be any of crystalline products, honey crystal products, and amorphous powders, and may be either water-containing crystals or anhydrous crystals. good.

  When preparing a hard coating product according to the present invention using the above saccharides and sugar alcohols as raw materials, maltitol, xylitol, sugar, and palatinit are particularly preferred saccharides and sugar alcohols in that the strength of the hard coating layer is increased. Among them, maltitol is finished in the hard coating layer having the highest strength. In addition, maltitol and xylitol can be exemplified as particularly preferred sugar alcohols in that a hard coating layer having excellent smoothness can be obtained, and among them, maltitol is most preferable. In addition, maltitol can be exemplified as the most preferable sugar alcohol in that a hard coating product having excellent crunch properties can be obtained.

  About the hard coating layer and hard coating product according to the present invention, the strength of the hard coating layer, the smoothness of the surface of the hard coating layer, the disintegration of the hard coating product, the crunchiness when biting the hard coating product, the drying of the hard coating product In view of the overall difficulty of cracking under conditions and the above qualities, among the saccharides and sugar alcohols exemplified by the present invention as the main component of the hard coating layer, preferred are sugar, maltitol, Xylitol, and a mixture of 1,6-GPS and 1,1-GPM, more preferably sugar, maltitol, and xylitol. Among them, maltitol and xylitol are particularly preferable, and maltitol is most preferable. is there.

  In the present invention, saccharides and sugar alcohols are employed as the main components constituting the hard coating layer. Here, the main component is a kind of component selected from the group of saccharides and sugar alcohols that can be employed in the present invention. It means that the content of is 50.0% by weight or more in terms of the solid component forming the hard coating layer. The preferable content of saccharides and sugar alcohols in the hard coating layer is 80.0% by weight or more, more preferably 90.0% by weight or more, particularly preferably 94% in terms of solid components of the formed hard coating layer. 0.0% by weight or more, and most preferably 95.0% by weight or more. In addition, the upper limit value of sugars and sugar alcohols in the hard coating layer can be exemplified by 99.9% by weight or less, preferably 99.0% by weight or less in consideration of the addition amount of the reinforcing agent, more preferably The upper limit is the amount corresponding to all the remainder except the reinforcing agent contained in the hard coating layer according to the present invention. Unless the implementation of the present invention is impeded, impurities and nectar components contained in saccharides and sugar alcohols employed as the main component of the hard coating layer, and coexistence of various saccharides and sugar alcohols other than the main components are Acceptable.

  In the present invention, the content of the hydroxyalkylated dextrin employed as a reinforcing agent for the hard coating layer is 0.1 to 10.0% by weight, preferably in terms of the solid component of the portion forming the hard coating layer, preferably 1.0 to 9.0% by weight, more preferably 3.0 to 6.0% by weight, and most preferably 4.0 to 5.0% by weight.

  If the content of the reinforcing agent in the hard coating layer is less than the above range, various effects brought about by the reinforcing agent cannot be sufficiently obtained. Moreover, even if it adds the quantity exceeding the above-mentioned range, the effect as high as the addition quantity is not acquired, and it is economically unpreferable. Furthermore, if the amount of reinforcing agent added is further increased, crystallization of sugars or sugar alcohols, which are the main components of the hard coating layer, is delayed, crystal crystallization itself is suppressed, and formation of the coating layer is delayed. May become difficult.

  The material applicable as the core material of the hard coating product according to the present invention is not limited as long as it is not a material that significantly impedes the formation of the coating layer, as long as it is a material known to be used as the core material of the coating layer, The present invention can also be applied. Specific core materials include, for example, gum, candy, troches, tablets, gummi, chocolate, jelly, bread, cakes, pretzels, crackers, toffee, dumplings, fried confectionery, snack confectionery, potato chips, sweet natto, and popcorn. , Various fruits, various vegetables, various beans and their dry matter, and other medicines can be used as a core material, and the shape is not particularly limited.

  In practicing the present invention, the material of the hard coating layer includes not only sugars and sugar alcohols which are the main components of the hard coating layer, and hydroxyalkylated dextrin which is a reinforcing agent for the hard coating layer, but does not interfere with the practice of the present invention. Known coating layers such as hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, pullulan, water-soluble pullulan derivatives, gelatin, gum arabic, starch, karaya gum, xanthan gum, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, oxidized starch, acid-treated starch Talc, kaolin, calcium carbonate, titanium dioxide, eggshell, which can form a coating layer substantially as a reinforcing agent for the coating layer, and can form a coating layer substantially and is difficult to insoluble in water Calcium, various bases such as shell calcium, may be used in combination thereof one or more.

  In addition, as long as it does not interfere with the practice of the present invention, various amino acids such as glycine, alanine, leucine, tyrosine, glutamic acid and salts thereof, ascorbic acid, citric acid, for the purpose of improving the taste and appearance of the hard coating layer Add various organic acids such as tartaric acid, malic acid, adipic acid, succinic acid and their salts, high sweetness sweeteners such as aspartame, sucralose, and acesulfame K, polishes, coloring agents, flavoring agents, surfactants, etc. May be.

  The coating solution as used in the field of this invention refers to the aqueous solution containing the raw material required in order to form a hard coating layer, and may be called a sugar coating liquid by those skilled in the art.

  The application of the coating solution to the core material in the present invention is not particularly limited as long as the coating solution is applied to the surface of the core material or brought into contact with the core material as long as the implementation of the present invention is not hindered. Any method represented by technical terms such as coating, spraying, spraying, and liquid coating is included.

  As a method for producing a hard coating product having a hard coating layer according to the present invention, it is possible to use a device used for forming a known coating layer as it is, and there are no particular restrictions on the means or type of device. No. As an example, the core material to be coated is placed in a coating pan that can be rotated intermittently or continuously, and if necessary, the coating solution is applied to the core material with rotation or as it is, and then the coating pan is applied. Is rotated to spread the coating solution evenly on the surface of the core material, and at the same time, the coating solution is urged to be dried by blowing air as necessary, and the solidified product is crystallized by drying the applied coating solution. Thereafter, the coating solution may be applied and dried repeatedly until a coating layer having a desired thickness is formed on the core material.

  When preparing a hard coating product, the solid content concentration of the coating solution is not particularly limited as long as a hard coating layer having a desired quality can be obtained by repeatedly applying the coating solution to the core and drying. For example, a solid content concentration of about 50 to 80% by weight can be exemplified as a suitable range.

  At any time during the process of forming the hard coating layer on the core material, the solid component of the coating solution can be sprayed or sprayed onto the core material with the same kind of sugar or sugar alcohol as the main component in the coating solution. The crystallization and solidification of the coating layer can be further promoted, and depending on the amount to be added, the texture of the coating layer can be changed or characterized.

  In the hard coating layer and the hard coating product according to the present invention, the strength of the hard coating layer, the smoothness of the surface of the hard coating layer, the disintegration property of the hard coating product, the crunch property when chewing the hard coating product, the drying of the hard coating product In order to suitably exhibit various effects such as the difficulty of cracking under conditions, it is desirable to provide a hard coating product in which a certain amount or more of a hard coating layer is formed on the core material. In the present invention, as a measure of the formation ratio of the hard coating layer, a method of obtaining the weight ratio of the hard coating layer when the core material weight is 100% (hereinafter, this weight ratio is referred to as coating coverage) is adopted. The Specifically, the weight of the formed hard coating layer may be obtained by dividing by the weight of the core material. The term “coating coverage” is sometimes called sugar coating ratio among those skilled in the art, and is used as an index indicating the thickness of the coating layer and the degree of coating. When the hard coating product according to the present invention is represented by this coating coverage, various protective functions by the coating layer are expressed at a very preferable level if it is 30% or more, preferably 40% or more, particularly preferably 50% or more. However, even if it is less than 30%, a coating layer can be formed, and a coated product can be obtained. As a method of measuring the weight of the hard coating layer, the formed hard coating layer may be separated from the core material, and the weight of the part may be directly measured. However, the weight of the core material before coating is determined from the weight of the hard coating product. The value obtained by subtracting may be used as the weight of the hard coating layer, and the coating coverage may be obtained based on the value.

  The hard coating layer and the hard coating product according to the present invention have high strength with respect to the strength of the hard coating layer, the surface of the hard coating layer has excellent smoothness, and the disintegration property of the hard coating product is good. It has good crunch properties when chewed with hard coating products, and it has good properties as a hard coating product, such as being hard to crack on the surface of the hard coating layer even if the hard coating product is stored under dry conditions. The These preferable effects brought about by the present invention are evaluated based on the following measurement methods.

  In the evaluation of various physical properties related to the hard coating product according to the present invention, lactose simulated tablets (tablet diameter: 10 mm, R: 8.5 mm, H: 1.63 mm, average weight: 360 mg / tablet, Sankei Health) Co., Ltd.) was used until the average weight of the hard coating product reached 540 mg / tablet, and a hard coating product with an average coating coverage of 50% was prepared. Sealed in a storage bag (trade name: Rami Zip AL16, manufactured by Nihon Shokuhin Co., Ltd.) and allowed to stand at room temperature for 2 weeks was used as a model product of a hard coating product, which was used as a specimen for various experiments. .

  The hard coating product according to the present invention is characterized in that the strength of the hard coating layer is improved and cracking is unlikely to occur even under impact. In the present invention, as a method for evaluating the strength of the hard coating layer, the hard coating product is freely dropped on a smooth marble plate from a height of 30 cm, and the number of drops required until the hard coating layer surface is cracked is measured. A method of evaluating the strength of the hard coating layer by performing 20 drop tests on the coating products prepared in each of the preparation examples and obtaining an average value thereof is adopted.

  At the production site, cracks of the hard coating layer due to various impacts, such as contact between hard coating products that occur when filling or transporting a hard coating product into a predetermined container, contact with the wall surface of the container or filling device, etc. Damage, peeling, etc. should be avoided most. From such a viewpoint, in the drop test, a coating product in which the average value of 20 samples is 1.0 times or more and less than 2.0 times has a risk that the coating layer is cracked, broken or peeled off by one impact. It is not preferable because it cannot be said to have a quality that can withstand manufacturing at an actual production site. In addition, a coated product having an average value of 20 samples of 2.0 times or more and less than 3.0 times can withstand a single impact, but it is not always satisfactory when the impact of the impact generated in the distribution process is taken into consideration. It is not a standard. Considering each process such as production, filling, distribution, etc. at the production site, the average value of 20 specimens in the drop test is at least 3.0 times or more, and 4.0 times or more for safety It can be said that there is a level desired as a hard coating product that can withstand practical use. According to this test method, the hard coating product according to the present invention is 4.0 times or more, preferably 5.0 times or more in a drop test, depending on the types of sugars and sugar alcohols forming the hard coating layer. The result is more preferably 6.0 times or more, particularly preferably 7.0 times or more, and most preferably 10.0 times or more, and has high strength.

  The hard coating product according to the present invention has a very smooth finish on the surface of the hard coating layer and has excellent smoothness. One of the reasons for this is considered to be the ease of spreading of the coating solution around the core material, the low stickiness, and the crystallinity of the solid component from the coating solution. In the present invention, as a method for evaluating the smoothness of the surface of the hard coating layer, 20 samples are arbitrarily taken out from the prepared product, and the unevenness of the surface of the coating layer is scored according to the following criteria by visual observation of 10 trained panelists. Then, the smoothness of the coating layer was evaluated from the score. The smoothness was evaluated as 3 points: “no unevenness”, 2 points: “almost unevenness”, 1 point: “slightly uneven”, 0 point: “many unevenness”, and the result was 30 Points to 26 as “smooth”, ◎, 25 to 16 as “slightly smooth”, 15 to 6 as “slightly uneven”, △, 5 points or less as “uneven” as x, An evaluation method is adopted. From the measurement results, the hard coating layer according to the present invention can be evaluated with ◎ or ○ for any saccharide and sugar alcohol as the main component, and has excellent smoothness. confirmed.

  Usually, many of the conventional reinforcing agents used in the coating layer are not soluble in water, and coating products using such reinforcing agents depend on the type and amount of the reinforcing agent, Generally, the degree of collapse tends to decrease. These tendencies sometimes persist unpleasant sensations such as feeling left over in the mouth and crispness when eating a coated product. On the other hand, the hard coating product according to the present invention dissolves relatively quickly in water and exhibits an excellent degree of disintegration, contrary to conventional knowledge, despite the use of a reinforcing agent. Specifically, in the case of a hard coating product according to the present invention, even when a reinforcing agent is added, the degradation degree is hardly decreased, and the degree of disintegration is the same as that of a coated product prepared without adding a reinforcing agent. And has characteristics not found in hard coating products obtained using conventional reinforcing agents. The excellent disintegration degree of the hard coating product according to the present invention is clarified by the disintegration test shown below.

  As an index for evaluating the disintegration degree of the hard coating product according to the present invention, a disintegration test using a disintegration tester (device name: NT-2H, manufactured by Toyama Sangyo Co., Ltd.) is performed, and the time required for the disintegration of the hard coating product Therefore, a method for evaluating the disintegration degree of each coated product is adopted. The disintegration degree was measured according to the method described in “58. Disintegration test method” described on pages B-619 to B-628 of the 14th revised Japanese Pharmacopoeia Manual (2001, published by Yodogawa Shoten). Is done. Specifically, a basket dedicated to the disintegration degree tester is attached to a receiving shaft, and the basket is smoothly placed in a beaker installed in the disintegration degree tester with 29 to 32 reciprocations per minute and an amplitude of 53 to 57 mm. Is adjusted to move up and down. When the basket is at the lowest position, the mesh surface of the bottom of the basket is 25 mm from the bottom of the beaker, and the amount of test liquid to be placed in the beaker is such that the top surface of the basket matches the surface of the liquid when the basket is at the lowest position. The temperature of the test solution is kept at 37 ± 2 ° C. Pure water is used as a test solution, and one hard coating product to be measured is put in each of six glass tubes in the basket. The basket is immersed in a test solution in a beaker whose temperature and amount have been adjusted in advance, and continues to move up and down for a certain period of time, and the time required until no residue is found in the glass tube is measured as the disintegration time. In the present invention, six samples were tested per product, and the average value of the disintegration time was adopted as an index of the disintegration degree.

  The hard coating product according to the present invention maintains almost the same degree of disintegration as the coating product mainly composed of sugars and sugar alcohols prepared without adding a reinforcing agent, and has the same degree of disintegration. Compared with coating products containing agents, the degree of disintegration is greatly improved. The index of disintegration is the average for each of the hard coating product according to the present invention using the same saccharide or sugar alcohol as the main component of the coating layer and the coating product prepared without adding a reinforcing agent as a control product. It is obtained by comparing the decay time. The disintegration time of the hard coating product according to the present invention is at most an increase time of 10% or less of the disintegration time of the control product, preferably an increase time of 6% or less of the disintegration time of the control product, more preferably It is an increase time of 3% or less of the disintegration time of the control product, and particularly preferably an increase time of 1% or less of the disintegration time of the control product. In some cases, the disintegration time may be shorter than the disintegration time of the control product.

  The hard coating product according to the present invention can be crushed with a favorable texture such as crunchy or crispy and tooth brittleness when chewed, and has good crunch properties. Regarding the crunch properties of the hard coating product according to the present invention, the hard coating product prepared by 10 trained panelists is orally ingested, chewed in the mouth, and the crispy texture that can be felt at that time is as follows. The scoring performance of the hard coating product was evaluated based on the score. Evaluation of crunch characteristics is 3 points: “Crispy texture is strong”, 2 points: “Crispy texture is felt”, 1 point: “Crispy texture is weak”, 0 points: “Crispy texture” The result is 30 to 26 points as “having good crunch properties”, 25 to 16 points as “having slightly good crunch properties”, 15 points A method is used in which -6 points are evaluated as "Crunch property is slightly poor", and 5 points or less are evaluated as "Crunch property is poor" as x. From the measurement results, the hard coating product according to the present invention can be evaluated with ◎ or ○ for any saccharide and sugar alcohol as a main component, and has a good crunch property. confirmed.

  The hard coating product according to the present invention has a feature that cracks are hardly generated on the surface of the hard coating layer even after long-term storage. In the present invention, as a method for evaluating the difficulty of cracking on the coating layer surface, it is stored in a desiccator containing silica gel (relative humidity 9%) at 20 ° C. for 3 months, and the coating layer surface is cracked within the storage period. A preservation test is employed that counts what has occurred. In the storage test, 10 specimens of hard coating products prepared in each preparation example were prepared, and the number of specimens cracked on the coating layer surface during the storage period was counted, and the total number of specimens used for the measurement was 100. The crack rate is required. According to this test method, the hard coating product according to the present invention is 30% or less, preferably 20% or less, particularly preferably 10% or less, in the storage test for any saccharide and sugar alcohol as a main component. Most preferably, it has a result of 0%, and it has been confirmed that the ratio is greatly improved as compared with the coating product with the conventional reinforcing agent.

  Hereinafter, the details of the hard coating layer, the hard coating product and the manufacturing method thereof according to the present invention will be described in detail with examples, but the technical scope of the present invention is not limited to the following examples. .

  The saccharides and sugar alcohols that are the main components of the hard coating layer used in each example were those described below. As the sugar, a commercially available product (trade name: granulated sugar, manufactured by Dainippon Meiji Sugar Co., Ltd.) was used. As the maltitol, a commercially available crystalline maltitol product (trade name: Resis (registered trademark), manufactured by Towa Kasei Kogyo Co., Ltd.) was used. As the xylitol, a commercially available crystalline xylitol product (trade name: Xylit, manufactured by Towa Kasei Kogyo Co., Ltd.) was used. As the lactitol, a commercially available crystal product of lactitol monohydrate (trade name: Milchen (registered trademark), manufactured by Towa Kasei Kogyo Co., Ltd., water content 5% by weight) was used. As a mixture of 1,6-GPS and 1,1-GPM, both equimolar mixture products (trade name: Paratinit PN, manufactured by Mitsui Sugar Co., Ltd., water content 5% by weight), and inclusion of 1,6-GPS Two types of products (trade name: Palatinit GS, manufactured by Mitsui Sugar Co., Ltd., moisture content 2% by weight) were used. As trehalose, a commercially available crystal product of trehalose dihydrate (trade name: Treha (registered trademark), manufactured by Hayashibara Corporation, water content 9.5% by weight) was used. As erythritol, a commercially available erythritol crystal product (trade name: erythritol, manufactured by Mitsubishi Chemical Foods Co., Ltd.) was used. As mannitol, a commercially available mannitol crystal product (trade name: Mannit S, manufactured by Towa Kasei Kogyo Co., Ltd.) was used.

  Six types of reinforcing agents shown in Table 1 below were used as the reinforcing agent for the hard coating layer used in each example according to the present invention.

  As the reinforcing agent A, a product (trade name: PENON PKW) commercially available from Nissho Kagaku Co., Ltd. was used. This reinforcing agent A is a DE produced by reacting propylene oxide with waxy corn starch to be hydroxypropylated to give a hydroxypropylated starch having a substitution degree of 0.06, which is crosslinked by phosphoric acid and hydrolyzed by enzymatic decomposition. Is a hydroxypropylated phosphate cross-linked dextrin derived from 1.2 waxy corn. This hydroxypropylated phosphate cross-linked dextrin had a viscosity of 270 cp when made into an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C.

  As the reinforcing agent B, a product commercially available from Nissho Kagaku Co., Ltd. (trade name: PENON PKW) was used. This reinforcing agent B was produced by reacting propylene oxide with waxy corn starch to give hydroxypropylated hydroxypropylated starch having a substitution degree of 0.06, which was subjected to hydrolytic treatment by phosphoric acid crosslinking and enzymatic decomposition. Is a hydroxypropylated phosphate cross-linked dextrin derived from waxy corn of 2.0. This hydroxypropylated phosphoric acid cross-linked dextrin had a viscosity of 150 cp when made into an aqueous solution with a solid content of 30% by weight and a temperature of 30 ° C.

  As the reinforcing agent C, a product commercially available from Nissho Kagaku Co., Ltd. (trade name: Amicol SQ) was used. This reinforcing agent C is a product obtained by reacting tapioca starch with propylene oxide to be hydroxypropylated to give a hydroxypropylated starch having a substitution degree of 0.18, which is subjected to phosphoric acid crosslinking and hydrolyzed by enzymatic decomposition. 1.9 Hydroxypropylated phosphate cross-linked dextrin derived from tapioca. This hydroxypropylated phosphate cross-linked dextrin had a viscosity of 110 cp when made into an aqueous solution with a solid content of 30% by weight and a temperature of 30 ° C.

  As reinforcing agent D, a hydroxypropylated dextrin derived from waxy corn prepared by the following method was used. This reinforcing agent D was obtained by reacting propylene oxide with waxy corn starch to make hydroxypropyl, which was converted to hydroxypropylated starch having a substitution degree of 0.06, and hydrolyzed by enzymatic decomposition, with a DE of 2.5. Hydroxypropylated dextrin. This hydroxypropylated dextrin had a viscosity of 240 cp when made into an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C.

  As the reinforcing agent E, hydroxypropylated dextrin derived from tapioca prepared by the following method was used. This reinforcing agent E is a hydroxypropylated starch obtained by reacting tapioca starch with propylene oxide to give a hydroxypropylated starch having a substitution degree of 0.12 and hydrolyzed by enzymatic decomposition. Propylated dextrin. This hydroxypropylated dextrin had a viscosity of 280 cp when made into an aqueous solution with a solid content of 30% by weight and a temperature of 30 ° C.

  As the reinforcing agent F, potato-derived hydroxypropylated dextrin prepared by the following method was used. This reinforcing agent F was produced by reacting potato starch with propylene oxide to produce hydroxypropyl, which was converted to hydroxypropylated starch having a substitution degree of 0.06, and hydrolyzed by enzymatic decomposition. Propylated dextrin. This hydroxypropylated dextrin had a viscosity of 230 cp when made into an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C.

  As conventional reinforcing agent components, those described below were used. For gum arabic, a reagent (reagent name: powdered gum arabic, deer grade 1) manufactured by Kanto Chemical Co., Ltd. was used. This gum arabic had a viscosity of 180 cp when made into an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C. As the gelatin, a product (trade name: gelatin E1) manufactured by Nippi Gelatin Industry Co., Ltd. was used. About this ceratin, it solidified on solid content concentration 30 weight% and temperature 30 degreeC conditions, and the viscosity was not able to be measured. As the maltodextrin, a product (trade name: Amicol 10) manufactured by Nissho Kagaku Co., Ltd. having a DE equivalent to 4.0 was used. This maltodextrin had a viscosity of 98 cp when made into an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C. As the hydrogenated dextrin, a product (trade name: PO-10) manufactured by Towa Kasei Kogyo Co., Ltd., obtained by hydrogenating a dextrin having a DE equivalent to 8.0 was used. This hydrogenated dextrin had a viscosity of 28 cp when made into an aqueous solution with a solid content of 30% by weight and a temperature of 30 ° C. As the hydroxypropylated starch, a product (trade name: Piostarch H) manufactured by Nissho Kagaku Co., Ltd. was used. This hydroxypropylated starch could not be measured because the viscosity exceeded 10,000 cp under conditions of an aqueous solution having a solid content of 10% by weight and a temperature of 30 ° C. As the acid-treated hydroxypropylated starch, a product (trade name: C ☆ AraSet) manufactured by Selestar Co., Ltd. was used. The acid-treated hydroxypropylated starch had a viscosity of 388 cp when made into an aqueous solution with a solid content of 30% by weight and a temperature of 30 ° C.

(Preparation of Invention 1 by maltitol coating)
Using commercially available crystalline maltitol (trade name: Resis (registered trademark), manufactured by Towa Kasei Kogyo Co., Ltd.) as maltitol, according to the blending ratio shown in Preparation Example 1 in Table 2, maltitol: 65 parts by weight, reinforcing agent A coating solution having a composition of 3 parts by weight of A and 32 parts by weight of water and having a liquid temperature of 50 ° C. was prepared. Next, using lactose simulated tablets (tablet diameter: 10 mm, R: 8.5 mm, H: 1.63 mm, average weight: 360 mg / tablet, manufactured by Sankei Health Co., Ltd.) as a core material, 300 g of prepared lactose simulated tablets Is put into a small sugar coating machine (device name: 16DS, manufactured by Kikusui Seisakusho), and 4.0 g of the prepared coating solution is applied to the core material in the small sugar coating machine continuously rotating at 25 rpm, and then small. The core material in the sugar coating machine is intermittently sent at room temperature with a blower (device name: TSK hot air generator, model: TSK-1, air volume adjustment dial: 8, manufactured by Taketsuna Manufacturing Co., Ltd.). The material surface was dried, the coating solution was applied and dried repeatedly, and the coating operation was carried out until the average weight reached 540 mg / tablet to prepare a hard coating product. Next, the product was placed in an aluminum storage bag with a zipper (trade name: Rami Zip AL16, manufactured by Nippon Nihon Co., Ltd.) and allowed to stand at room temperature for 2 weeks to obtain Invention Product 1.

(Preparation of inventions 2 to 9 by maltitol coating)
According to the blending ratios shown in Preparation Examples 2 to 9 in Table 2, coating solutions were prepared using the same maltitol as in Preparation Example 1. The calcium carbonate used in Preparation Examples 2 and 3 is a reagent manufactured by Kanto Chemical Co., Ltd. (reagent name: calcium carbonate, deer grade 1), and talc is a reagent manufactured by Kanto Chemical Co., Ltd. (reagent name: talc). It was used. Thereafter, for each of the preparation examples, a hard coating product was prepared by the same preparation method as in Preparation Example 1. The hard coating product prepared according to the blending ratio shown in Preparation Example 2 was prepared according to Invention 2 and the hard coating product prepared according to the blending ratio shown in Preparation Example 3 was prepared according to Invention 3 and the blending ratio shown in Preparation Example 4. The hard coating product prepared in accordance with the invention 4, the hard coating product prepared according to the blending ratio shown in Preparation Example 5, the inventive product 5, the hard coating product prepared according to the blending ratio shown in Preparation Example 6, and the inventive product 6. The hard coating product prepared according to the mixing ratio shown in Preparation Example 7 was prepared according to Invention 7 and the hard coating product prepared according to the mixing ratio shown as Preparation Example 8 was prepared according to Invention 8 and the mixing ratio shown in Preparation Example 9. The hard coating product is referred to as invention product 9, respectively.

(Preparation of control products 1-8 by maltitol coating)
According to the blending ratios shown in Comparative Examples 1 to 8 in Table 3, coating solutions were prepared using the same maltitol as in Preparation Example 1. In addition, the calcium carbonate used in Comparative Example 3 uses a reagent manufactured by Kanto Chemical Co., Ltd. (reagent name: calcium carbonate, deer grade 1), and the talc uses a reagent manufactured by Kanto Chemical Co., Ltd. (reagent name: talc). did. Thereafter, for each preparation example, a coated product was prepared by the same preparation method as that for Invention Product 1. The coating product prepared according to the blending ratio shown in Comparative Example 1 is Control 1 and the coating product prepared according to the blending ratio shown in Comparative Example 2 is Control 2 and the coating prepared according to the blending ratio shown in Comparative Example 3 The product is Control 3 and the coating product prepared according to the blending ratio shown in Comparative Example 4 is Control 4 and the coating product prepared according to the blending ratio shown in Comparative Example 5 is Control 5 and Comparative Example 6. The coated product prepared according to the blending ratio is Control Product 6, the coated product prepared according to the blending ratio shown in Comparative Example 7 is Control Product 7, and the coated product prepared according to the blending ratio shown in Comparative Example 8 is Control Product 8. Respectively.

(Preparation of invention products 10-11 and control product 9 by xylitol coating)
A commercially available xylitol crystal (trade name: Xylit, manufactured by Towa Kasei Kogyo Co., Ltd.) was used as xylitol, and coating solutions were prepared according to the blending ratios shown in Preparation Examples 10 to 11 and Comparative Example 9 in Table 4. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 10 was prepared according to the invention 10 and the hard coating product prepared according to the blending ratio shown as Preparation Example 11 was prepared according to the invention 11 and the blending ratio shown in Comparative Example 9. The coated product is referred to as the control product 9, respectively.

(Preparation of invention products 12 to 13 and control product 10 by lactitol coating)
Using commercially available lactitol crystal monohydrate (trade name: Milchen (registered trademark), manufactured by Towa Kasei Kogyo Co., Ltd.) as lactitol, according to the blending ratios shown in Preparation Examples 12 to 13 and Comparative Example 10 in Table 5, A coating solution was prepared for each. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 12 was prepared according to Invention 12, and the hard coating product prepared according to the blending ratio shown as Preparation Example 13 was prepared according to Invention 13 and according to the blending ratio shown in Comparative Example 10. The coated product is referred to as the control product 10, respectively.

(Preparation of invention products 14 to 16 and control products 11 to 12 by palatinit coating)
As palatinit, commercially available palatinit products (trade name: Paratinit GS type, manufactured by Mitsui Sugar Co., Ltd.) and palatinit products (trade name: Paratinit PN type, manufactured by Mitsui Sugar Co., Ltd.) are used. Coating solutions were prepared according to the blending ratios shown in Preparation Examples 14 to 16 and Comparative Examples 11 to 12 in Table 6, respectively. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 14 was prepared according to Invention 14 and the hard coating product prepared according to the blending ratio shown as Preparation Example 15 was prepared according to Invention 15 and the blending ratio shown in Preparation Example 16. The hard coating product is referred to as Invention Product 16, the coating product prepared according to the blending ratio shown in Comparative Example 11 is referred to as Control Product 11, and the coating product prepared according to the blending ratio illustrated in Comparative Example 12 is referred to as Control Product 12. .

(Preparation of invention products 17-18 and control product 13 by erythritol coating)
Commercially available erythritol crystals (trade name: erythritol, manufactured by Mitsubishi Chemical Foods Co., Ltd.) were used as erythritol, and coating solutions were prepared according to the blending ratios shown in Preparation Examples 17 to 18 and Comparative Example 13 in Table 7. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 17 was prepared according to Invention 17 and the hard coating product prepared according to the blending ratio shown as Preparation Example 18 was prepared according to Invention 18 and according to the blending ratio shown in Comparative Example 13. The coated product is referred to as the control product 13, respectively.

(Preparation of invention products 19 to 20 and control product 14 by trehalose coating)
Using a commercially available trehalose crystal (trade name: Treha (registered trademark), manufactured by Hayashibara Shoji Co., Ltd.) as trehalose, a coating solution was prepared according to the blending ratios shown in Preparation Examples 19 to 20 and Comparative Example 14 in Table 8. did. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 19 was prepared according to Invention 19 and the hard coating product prepared according to the blending ratio shown as Preparation Example 20 was prepared according to Invention 20 and the blending ratio shown in Comparative Example 14. The coated product is referred to as the control product 14, respectively.

(Preparation of invention products 21 to 22 and control product 15 by sugar coating)
Commercially available sugar crystals (trade name: granulated sugar, manufactured by Dainippon Meiji Sugar Co., Ltd.) were used as the sugar, and coating solutions were prepared according to the blending ratios shown in Preparation Examples 21 to 22 and Comparative Example 15 in Table 9. . Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 21 was prepared according to Invention 21 and the hard coating product prepared according to the blending ratio shown as Preparation Example 22 was prepared according to Invention 22 and the blending ratio shown in Comparative Example 15. The coated product is referred to as the control product 15, respectively.

(Preparation of invention products 23 to 24 and control products 16 to 17 by mannitol coating)
Commercially available mannitol crystals (trade name: Mannit S, manufactured by Towa Kasei Kogyo Co., Ltd.) are used as mannitol, and the coating solutions are prepared according to the blending ratios shown in Preparation Examples 23 to 24 and Comparative Examples 16 to 17 in Table 10. Prepared. In addition, the calcium carbonate used in Preparation Example 23, Preparation Example 24, and Comparative Example 3 uses a reagent (reagent name: calcium carbonate, deer first grade) manufactured by Kanto Chemical Co., and talc is a reagent manufactured by Kanto Chemical Co., Ltd. (Reagent name: Talc) was used. Thereafter, a hard coating product was prepared by the same preparation method as that of Invention Product 1 for each preparation example. The hard coating product prepared according to the blending ratio shown in Preparation Example 23 was prepared according to Invention 23 and the hard coating product prepared according to the blending ratio shown as Preparation Example 24 was prepared according to Invention 24 and the blending ratio shown in Comparative Example 16. The coated product is referred to as the control product 16, respectively. In addition, although coating operation was performed according to the mixture ratio shown in the comparative example 17, a coating layer was not formed and the control | contrast goods 17 could not be obtained.

  Evaluation products 1: Hard coating layer strength, evaluation test 2: Smoothness of hard coating layer surface, evaluation for invention products 1-24 and control products 1-17 prepared by the methods described in the above preparation examples and comparative examples Test 3: Disintegration property of hard coating product, evaluation test 4: Crack rate of hard coating product by storage under dry condition, evaluation test 5: Crunch property of hard coating product, the above five items were evaluated. The evaluation test implementation method and evaluation criteria are as follows.

(Evaluation Test 1) Strength of Hard Coating Layer For the inventive product obtained in each preparation example and the control product obtained in each comparative example, 20 samples of each product were arbitrarily taken out and placed on the marble from a height of 30 cm. A drop test was performed in which the sample was dropped freely and the number of drops required until the surface of the hard coating layer was cracked was measured. The average value of 20 samples was used as the strength of the hard coating layer, and the result was evaluated.

(Evaluation test 2) Smoothness of hard coating layer For the invention product obtained in each preparation example and the control product obtained in each comparative example, 20 samples of each product were arbitrarily taken out and 10 trained panelists The surface roughness of the coating layer was visually scored according to the following criteria, and the smoothness of the coating layer was evaluated from the score. The smoothness was evaluated as 3 points: “no unevenness”, 2 points: “almost unevenness”, 1 point: “slightly uneven”, 0 point: “many unevenness”, and the result was 30 Points to 26 are “smooth”, ◎, 25 to 16 are “slightly smooth”, 15 to 6 are “slightly uneven”, Δ is 5 points or less are “uneven”, and × expressed.

(Evaluation test 3) Disintegration property of hard coating product About the invention product obtained in each example and the control product obtained in each comparative example, 6 samples of each product were taken out arbitrarily, and disintegration property by disintegration tester A test was performed, the average value of the disintegration time of 6 specimens was determined, and the disintegration property was evaluated.

(Evaluation Test 4) Cracking rate of hard coating product by storage under dry conditions For the invention product obtained in each example and the control product obtained in each comparative example, 10 samples of each product were taken out arbitrarily, It was stored in a desiccator containing silica gel (relative humidity 9%) at 20 ° C. for 3 months in the dark, and the state of the hard coating product was observed. Of the specimens used in the experiment, those with cracks on the surface of the hard coating product were counted, and the cracking rate was determined by the following calculation formula A.
Calculation formula A: Crack rate (%) = (Number of specimens with cracks) / (Total number of specimens) × 100

(Evaluation test 5) Crunch properties of hard coating products For the inventive product obtained in each example and the control product obtained in each comparative example, each product was arbitrarily taken out and 10 trained panelists were each hard. The coated product was taken, chewed in the mouth, and the texture that can be felt at that time was scored according to the following criteria, and the crunch properties of the hard coated product were evaluated from the score. Evaluation of crunch characteristics is 3 points: “I feel a strong crispy texture”, 2 points: “I feel crispy texture”, 1 point: “Weak crispy texture”, 0 point: “ The results are tabulated as “no crispy texture”, and the results are 30 to 26 points as “good crunch” ◎, 25 to 16 points as “slightly good crunch” ○, 15 Points to 6 were expressed as “A crunch property is slightly poor”, Δ, and 5 points or less were expressed as “Crunchy property is bad”.

  The results of the above evaluation tests 1 to 5 carried out for the invention products obtained in each example and the control products obtained in each comparative example are shown in the table as follows. The results of Inventions 1 to 9 based on maltitol are shown in Table 11. Table 12 shows the results of the control products 1 to 8 containing maltitol as a main component. Table 13 shows the results of Invention Products 10 to 11 and Control Product 9 containing xylitol as a main component. Table 14 shows the results of Invention Products 12 to 13 and Control Product 10 mainly composed of lactitol. Table 15 shows the results of invention products 14 to 16 and control products 11 to 12 mainly composed of paratinite. Table 16 shows the results of Invention Products 17 to 18 and Control Product 13 containing erythritol as a main component. Table 17 shows the results of invention products 19 to 20 and control product 14 mainly composed of trehalose. Table 18 shows the results of invention products 21 to 22 and control product 15 containing sugar as a main component. Table 19 shows the results of Invention Products 23 to 24 and Control Products 16 to 17 containing mannitol as a main component.

Claims (7)

As main components, sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1,1-GPM (α-D -Glucopyranosyl-1,1-D-mannitol), any one selected from the group of the above saccharides and sugar alcohols, and hydroxyalkylated dextrin as a reinforcing agent in terms of solids in the hard coating layer. A hard coating layer containing from 1 to 10.0% by weight. The hard coating layer according to claim 1, wherein the hydroxyalkylated dextrin is hydroxypropylated dextrin. The hard coating layer according to claim 1 or 2, wherein the dextrose equivalent (DE) of the hydroxyalkylated dextrin is 0.1 or more and less than 5.0. The hard coating layer according to any one of claims 1 to 3, wherein the hydroxyalkylated dextrin is crosslinked by a crosslinking agent. The hard coating layer according to any one of claims 1 to 4, wherein the hydroxyalkylated dextrin has a viscosity of 50 to 350 cp when it is an aqueous solution having a solid content of 30% by weight and a temperature of 30 ° C. A hard coating product in which a core material is coated with the hard coating layer according to any one of claims 1 to 5. As main components in the solid component of the coating solution, sugar, trehalose, maltitol, xylitol, mannitol, erythritol, lactitol, or 1,6-GPS (α-D-glucopyranosyl-1,6-D-sorbitol) and 1, A mixture of 1-GPM (α-D-glucopyranosyl-1,1-D-mannitol), any one selected from the group of the above saccharides and sugar alcohols, and a hydroxyalkylated dextrin as a reinforcing agent A method for producing a hard coating product, in which a coating solution is applied to a core, dried to crystallize solids from the coating solution, and the coating solution is repeatedly applied and dried.