Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
  • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B31/00—Preparation of derivatives of starch
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P19/00—Preparation of compounds containing saccharide radicals
  • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds

Definitions

• the present invention relates to processed starch-containing particles and a method for producing the particles.
• Particles containing starch have conventionally been used in a wide range of applications as additives to cosmetics, pharmaceuticals, foods, paints, etc.
• Patent Document 1 describes a phosphoric acid cross-linked starch obtained by subjecting raw starch to phosphoric acid cross-linking treatment, and a paste obtained by suspending the raw starch in water to a concentration of 7% by weight on an anhydrous basis.
• the phosphoric acid cross-linked starch has a particle size of about 70% or more on a volume basis of 18 to 35 ⁇ m, and the dietary fiber in the phosphoric acid cross-linked starch has a particle size of 18 to 35 ⁇ m.
• Phosphoric acid crosslinked starch is described, the content of which is about 50% or more by weight.
• Patent Document 2 describes a method for producing phosphoric acid cross-linked starch, which is characterized by reacting starch and sodium trimetaphosphate at 10 to 45°C in the presence of calcium salts at pH 8 to 12.
• Patent Document 3 describes particles containing starch with an amylopectin content of 90% by weight or more, an average particle diameter d1 of 0.5 to 20 ⁇ m, a maximum particle diameter d2 of less than 30 ⁇ m, and Particles are described that are characterized in that they are less than 3.0 times the diameter.
• Patent Documents 1 and 2 do not have their proteins removed by protease treatment, and contain a large amount of globulin, which is an allergy-causing substance, in the proteins contained in the starch, so they cannot be incorporated into cosmetics. There is an unavoidable problem of allergic reactions when using the product.
• the starch is not cross-linked using a phosphoric acid compound, and when the particles are heated in the presence of water, gelatinization of the starch contained in the particles occurs. Inevitable. Therefore, when the particles are blended into cosmetics and used, stickiness occurs and the texture becomes poor.
• the present invention has been made in view of the above, and aims to provide processed starch-containing particles that can suppress gelatinization and have a low protein content, and a method for producing the particles.
• the present inventors succeeded in developing desired particles containing processed starch, and discovered that the above object could be achieved by using the particles.
• the present invention has been completed through further research.
• the present invention contains modified starch,
• the protein content is 500 mass ppm or less, Provided are processed starch-containing particles having a water absorption rate of 650% or less.
• the processed starch-containing particles of the present invention can suppress gelatinization and have a low protein content.
• the processed starch-containing particles of the present invention suppress gelatinization, so when incorporated into external preparations such as cosmetics, they can impart heat resistance, smooth feel (flowy feel), etc. to the external preparation. Since the processed starch-containing particles of the present invention have a low protein content, coloration and off-odor of the particles can be suppressed. Since the processed starch-containing particles of the present invention have a low protein content, when used in external preparations such as cosmetics, allergic reactions can be suppressed.
• the method for producing processed starch-containing particles of the present invention continuously performs crosslinking treatment to suppress gelatinization and protease treatment to reduce protein content, so processed starch-containing particles are manufactured in a simple manner. can do.
• the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.
• the upper limit or lower limit of the numerical range may be replaced with a value shown in the Examples or a value that can be uniquely derived from the Examples.
• numerical values connected by " ⁇ " mean a numerical range that includes the numerical values before and after the " ⁇ " as lower and upper limits.
• a and/or B means “one of A and B” or “both A and B”, and specifically, “A", “B”, or “A and B”.
• starch As used herein, “gelatinization” means that when starch is heated in the presence of water, it absorbs surrounding water and swells, thereby increasing its viscosity.
• raw starch refers to starch made from corn, potato, sweet potato, wheat, rice, tapioca, sago palm, pea, etc.
• room temperature means a temperature within the range of 15°C or higher and 30°C or lower.
• (meth)acrylic means acrylic or methacrylic
• (meth)acrylate means acrylate or methacrylate
• Processed starch-containing particles The processed starch-containing particles of the present invention have the following configurations (i) to (iii): (i) Contains modified starch. (ii) The protein content is 500 mass ppm or less. (iii) Water absorption rate is 650% or less.
• the processed starch-containing particles of the present invention have the above-described configurations (i) to (iii), thereby achieving the effects of the present invention.
• the processed starch-containing particles of the present invention having the above-mentioned configurations (i) to (iii) may be simply referred to as "particles of the present invention.”
• the particles of the present invention usually contain processed starch as a main component.
• "Contained as a main component” means that the content of processed starch in the particles of the present invention is more than 50% by mass.
• the content of modified starch in the particles of the present invention is preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass or more, even more preferably 99% by mass or more.
• the content is .9% by mass or more, particularly preferably 99.95% by mass or more.
• the processed starch-containing particles consist only of processed starch and protein.
• unavoidable impurities other than processed starch and protein for example, extremely small amounts remaining due to poor washing etc. during the manufacturing process of processed starch-containing particles) raw material starch, etc.
• the processed starch-containing particles consist only of processed starch and do not contain protein (protein content is 0% by mass).
• protein content is 0% by mass.
• unavoidable impurities other than processed starch for example, particles that remain due to poor washing during the manufacturing process of processed starch-containing particles) Containment of trace amounts of raw material starch, etc.
• Particles of the invention typically contain protein.
• the particles of the present invention have a protein content of 500 mass ppm (0.05 mass %) or less.
• the protein is at least one selected from the group consisting of albumin, globulin, prolamin, and glutelin, and the total content of the protein (total content) is 500 mass ppm or less.
• the protein is at least one selected from the group consisting of globulin, albumin, prolamin, and glutelin, and the total content of the protein is 500 mass ppm or less.
• the proteins are globulin, albumin, prolamin, and glutelin, and the total content of the proteins is 500 ppm by mass or less.
• the processed starch-containing particles preferably do not contain proteins other than globulin, albumin, prolamin, and glutelin.
• the protein content is more than 500 ppm by mass, there is a risk that the particles will be colored and a strange odor will occur.
• the protein content is more than 500 ppm by mass, a large amount of globulin is contained in the protein, so if the particles of the present invention are used in external preparations such as cosmetics, allergic reactions may occur. may occur.
• a specific method for measuring the protein content will be described in Examples below.
• the protein content can be reduced to a value of 500 mass ppm or less by treating raw starch and/or processed starch with protease.
• the protease used in the protease treatment is preferably alkaline protease.
• the protease used in the protease treatment is more preferably at least one selected from the group consisting of orientase, alcalase, sumizyme, aloase, maxipro, and bioplase, and at least one selected from the group consisting of orientase, alcalase, and sumizyme. It is even more preferable that it be one type.
• the protease used in the protease treatment is particularly preferably orientase.
• a wide variety of known commercially available products can be used.
• Commercially available products include, for example, Orientase 22BF (manufactured by HBI Co., Ltd.), Alcalase 2.4 L FG (manufactured by Novozymes Japan Co., Ltd.), Sumiteam MP (manufactured by Shin Nihon Kagaku Kogyo Co., Ltd.), and Aloase XA-10 (manufactured by Shin Nihon Kagaku Kogyo Co., Ltd.).
• step (B) commercially available proteases are preferably Orientase 22BF (manufactured by HBI Co., Ltd.), Alcalase 2.4 L FG (Novozymes). Japan Co., Ltd.) and Sumiteam MP (manufactured by Shin Nihon Kagaku Kogyo Co., Ltd.), and particularly preferably Orientase 22BF (manufactured by HBI Co., Ltd.).
• the protein content is 500 mass ppm or less, preferably 400 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 200 mass ppm or less, still more preferably 150 mass ppm or less, and even more preferably is 100 mass ppm or less, particularly preferably 75 mass ppm or less, and the upper limit of the protein content is 450 mass ppm, 400 mass ppm, 350 mass ppm, 300 mass ppm, 250 mass ppm, 200 mass ppm, 175 Mass ppm, 150 mass ppm, 140 mass ppm, 130 mass ppm, 120 mass ppm, 110 mass ppm, 100 mass ppm, 95 mass ppm, 90 mass ppm, 85 mass ppm, 80 mass ppm, 75 mass ppm and 70 mass ppm
• the lower limit of the protein content is 0 mass ppm (0 mass %), more than 0 mass ppm, 0.001 mass ppm, 0.005 mass ppm,
• the particles of the present invention have a water absorption rate of 650% or less.
• the particles of the present invention may become gelatinized, and therefore, when the particles of the present invention are used in external preparations such as cosmetics, they tend to become sticky.
• a specific method for measuring the water absorption rate will be explained in Examples described later.
• the water absorption rate can be reduced to a value of 650% or less by crosslinking the raw starch with a phosphoric acid compound.
• a smaller water absorption value indicates that gelatinization of processed starch particles is suppressed.
• the water absorption rate is usually 50% to 550%, preferably 75% to 525%, more preferably 100% to 500%, even more preferably 125% to 475%, and even more preferably 150% to 525%. % or more and 450% or less, even more preferably 175% or more and 425% or less, particularly preferably 200% or more and 400% or less, and the upper limit of the water absorption rate is 600%, 575%, 550%, 525%, 500%.
• the lower limit of the water absorption rate is 50%, 75%, 100%, 125%, 150%, 175 %, 200%, 225%, 250%, 275% and 300%, and these upper and lower limits can be arbitrarily combined.
• processed starch refers to starches made from corn, potato, sweet potato, wheat, rice, tapioca, sago palm, peas, etc., which are subjected to chemical treatment, physical treatment, or enzymatic treatment. , means starch with improved characteristics of raw material starch.
• the above chemical treatments include crosslinking treatment (preferably phosphoric acid crosslinking treatment); acid treatment, alkali treatment, oxidation treatment; esterification treatment such as acetylation, phosphorylation, octenyl succination; etherification treatment such as hydroxypropylation. etc.
• Such treatments may be performed by one type of treatment alone or by a combination of two or more types of treatment.
• Examples of the physical treatment include heat treatment, gelatinization treatment, moist heat treatment, ball mill treatment, pulverization treatment, and the like. Such treatments may be performed by one type of treatment alone or by a combination of two or more types of treatment.
• Examples of the enzymatic treatment include treatment with enzymes such as amylase. Such treatments may be performed by one type of treatment alone or by a combination of two or more types of treatment.
• processed starch obtained by chemically treating raw starch is preferred, processed starch obtained by crosslinking raw starch is more preferred, and processed starch obtained by crosslinking raw starch with phosphoric acid is even more preferred.
• the raw starch is preferably at least one selected from the group consisting of corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, sago palm starch, and pea starch, and rice starch is more preferable.
• rice starch is more preferable.
• non-glutinous rice and glutinous rice are preferred, and non-glutinous rice is more preferred.
• the volume average particle diameter of the raw material starch is preferably 3.0 ⁇ m or more in order to improve the texture and light diffusivity when the particles of the present invention are used in external preparations such as cosmetics. It is 20.0 ⁇ m or less.
• the volume average particle diameter of the raw material starch can be determined using, for example, a precision particle size distribution analyzer (for example, "Coulter Multisizer (registered trademark) 4e” manufactured by Beckman Coulter Co., Ltd., “Coulter Multisizer (registered trademark) 4e” manufactured by Beckman Coulter Co., Ltd.). (Registered Trademark) 3, etc.).
• the processed starch includes, for example, phosphoric acid crosslinked starch and its metal salt, acetylated adipic acid crosslinked starch and its metal salt, acetylated oxidized starch and its metal salt, acetylated phosphoric acid crosslinked starch and its metal salt.
• oxidized starch and its metal salts hydroxypropyl starch and its metal salts, hydroxypropylated phosphate-crosslinked starch and its metal salts, carboxymethyl starch and its metal salts, acetic acid starch and its metal salts, alkenylsuccinic acid starch and its metal salts salt, phosphoric acid starch and its metal salt, phosphoric acid monoesterified phosphoric acid crosslinked starch and its metal salt.
• the metal salt is preferably a sodium salt, potassium salt, magnesium salt, calcium salt or aluminum salt, more preferably a sodium salt.
• the processed starch includes phosphoric acid cross-linked starch, metal salt of phosphoric acid cross-linked starch, acetylated phosphoric acid cross-linked starch, metal salt of acetylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, At least one selected from the group consisting of metal salts of acid-crosslinked starches, phosphoric acid-monoesterified phosphoric acid-crosslinked starches, and phosphoric acid-monoesterified phosphoric acid-crosslinked starches is preferred, and the metal salts are preferably sodium salts. , potassium salt, magnesium salt, calcium salt or aluminum salt, and more preferably sodium salt.
• the modified starch is more preferably at least one selected from the group consisting of phosphoric acid crosslinked starch, acetylated phosphoric acid crosslinked starch, hydroxypropylated phosphoric acid crosslinked starch, and phosphoric acid monoesterified phosphoric acid crosslinked starch.
• the processed starch is particularly preferably phosphoric acid crosslinked starch.
• the modified starch-containing particles preferably do not contain any modified starch other than phosphoric acid crosslinked starch.
• phosphoric acid crosslinked starch is obtained by subjecting raw starch to phosphoric acid crosslinking treatment.
• the phosphoric acid crosslinked starch intramolecular hydroxyl groups or intermolecular hydroxyl groups of the raw starch are crosslinked by the phosphoric acid crosslinking treatment, and as a result, gelatinization is suppressed.
• glucose residues in raw starch are crosslinked with a phosphoric acid compound.
• the phosphoric acid compound used in the phosphoric acid crosslinking treatment is preferably at least one selected from the group consisting of sodium trimetaphosphate, phosphorus oxychloride, orthophosphoric acid, potassium orthophosphate, sodium orthophosphate, and sodium tripolyphosphate. .
• the phosphoric acid compound used in the phosphoric acid crosslinking treatment is more preferably sodium trimetaphosphate and/or phosphorus oxychloride, even more preferably sodium trimetaphosphate.
• the particles of the present invention preferably have a light diffusivity of 50% to 210%. If the light diffusion rate is within the above range, when the particles of the present invention are used in external preparations such as cosmetics, it can be expected to produce a soft focus effect that corrects skin imperfections such as wrinkles and spots. . A specific method for measuring the light diffusivity will be explained in Examples described later.
• the light diffusion rate is more preferably 60% to 210%, even more preferably 70% to 210%, still more preferably 80% to 210%, and even more preferably It is preferably 90% to 210%, particularly preferably 100% to 210%.
• the particles of the present invention may have a hollow structure in which a cavity is formed inside an outer shell made of processed starch, or a solid structure in which the inside of the particle is filled with processed starch. It may have.
• the volume average particle diameter of the particles of the present invention is usually 3.0 ⁇ m or more and 20.0 ⁇ m in order to improve the feel and light diffusivity when the particles of the present invention are used in external preparations such as cosmetics.
• the thickness is 4.0 ⁇ m or more and 10.0 ⁇ m or less.
• the volume average particle diameter of the processed starch-containing particles is measured using a precision particle size distribution measuring device (for example, "Coulter Multisizer (registered trademark) 4e” manufactured by Beckman Coulter Co., Ltd., a product manufactured by Beckman Coulter Co., Ltd.). It means the arithmetic mean diameter in the volume-based particle size distribution of 100,000 particles obtained using a product such as "Coulter Multisizer (registered trademark) 3").
• a specific method for measuring the volume average particle diameter will be explained in Examples described below.
• the method for producing processed starch-containing particles of the present invention comprises a step (A) of treating starch with a phosphoric acid compound, a step (B) of treating starch with a protease, and It is characterized in that step (A) and step (B) are performed continuously.
• the production method of the present invention (i) contains processed starch, (ii) has a protein content of 500 mass ppm or less, and (iii) has a water absorption rate. 650% or less can be produced.
• the production method of the present invention continuously performs crosslinking treatment to suppress gelatinization of starch and protease treatment to reduce protein content, so processed starch-containing particles can be manufactured by a simple method. be able to.
• step (A) of treating starch with a phosphate compound in the production method of the present invention is simply referred to as “step (A)"
• step (B) of treating starch with a protease in the production method of the present invention is referred to as “step (A)”.
• step (B) may also be simply written as "step (B)”.
• the processed starch-containing particles obtained by the production method of the present invention include (1) particles obtained by passing through step (B) after passing through step (A), and (2) particles obtained by passing through step (B). (3) particles obtained by performing step (A) and step (B) at the same time, but to the extent that the effects of the present invention are not affected. , particles obtained only through step (A) and particles obtained only through step (B).
• the processed starch-containing particles obtained by the production method of the present invention are particles obtained by passing through step (B) after passing through step (A).
• the processed starch-containing particles obtained by the production method of the present invention are particles obtained by passing through step (A) after passing through step (B).
• the processed starch-containing particles obtained by the production method of the present invention are particles obtained by performing step (A) and step (B) simultaneously.
• One embodiment of the present invention includes a step (A) of treating starch with a phosphoric acid compound to obtain a modified starch, and a step (B) of treating the modified starch obtained in the step (A) with a protease.
• This is a method for producing processed starch-containing particles, in which step (A) and step (B) are performed continuously.
• One embodiment of the present invention includes a step (B) of treating starch with a protease, and a step (A) of treating the protease-treated starch obtained in step (B) with a phosphoric acid compound to obtain a processed starch.
• This is a method for producing processed starch-containing particles, comprising the steps of step (A) and step (B).
• One embodiment of the present invention comprises a step (A) of treating starch with a phosphoric acid compound to obtain a processed starch, and a step (B) of treating starch with a protease, the step (A) and the step
• This is a method for producing processed starch-containing particles in which (B) and (B) are carried out simultaneously and continuously.
• Step (A) is a step of treating starch (raw material starch) as a raw material with a phosphoric acid compound (phosphoric acid crosslinking treatment step).
• a phosphoric acid compound is used as a crosslinking agent.
• step (A) it is possible to obtain particles containing processed starch in which raw starch is treated with a phosphoric acid compound (phosphoric acid crosslinking treatment).
• the content of processed starch in the particles is usually more than 50% by mass, preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass or more, It is even more preferably 99.9% by mass or more, particularly preferably 99.95% by mass or more.
• the particles after the phosphoric acid crosslinking treatment consist only of processed starch and protein.
• unavoidable impurities other than processed starch and protein for example, a trace amount of raw starch that has not been subjected to phosphoric acid cross-linking treatment, etc.
• the inclusion of is permissible.
• the particles after the phosphoric acid crosslinking treatment consist of only processed starch and do not contain protein (protein content is 0% by mass).
• protein content is 0% by mass.
• unavoidable impurities other than processed starch for example, a trace amount of raw starch that has not been subjected to phosphoric acid cross-linking treatment, etc.
• the raw starch is preferably at least one selected from the group consisting of corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, sago palm starch, and pea starch, and rice starch is more preferable.
• the type of rice in the rice starch is preferably non-glutinous rice or glutinous rice, more preferably non-glutinous rice.
• the processed starch includes phosphoric acid crosslinked starch, metal salt of phosphoric acid crosslinked starch, acetylated phosphoric acid crosslinked starch, metal salt of acetylated phosphoric acid crosslinked starch, hydroxypropylated phosphoric acid crosslinked starch, hydroxypropyl
• a metal salt of a phosphoric acid crosslinked starch, a phosphoric acid crosslinked starch converted to a phosphoric acid monoester, and a metal salt of a phosphoric acid crosslinked starch converted to a phosphoric acid monoester is preferable, and the metal salt is preferably A sodium salt, a potassium salt, a magnesium salt, a calcium salt or an aluminum salt, and more preferably a sodium salt.
• the modified starch is at least one selected from the group consisting of phosphoric acid cross-linked starch, acetylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, and phosphoric acid monoesterified phosphoric acid cross-linked starch. preferable.
• the processed starch is particularly preferably phosphoric acid crosslinked starch.
• step (A) the raw starch is usually suspended in water to form a dispersion (a dispersion containing the raw starch).
• water examples include natural water, purified water, distilled water, ion exchange water, pure water, etc. Among these, ion exchange water is preferable.
• the starch concentration of the dispersion containing raw starch is preferably 20% by mass or more and 55% by mass or less, more preferably 22% by mass or more and 50% by mass or less, even more preferably 25% by mass or more and 40% by mass or less.
• the phosphoric acid compound is preferably at least one selected from the group consisting of sodium trimetaphosphate, phosphorus oxychloride, orthophosphoric acid, potassium orthophosphate, sodium orthophosphate, and sodium tripolyphosphate.
• the phosphoric acid compound sodium trimetaphosphate and/or phosphorus oxychloride are more preferable, and sodium trimetaphosphate is even more preferable.
• the amount of the phosphoric acid compound used is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the raw starch. Preferably it is 2 parts by mass or more and 10 parts by mass or less.
• the temperature at which step (A) is performed is preferably 10°C or higher and 50°C or lower, more preferably 20°C or higher and 48°C or lower, even more preferably 25°C or higher and 45°C or lower.
• the time for performing step (A) is preferably 1 hour or more and 30 hours or less, more preferably 3 hours or more and 27 hours or less, even more preferably 5 hours or more and 24 hours or less, even more preferably 7 hours or more and 22 hours or less, especially Preferably it is 8 hours or more and 20 hours or less.
• Step (B) is a step of treating starch with protease (protease treatment step). By treating starch with protease, it is possible to reduce the protein content contained in starch.
• the starch before being treated with protease is usually raw starch.
• the raw starch is preferably at least one selected from the group consisting of corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, sago palm starch, and pea starch, and rice starch is more preferable.
• the type of rice in the rice starch is preferably non-glutinous rice or glutinous rice, and more preferably non-glutinous rice.
• step (B) the raw starch is usually suspended in water to form a dispersion (a dispersion containing the raw starch).
• water examples include natural water, purified water, distilled water, ion exchange water, pure water, etc. Among these, ion exchange water is preferable.
• the starch concentration of the dispersion containing raw starch is preferably 20% by mass or more and 55% by mass or less, more preferably 22% by mass or more and 50% by mass or less, even more preferably 25% by mass or more and 40% by mass or less.
• the starch before being treated with protease is a particle containing processed starch in which raw starch obtained through step (A) is treated with a phosphoric acid compound.
• the particles containing processed starch by treating the particles containing processed starch with protease, it is possible to reduce the protein content contained in the particles containing processed starch.
• the content of modified starch in the particles after protease treatment is usually more than 50% by mass, preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass. % or more, even more preferably 99.9% by mass or more, particularly preferably 99.95% by mass or more.
• the protease-treated particles consist only of processed starch and protein.
• unavoidable impurities other than processed starch and protein for example, trace amounts of raw materials that were not cross-linked with phosphoric acid in step (A)] Containment of starch, etc.
• the particles after protease treatment consist only of processed starch and do not contain protein (protein content is 0% by mass).
• protein content is 0% by mass.
• unavoidable impurities other than processed starch for example, trace amounts of particles that were not cross-linked with phosphoric acid in step (A)) Raw material starch, etc.
• the processed starch includes phosphoric acid crosslinked starch, metal salt of phosphoric acid crosslinked starch, acetylated phosphoric acid crosslinked starch, metal salt of acetylated phosphoric acid crosslinked starch, hydroxypropylated phosphoric acid crosslinked starch, hydroxypropyl
• At least one selected from the group consisting of metal salts of phosphoric acid crosslinked starch, phosphoric acid crosslinked starch converted to phosphoric acid monoester, and metal salts of phosphoric acid crosslinked starch converted to phosphoric acid monoester is preferable.
• the metal salt is preferably a sodium salt, potassium salt, magnesium salt, calcium salt or aluminum salt, more preferably a sodium salt.
• the modified starch is at least one selected from the group consisting of phosphoric acid cross-linked starch, acetylated phosphoric acid cross-linked starch, hydroxypropylated phosphoric acid cross-linked starch, and phosphoric acid monoesterified phosphoric acid cross-linked starch. preferable.
• the processed starch is particularly preferably phosphoric acid crosslinked starch.
• the amount of protease used is usually 0.05 parts by mass or more and 10 parts by mass or less, preferably 0.10 parts by mass or more and 8 parts by mass or less, more preferably 0. .20 parts by mass or more and 6 parts by mass or less, even more preferably 0.30 parts by mass or more and 5 parts by mass or less, still more preferably 0.40 parts by mass or more and 4 parts by mass or less, particularly preferably 0.50 parts by mass or more and 3 parts by mass. below.
• the protease is preferably an alkaline protease, more preferably at least one selected from the group consisting of orientase, alcalase, sumizyme, alloase, maxipro and bioplase, even more preferably orientase, alcalase and sumizyme. At least one selected from the group consisting of orientase is particularly preferred.
• step (B) a wide variety of known commercial products can be used as the preferred protease.
• Commercially available products include, for example, Orientase 22BF (manufactured by HBI Co., Ltd.), Alcalase 2.4 L FG (manufactured by Novozymes Japan Co., Ltd.), Sumiteam MP (manufactured by Shin Nihon Kagaku Kogyo Co., Ltd.), and Aloase XA-10 (manufactured by Shin Nihon Kagaku Kogyo Co., Ltd.).
• step (B) commercially available proteases include Orientase 22BF (manufactured by HBI Co., Ltd.), Alcalase 2.4 L FG (Novozymes Japan Co., Ltd.) Orientase 22BF (manufactured by HBI Co., Ltd.) is particularly preferred.
• the temperature at which step (B) is performed is preferably 10°C or higher and 75°C or lower, more preferably 20°C or higher and 70°C or lower, even more preferably 25°C or higher and 65°C or lower.
• the time for performing step (B) is usually 0.5 hours or more and 30 hours or less, preferably 1 hour or more and 28 hours or less, more preferably 1.5 hours or more and 26 hours or less, and even more preferably 2 hours or more and 24 hours or less. , more preferably 2.5 hours or more and 22 hours or less, particularly preferably 3 hours or more and 20 hours or less.
• performing step (A) and step (B) continuously usually means performing step (A) and step (B) continuously in the same container, or This refers to performing step (A) and step (B) in parallel in the same container.
• “carrying out continuously” or “carrying out in parallel” does not mean only that step (A) and step (B) are carried out constantly; This also includes cases where A) and/or step (B) are temporarily stopped.
• the phosphoric acid compound and protease are not additionally added.
• the timings at which the addition of the phosphoric acid compound and the protease end can be set as appropriate.
• the addition of the phosphate compound may be finished before the addition of the protease, or the addition of the protease may be finished before the addition of the phosphate compound is finished, or the timing of the completion of the addition of the phosphate compound and the protease is the same. You can also do this.
• step (A) and step (B) are preferably performed continuously in the presence of a sodium salt and/or a pH adjuster (preferably a sodium salt and a pH adjuster).
• a sodium salt and/or a pH adjuster preferably a sodium salt and a pH adjuster.
• Sodium salts are used to suppress starch swelling.
• a pH adjuster is used for the purpose of promoting crosslinking reaction.
• Examples of the above sodium salts include sodium chloride, sodium sulfate, and sodium carbonate.
• sodium chloride and/or sodium sulfate are preferable, and sodium sulfate is more preferable, from the viewpoint of further suppressing the swelling of starch.
• the amount of sodium salt used is preferably 10 parts by mass or more and 55 parts by mass or less, more preferably 15 parts by mass or more and 52 parts by mass or less, even more preferably 20 parts by mass or more and 48 parts by mass, based on 100 parts by mass of the raw starch.
• the content is preferably 25 parts by mass or more and 45 parts by mass or less.
• the amount of sodium salt to be used is preferably 10 parts by mass or more and 55 parts by mass or less, more preferably 15 parts by mass or more and 52 parts by mass or less, even more preferably 20 parts by mass, per 100 parts by mass of water used for starch dispersion. It is 48 parts by mass or less, more preferably 25 parts by mass or more and 45 parts by mass or less.
• water used for dispersing starch include natural water, purified water, distilled water, ion exchange water, pure water, etc. Among these, ion exchange water is preferable.
• the pH adjuster examples include sodium hydroxide, sodium carbonate, and the like.
• sodium hydroxide is preferred.
• the pH when performing step (A) and step (B) continuously is usually 8 or more and 13 or less, preferably 8.5 or more and 12.5 or less, more preferably 9 or more. Adjust to 12 or less.
• the amount of the pH adjuster used is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.3 parts by mass or more and 4 parts by mass or less, even more preferably 0.1 parts by mass or more and 5 parts by mass or less, even more preferably 0.3 parts by mass or less and 4 parts by mass or less, based on 100 parts by mass of the raw starch. It is 5 parts by mass or more and 3 parts by mass or less.
• the amount of pH adjuster used is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.3 parts by mass or more and 4 parts by mass or less, and even more preferably 0.3 parts by mass or more and 4 parts by mass or less, per 100 parts by mass of water used for dispersing starch.
• the water used for dispersing starch includes natural water, purified water, distilled water, ion exchange water, pure water, etc. Among these, ion exchange water is preferable.
• the manufacturing method of the present invention may further include a separation step and a drying step in addition to step (A) and step (B).
• a separation step is also referred to as step (C)
• the drying step is also referred to as step (D).
• step (C) solid content is separated from the dispersion of processed starch-containing particles obtained by continuously performing step (A) and step (B), for example, by a method such as filtration or centrifugation. This is the process of After the separation step, a cake-like material of modified starch-containing particles is obtained.
• the dispersion of processed starch-containing particles may be neutralized by adding hydrochloric acid or the like.
• Filtration can be performed using a pressure filtration device, a centrifugal separator, etc. Centrifugation can be performed using a centrifugal separator or the like.
• the cake-like material obtained in step (C) may be washed with ion exchange water, pure water, etc. By washing, impurities such as inorganic salts can be reduced. Furthermore, the washed cake-like material may be dehydrated using a centrifugal dehydrator or the like. After washing and dehydration, a powder is obtained.
• Step (D) is a step of evaporating the aqueous medium contained in the cake-like substance or powder obtained in step (C) by heating under normal pressure or reduced pressure. Processed starch-containing particles are obtained through step (D).
• the heating temperature is preferably 40°C or higher and 150°C or lower, more preferably 45°C or higher and 130°C or lower, even more preferably 50°C or higher and 110°C or lower, and still more preferably 55°C or higher and 95°C or lower. Particularly preferably the temperature is 60°C or more and 90°C or less.
• the heating time is preferably 3 hours or more.
• the particles of the present invention can be used as additives for external medicines, cosmetics, etc.; additives for coating materials such as matting agents for paints and powder coatings; resins for automobile materials, building materials, etc. It can be suitably used as an additive for a composition; an additive for an antiblocking agent; or an additive for a light-diffusing film.
• the particles of the present invention can be more suitably used as an additive for external preparations such as external medicines and cosmetics.
• the polysaccharide-containing particles of the present invention can be particularly suitably used as an additive for cosmetics.
• External preparation Embodiments of external preparations containing the particles of the present invention are illustrated below.
• the external preparation contains the particles of the present invention.
• External preparations can make pores, spots, wrinkles, etc. less noticeable by being applied to the skin.
• the content ratio of the particles of the present invention in the external preparation can be appropriately set depending on the type of the external preparation, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass.
• the content is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less.
• the external preparation can be used, for example, as an external medicine or cosmetic.
• external medicines include creams, ointments, emulsions, and the like.
• the dosage form of the cosmetic is not particularly limited, and any of aqueous, solubilized, oil-in-water, water-in-oil, and oil-based dosage forms can be applied.
• cosmetics include soaps, body shampoos, facial cleansing creams, facial scrubs, toothpastes, and other cleaning cosmetics; face powders, face powders (loose powders, pressed powders, etc.), foundations (powder foundations, liquid foundations, emulsified foundations) Make-up cosmetics such as foundation, etc.), lipstick, lip balm, blusher, eyebrow cosmetics (eye shadow, eyeliner, mascara, etc.), nail polish; Lotion agents such as pre-shave lotion and body lotion; Body powder such as body powder and baby powder External preparations; skin care products such as lotions, creams, and emulsions (cosmetic emulsions); antiperspirants (liquid antiperspirants, solid antiperspirants, cream antiperspirants, etc.), packs, hair washing cosmetics, and hair dyes. Examples include hair products, hair styling products, aromatic cosmetics, bath additives, sunscreen products, suntan products, and shaving creams.
• main ingredients or additives can be added to the above cosmetic according to the purpose, within a range that does not impair the effects of the present invention.
• Such main ingredients or additives include, for example, water, lower alcohols (alcohols with 5 or less carbon atoms), oils and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metallic soaps, humectants, Surfactants, polymer compounds, coloring materials, fragrances, clay minerals, preservatives/sterilizers, anti-inflammatory agents, antioxidants, ultraviolet absorbers, organic-inorganic composite particles, pH adjusters (triethanolamine, etc.), Examples include specially formulated additives and pharmaceutical active ingredients.
• oils and waxes examples include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame oil, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, Macadamia nut oil, mink oil, egg yolk oil, Japanese wax, coconut oil, rosehip oil, hydrogenated oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, spermaceti wax, jojoba oil, montan wax, beeswax, lanolin, etc. .
• hydrocarbons examples include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane, and the like.
• higher fatty acids include fatty acids having 11 or more carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids. Can be mentioned.
• Examples of the higher alcohol include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, Examples include alcohols having 6 or more carbon atoms such as decyltetradecanol.
• Examples of the above-mentioned sterols include cholesterol, dihydrocholesterol, phytocholesterol, and the like.
• fatty acid esters examples include linoleic acid esters such as ethyl linoleate; lanolin fatty acid esters such as isopropyl lanolin fatty acid; lauric acid esters such as hexyl laurate; isopropyl myristate, myristyl myristate, cetyl myristate, and octyl myristate.
• Myristic acid esters such as dodecyl; Oleic acid esters such as decyl oleate and octyldodecyl oleate; Dimethyloctanoic acid esters such as hexyldecyl dimethyloctoate; Isooctanoic acid esters such as cetyl isooctanoate (cetyl 2-ethylhexanoate); Palmitic acid esters such as decyl palmitate; glyceryl trimyristate, tri(caprylic/capric) glycerin, propylene glycol dioleate, glyceryl triisostearate, glyceryl triisooctoate, cetyl lactate, myristyl lactate, diisostearyl malate, Examples include cyclic alcohol fatty acid esters such as cholesteryl isostearate and cholesteryl 12-hydroxystearate.
• metal soap examples include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc undecylenate, and the like.
• humectant examples include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylit, maltitol, and the like.
• surfactant examples include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates, and phosphate ester salts; cationic surfactants such as amine salts and quaternary ammonium salts.
• Agents Betaine type, amino acid type, imidazoline type, amphoteric surfactants such as lecithin; Examples include ionic surfactants.
• polymer compounds examples include natural polymer compounds such as gum arabic, gum tragacanth, guar gum, locust bean gum, gum karaya, iris moss, quince seed, gelatin, shellac, rosin, and casein; sodium carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose.
• ethyl cellulose sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, crystalline cellulose and other semi-synthetic polymer compounds; polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil , nylon particles, poly(meth)acrylate particles (for example, polymethyl methacrylate particles, etc.), polystyrene particles, silicone particles, urethane particles, polyethylene particles, silica particles, and other synthetic polymer compounds.
• Examples of the above-mentioned color material raw materials include iron oxide (red iron oxide, yellow iron oxide, black iron oxide, etc.), ultramarine, konjou, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc. , kaolin, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, ceramic powder, etc.
• iron oxide red iron oxide, yellow iron oxide, black iron oxide, etc.
• ultramarine chromium oxide
• chromium hydroxide carbon black
• manganese violet titanium oxide
• titanium oxide zinc oxide
• talc. kaolin
• calcium carbonate magnesium carbonate
• mica aluminum silicate
• barium silicate calcium silicate
• magnesium silicate silica
• Examples include inorganic pigments such as azo-based, nitro-based, nitroso-based, xanthene-based, quinoline-based, anthraquinoline-based, indigo-based, triphenylmethane-based, phthalocyanine-based, and pyrene-based tar pigments.
• inorganic pigments such as azo-based, nitro-based, nitroso-based, xanthene-based, quinoline-based, anthraquinoline-based, indigo-based, triphenylmethane-based, phthalocyanine-based, and pyrene-based tar pigments.
• powder raw materials such as the above-mentioned powder raw materials for polymeric compounds and color material raw materials can also be used that have been surface-treated in advance.
• a surface treatment method known surface treatment techniques can be used, such as oil treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc.
• Treatment methods include polyethylene treatment, moisture retention treatment, inorganic compound treatment, and mechanochemical treatment.
• clay minerals examples include ingredients that have several functions such as extender pigments and adsorbents, such as talc, mica, sericite, titanium sericite (sericite coated with titanium oxide), and muscovite. , VEEGUM (registered trademark) manufactured by Vanderbilt, etc.
• Examples of the above perfume include anisaldehyde, benzyl acetate, geraniol, and the like.
• preservatives and disinfectants examples include methylparapen, ethylparapen, propylparapen, benzalkonium, benzethonium, and the like.
• antioxidants examples include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol, and the like.
• ultraviolet absorbers examples include inorganic absorbers such as fine titanium oxide, fine zinc oxide, fine cerium oxide, fine iron oxide, and fine zirconium oxide, benzoic acid, para-aminobenzoic acid, anthranilic acid, salicylic acid, Examples include organic absorbents such as cinnamic acid, benzophenone, and dibenzoylmethane.
• hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, and prednisone
• vitamins such as vitamin A, vitamin B, vitamin C, and vitamin E, citric acid, tartaric acid, lactic acid, Skin astringents such as aluminum chloride, aluminum/potassium sulfate, allantoin chlorohydroxyalumnium, zinc paraphenolsulfonate, zinc sulfate, cantharis tincture, capsicum tincture, ginger tincture, Jasperia japonica extract, garlic extract, hinokitiol, carpronium chloride , pentadecanoic acid glyceride, vitamin E, estrogen, hair growth promoters such as photosensors, and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.
• the coating agent comprises particles of the invention.
• the content ratio of the particles of the present invention in the coating agent can be appropriately set depending on the type of coating agent, but is preferably 1 to 90% by mass, more preferably 3 to 80% by mass.
• the coating material can contain a binder resin, an ultraviolet curable resin, and a solvent, if necessary.
• the binder resin include acrylic resin, alkyd resin, polyester resin, polyurethane resin, chlorinated polyolefin resin, and amorphous polyolefin resin. These resins can be used alone or in combination of two or more.
• a polyfunctional (meth)acrylate resin is preferable, and a polyhydric alcohol polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule is more preferable.
• the polyhydric alcohol polyfunctional (meth)acrylate resin having three or more (meth)acryloyl groups in one molecule includes trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate , 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Examples include tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, and the like. These resins can be used alone or in combination of two or more.
• a photopolymerization initiator is added to the ultraviolet curable resin to form a binder resin.
• photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, and peroxides.
• 2,3-dialkyldione compounds examples include 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyl oxime Examples include esters.
• These photopolymerization initiators can be used alone or in combination of two or more.
• solvents examples include, for oil-based paints, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane and ethylene glycol.
• hydrocarbon solvents such as toluene and xylene
• ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
• ester solvents such as ethyl acetate and butyl acetate
• dioxane and ethylene glycol examples include ether solvents such as diethyl ether and ethylene glycol monobutyl ether, and in the case of water-based paints, water, alcohols, and the like. These solvents can be used alone or in combination of two or more.
• the coating material may include a known coating surface conditioner, fluidity conditioner, ultraviolet absorber, light stabilizer, curing catalyst, extender pigment, coloring pigment, metal pigment, mica powder pigment, It may also contain a dye or the like.
• examples of the coating film forming method using the coating material include known coating film forming methods such as spray coating, roll coating, and brush coating.
• the coating material may be diluted with a diluent to adjust the viscosity as needed.
• diluents include aromatic compound solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; Water such as natural water, purified water, distilled water, ion-exchanged water, and pure water; alcoholic solvents such as methanol, ethanol, and isopropyl alcohol; and the like. These diluents can be used alone or in combination of two or more.
• a cross-coating film can be formed by applying the coating to any desired coating surface such as a base material, drying this coating film, and then curing the coating film as necessary. can do.
• the coating film using the coating material can be used by coating various base materials, including metal, wood, glass, plastic, etc., but is not particularly limited. It can also be used by coating a transparent substrate such as polyethylene terephthalate (PET), polycarbonate (PC), or acrylic resin.
• the resin composition includes a base resin and the particles of the present invention.
• Examples of the base resin include polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(ethylene succinate terephthalate), and poly(butylene succinate terephthalate).
• the content of the particles of the present invention in the resin composition is preferably 0.1 to 70% by mass, more preferably 0.1% to 70% by mass, based on the total mass of the base resin and the particles of the present invention. .5 to 50% by weight, and even more preferably 1 to 30% by weight.
• the resin composition may contain known additives as necessary.
• additives include reinforcing fibers such as glass fibers and carbon fibers, flame retardants, fluidity regulators, ultraviolet absorbers, heat stabilizers, light stabilizers, lubricants, extender pigments, color pigments, metal pigments, dyes, etc. be able to.
• the method for producing the resin composition is not particularly limited, and the resin composition can be produced by mixing the base resin and the particles of the present invention by a conventionally widely known method such as a mechanical grinding and mixing method. .
• the base resin and the particles of the present invention are mixed and stirred using a device such as a Henschel mixer, a V-type mixer, a Turbula mixer, a hybridizer, a rocking mixer, etc.
• a resin composition can be manufactured.
• the method for forming a molded article using the resin composition is not particularly limited, and any known method can be used.
• the base resin and the particles of the present invention are mixed in a mixer and kneaded in a melt kneader such as an extruder to obtain pellets made of a resin composition, and then the pellets are extruded, injected, blown, etc.
• a melt kneader such as an extruder
• the particles of the present invention are anti-blocking agents that provide unevenness to the surface of a resin film in order to prevent the surfaces of the resin films that are in contact with each other from sticking together and not being peeled off (blocking) when the resin film is wound up. Can be used as an agent.
• the antiblocking agent may contain, in addition to the particles of the present invention, a known antioxidant, fluidity modifier, light stabilizer, color pigment, etc., as necessary.
• the content of the particles of the present invention in the antiblocking agent is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.
• examples of the resin constituting the resin film in which an antiblocking agent can be used include polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, and poly(ethylene succinate).
• the content of the particles of the present invention in the resin film is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, even more preferably 0.01 to 3% by mass. It is % by mass, particularly preferably 0.01 to 1 % by mass.
• the light diffusing film comprises particles of the invention.
• the content of the particles of the present invention in the light diffusing film can be appropriately set depending on the type of the light diffusing film, but is preferably 1 to 90% by mass, more preferably 3 to 80% by mass.
• the light-diffusing film can be prepared by, for example, mixing the particles of the present invention, a binder resin, a diluent, etc. using a known method to prepare a dispersion liquid, and applying this onto a film serving as a base material using a known method.
• a binder resin e.g., polyethylene glycol dimethacrylate copolymer
• a diluent e.g., polystylene oxide, etc.
• the base material used for manufacturing the light diffusion film includes, for example, glass; a plastic sheet made of polycarbonate (PC), acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), etc.; Examples include plastic lenses and plastic panels.
• PC polycarbonate
• PET polyethylene terephthalate
• TAC triacetyl cellulose
• examples of the binder resin used for manufacturing the light diffusion film include acrylic resin, alkyd resin, polyester resin, polyurethane resin, chlorinated polyolefin resin, amorphous polyolefin resin, and the like. These resins can be used alone or in combination of two or more.
• diluents used in the production of the light diffusion film include aromatic compounds such as toluene and xylene; ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone; and ester compounds such as ethyl acetate and butyl acetate.
• Ether compounds such as dioxane and ethylene glycol diethyl ether; Water such as natural water, purified water, distilled water, ion exchange water, and pure water; Alcohols such as methanol, ethanol, and isopropyl alcohol.
• room temperature means a temperature within the range of 15°C or more and 30°C or less.
• the value obtained by subtracting the solid content weight of the sample before water absorption from the sample weight after water absorption (g) was defined as the weight increase after centrifugation (g).
• the solid content weight of the sample before water absorption is the solid content percentage measured using an infrared moisture meter (product name "FD-620", manufactured by Kett Science Institute Co., Ltd.) on the sample weight (0.5 g) before water absorption. It was calculated by multiplying the values.
• the solid content measurement conditions were a temperature of 120° C. and a measurement time of 20 minutes.
• BSA Standard Repeat the 2-fold dilution from the solution, and make a total of 7 levels (0.25 mg/mL, 0.125 mg/mL, 0.063 mg/mL, 0.0315 mg/mL, 0.0156 mg/mL, 0.0078 mg/mL, and 0.0078 mg/mL). 0039 mg/mL) was prepared.
• BSA Standard solutions (15 ⁇ L) of each concentration were mixed with 4 ⁇ Sample buffer (5.0 ⁇ L, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 2-mercaptoethanol (1.0 ⁇ L, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).
• the reflection intensity was measured using a variable angle photometer (device name: "GC-5000L", manufactured by Nippon Denshoku Kogyo Co., Ltd.). Light from the light source is made incident on the test sample at an angle of -45° with respect to the normal line (0°) of the test sample, and the reflection intensity of the reflected light at angles of 5°, 20°, and 70° is varied. Measured with a goniophotometer. The light diffusion rate was calculated according to the following formula (2).
• volume average particle diameter The volume average particle diameter of the particles to be measured was measured using a precision particle size distribution analyzer (product name: "Coulter Multisizer (registered trademark) 3" manufactured by Beckman Coulter, Inc.). Measurements were performed using an aperture calibrated according to the Multisizer® 3 User's Manual published by Beckman Coulter, Inc. The aperture used in the measurement was appropriately selected depending on the size of the particle to be measured.
• an aperture with a size of 10 ⁇ m when measuring in the particle size range of 0.2 ⁇ m to 6 ⁇ m, select an aperture with a size of 10 ⁇ m, and when measuring in the particle size range of 0.4 ⁇ m to 16 ⁇ m, select an aperture with a size of 20 ⁇ m.
• an aperture with a size of 100 ⁇ m was selected.
• 0.1 g of particles to be measured was added to 10 mL of a 0.1% by mass nonionic surfactant aqueous solution (Kao Corporation, "Perex SS-H"), and a touch mixer (Yamato Scientific Co., Ltd.) was used.
• a dispersion liquid was used by dispersing using an ultrasonic cleaner ("ULTRASONIC CLEANER VS-150", manufactured by Vervo Crea Co., Ltd.) and an ultrasonic cleaner ("ULTRASONIC CLEANER VS-150", manufactured by Vervo Crea Co., Ltd.).
• an ultrasonic cleaner ULTRASONIC CLEANER VS-150
• ULTRASONIC CLEANER VS-150 manufactured by Vervo Crea Co., Ltd.
• Example 1 In a container, 121 parts by mass of ion-exchanged water, 35 parts by mass of sodium chloride ("Mishio", manufactured by Ako Kasei Co., Ltd.) as a sodium salt, and sodium hydroxide ("Mishio", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a pH adjuster were added. 1.2 parts by mass of "sodium oxide”) was added thereto and dissolved by stirring at room temperature to prepare an aqueous solution.
• sodium chloride (“Mishio”, manufactured by Ako Kasei Co., Ltd.)
• sodium hydroxide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• processed starch-containing particles contained four proteins: albumin, globulin, prolamin, and glutelin.
• Example 2 Processed starch-containing particles were prepared in the same manner as in Example 1, except that 1.13 parts by mass of Orientase 22BF was used as the alkaline protease, and the reaction was maintained at 40°C using a stirrer for 18 hours. I got it. It was confirmed that the obtained processed starch-containing particles contained four proteins: albumin, globulin, prolamin, and glutelin.
• Example 3 In a container, 137 parts by mass of ion-exchanged water, 45 parts by mass of sodium sulfate ("Sodium Sulfate” manufactured by Kanto Kagaku Co., Ltd.) as a sodium salt, and sodium hydroxide ("New Crystal” manufactured by Nippon Soda Co., Ltd.) as a pH adjuster. 1.6 parts by mass was added and dissolved by heating to 45° C. with stirring to prepare an aqueous solution.
• sodium sulfate manufactured by Kanto Kagaku Co., Ltd.
• sodium hydroxide New Crystal manufactured by Nippon Soda Co., Ltd.
• Example 1 shows the results of each Example and each Comparative Example. Note that the amount of ion-exchanged water used in Example 3 means the total amount of ion-exchanged water used. "Volume average particle size” in Table 1 means the volume average particle size ( ⁇ m) of the processed starch-containing particles obtained in Examples 1 to 3 and Comparative Example 1.
• Item 1 Contains modified starch
• the protein content is 500 mass ppm or less, Processed starch-containing particles having a water absorption rate of 650% or less.
• the light diffusivity is preferably 50% to 210%, more preferably 60% to 210%, even more preferably 70% to 210%, still more preferably 80% to 210%, even more preferably 90% to 210%. , particularly preferably from 100% to 210%.
• Item 3. Item 3.
• Item 4. Item 4.
• Item 4. The processed starch-containing particles according to any one of Items 1 to 3, wherein the protein is at least one selected from the group consisting of globulin, albumin, prolamin, and glutelin.
• Item 6. Item 4. The processed starch-containing particles according to any one of Items 1 to 3, wherein the protein is globulin, albumin, prolamin, and glutelin. Section 7.
• the processed starch is phosphoric acid crosslinked starch, metal salt of phosphoric acid crosslinked starch, acetylated phosphoric acid crosslinked starch, metal salt of acetylated phosphoric acid crosslinked starch, hydroxypropylated phosphoric acid crosslinked starch, hydroxypropylated phosphate crosslinked starch 7.
• the starch according to any one of Items 1 to 6, which is at least one selected from the group consisting of metal salts of phosphoric acid crosslinked starch, phosphoric acid monoesterified phosphoric acid crosslinked starch, and phosphoric acid crosslinked starch phosphoric acid monoesterified. Modified starch-containing particles. Section 8.
• the processed starch is at least one selected from the group consisting of phosphoric acid crosslinked starch, acetylated phosphoric acid crosslinked starch, hydroxypropylated phosphoric acid crosslinked starch, and phosphoric acid monoesterified phosphoric acid crosslinked starch.
• the modified starch-containing particles according to any one of Items 1 to 6, wherein the modified starch is preferably phosphoric acid crosslinked starch or a metal salt of phosphoric acid crosslinked starch, more preferably phosphoric acid crosslinked starch.
• Item 11. The processed starch-containing particles according to any one of Items 1 to 10, wherein the processed starch is treated with a protease.
• the protease is preferably an alkaline protease, more preferably at least one selected from the group consisting of orientase, alcalase, sumizyme, alloase, maxipro and bioplase, even more preferably selected from the group consisting of orientase, alcalase and sumizyme. Item 12.
• the content of the modified starch is usually more than 50% by mass, preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, still more preferably 99% by mass or more, even more preferably 13.
• Item 14 The processed starch-containing particles according to any one of Items 3 to 13, consisting only of processed starch and protein.
• the content of the protein is preferably 400 mass ppm or less, more preferably 300 mass ppm or less, even more preferably 200 mass ppm or less, still more preferably 150 mass ppm or less, even more preferably 100 mass ppm or less, particularly preferably is 75 mass ppm or less, the modified starch-containing particles according to any one of Items 1 to 15.
• the water absorption rate is usually 50% or more and 550% or less, preferably 75% or more and 525% or less, more preferably 100% or more and 500% or less, even more preferably 125% or more and 475% or less, and still more preferably 150% or more and 450% or more. % or less, even more preferably from 175% to 425%, particularly preferably from 200% to 400%.
• the volume average particle diameter is usually 3.0 ⁇ m or more and 20.0 ⁇ m or less, preferably 3.2 ⁇ m or more and 18.0 ⁇ m or less, more preferably 3.4 ⁇ m or more and 16.0 ⁇ m or less, and even more preferably 3.6 ⁇ m or more and 14.0 ⁇ m.
• Item 19 A method for producing processed starch-containing particles according to any one of items 1 to 18, comprising: a step (A) of treating starch with a phosphoric acid compound; a step (B) of treating the starch with protease; Equipped with A method for producing processed starch-containing particles, wherein the step (A) and the step (B) are performed continuously. Section 20.
• the protease is preferably an alkaline protease, more preferably at least one selected from the group consisting of orientase, alcalase, sumizyme, alloase, maxipro and bioplase, even more preferably selected from the group consisting of orientase, alcalase and sumizyme.
• Item 20 The method for producing processed starch-containing particles according to item 19, which is at least one type of starch, particularly orientase.
• Section 21. Item 21. The method for producing processed starch-containing particles according to Item 19 or 20, wherein the starch is rice starch. Section 22. Item 22.

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• 2023
  • 2023-06-21 WO PCT/JP2023/022989 patent/WO2024048030A1/ja not_active Ceased
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