Silicone-modified pullulan, composition containing the same, and cosmetic

Abstract

To provide a silicone-modified pullulan improved in stability, a silicone-modified pullulan-containing composition, and a method for producing the same.SOLUTION: The silicone-modified pullulan is an addition reaction product of the following components (a) and (b): (a) a pullulan having a water content of 1.0 mass% or less and a calcium content of less than 100 ppm; and (b) an isocyanate group-containing silicone represented by formula (1). In the silicone-modified pullulan, the calcium content is less than 100 ppm and the content of a urea group-containing silicone represented by the following formula (2) is less than 2,000 ppm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to silicone-modified pullulan, a composition containing the modified pullulan, and a cosmetic. More specifically, the present invention relates to silicone-modified pullulan with reduced impurity levels and a method for producing the silicone-modified pullulan. [Background technology]

[0002] Silicone-modified polysaccharides, in which polysaccharides are modified with silicone, have been studied for some time (Patent Documents 1 and 2). For example, Patent Document 1 describes a siloxane-containing cellulose derivative that possesses the properties of both cellulose and silicone. Patent Document 2 describes a siloxane-containing pullulan that combines the properties of both pullulan and silicone compounds. The incorporation of silicone-modified polysaccharides into cosmetics has also been studied (Patent Documents 3-6). Patent Document 3 describes a sunscreen cosmetic characterized by the combined use of a specific silicone-modified polysaccharide compound with an organic UV absorber. Patent Document 4 describes a water-in-oil emulsion cosmetic containing a silicone-modified polysaccharide compound. Patent Document 6 describes an eye cosmetic composition containing silicone-modified pullulan. As described in Patent Documents 3 to 6, cosmetics containing silicone-modified polysaccharides have high water resistance and oil resistance and are also excellent in feel when used. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 6-145201 [Patent Document 2] Japanese Patent Application Publication No. 8-134103 [Patent Document 3] Japanese Patent Application Publication No. 10-29921 [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-278729 [Patent Document 5] International Publication No. 2012 / 133293 [Patent Document 6] Japanese Patent Application Publication No. 2017-218413 Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional silicone-modified polysaccharides have problems with storage stability when dissolved in organic oils. More specifically, they can appear cloudy or exhibit needle-like crystal precipitation. This is thought to be due to the presence of residual ionic metal salts and the precipitation of dimers of unreacted monomers. Therefore, there has been a demand for silicone-modified pullulan that is stable when formulated into a composition. Furthermore, because the unreacted monomers contain isocyanate groups, there is concern that a large amount of residual monomers may cause skin irritation. [Means for solving the problem]

[0005] The present invention has been made in consideration of the above problems, and aims to provide a silicone-modified pullulan-containing composition containing a silicone-modified pullulan and an oil agent, which has improved stability, and a method for producing the same. In particular, the present invention aims to provide a composition containing silicone-modified pullulan with a low amount of impurities, which has high storage stability, and which does not cause a deterioration in the feel when incorporated into cosmetics. Such a silicone-modified pullulan-containing composition can provide a highly safe and transparent composition.

[0006] Pullulan is generally produced by culturing pullulan-producing bacteria, and ionic inorganic salts are used in the culture medium during this process. The present inventors conducted extensive research into the conventional problems and found that when pullulan contains inorganic salts such as calcium, compositions containing silicone-modified pullulan become cloudy, and that side reactions occur predominantly when silicone-modifying pullulan. Furthermore, pullulan absorbs moisture over time due to its hydroxyl groups. This moisture-induced side reaction produces urea-containing silicones during the production of silicone-modified pullulan, and these urea-containing silicones are difficult to remove even after a washing process. Therefore, the inventors discovered that the production of urea-containing silicones during the production of silicone-modified pullulan can be suppressed by dehydrating pullulan in advance.

[0007] Furthermore, organotin and amine catalysts have traditionally been used as reaction catalysts for pullulan and silicone-modified isocyanate. However, organotin catalysts have safety issues, and amine catalysts have low catalytic activity. Therefore, the production method of the present invention has found that by using a specific catalyst, the silicone addition rate can be improved and silicone-modified pullulan with a glass transition temperature of 100 to 150°C can be provided.

[0008] That is, the present invention provides a silicone-modified pullulan which is an addition reaction product of the following components (a) and (b): (a) Pullulan having a moisture content of 1.0% by mass or less and a calcium content of less than 100 ppm (b) Isocyanate group-containing silicone represented by the following formula (1): [ka] (In the formula, R 1 are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 10, and a is an integer of 0 to 3. The calcium content in the silicone-modified pullulan is less than 100 ppm, And the following formula (2) [ka] (In the formula, R 1 , R 2 , n, and a are as above) The content of the urea group-containing silicone represented by the formula (I) is less than 2,000 ppm. The silicone-modified pullulan is provided. Furthermore, the present invention provides a composition containing the silicone-modified pullulan, a cosmetic containing the composition, and a method for producing the silicone-modified pullulan. [Effects of the Invention]

[0009] The silicone-modified pullulan of the present invention has a low content of impurities such as by-products. The silicone-modified pullulan-containing composition of the present invention has improved storage stability due to the low content of impurities, and when incorporated into cosmetics, it does not cause a deterioration in the feel of use. Furthermore, its high safety and transparency make it suitable for addition to coating agents and paints. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will now be described in more detail.

[0011] The silicone-modified pullulan of the present invention is characterized by being an addition reaction product of the following components (a) and (b): (a) Pullulan having a moisture content of 1.0% by mass or less and a calcium content of less than 100 ppm (b) Isocyanate group-containing silicone represented by the following formula (1): [ka] (In the formula, R 1are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 10, and a is an integer of 0 to 3.

[0012] The silicone-modified pullulan of the present invention has a calcium content of less than 100 ppm, And the following formula (2) [ka] (In the formula, R 1 , R 2 , n, and a are as above) The content of the urea group-containing silicone represented by the formula (1) is less than 2,000 ppm. More preferably, the residual amount of the isocyanate group-containing silicone represented by the formula (1) is less than 2,000 ppm.

[0013] In the present invention, (a) pullulan is characterized by having a water content of 1.0% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, based on the total pullulan. There is no particular lower limit for the water content, and the lower the better. It is preferably 0.001% by mass or more, and more preferably 0.005% by mass or more. If the water content exceeds the upper limit, a large amount of urea group-containing silicone represented by the above formula (2) may be produced as a by-product during reaction with (b) isocyanate group-containing silicone, which is undesirable. The water content in pullulan can be measured by the Karl Fischer method. There are no particular limitations on the method for reducing the moisture content of pullulan to 1.0% by mass or less. Examples include drying pullulan under reduced pressure at 50 to 120°C, or removing water by azeotropic dehydration with hexane, toluene, or the like.

[0014] The calcium content of the pullulan of the present invention is characterized by being less than 100 ppm of the total pullulan, preferably 50 ppm or less, and more preferably 30 ppm or less. There is no particular lower limit for the calcium content, and the lower the better. It is preferably 0.01 ppm or more, and more preferably 0.1 ppm or more. If the calcium content is above the upper limit, there is a risk of a large amount of urea group-containing silicone represented by the above formula (2) being produced as a by-product during the reaction. This is also undesirable because the appearance of the resulting composition may become cloudy. In the present invention, the calcium content refers to the value calculated as elemental calcium measured by ICP atomic emission spectroscopy.

[0015] The pullulan preferably has a weight-average molecular weight of 1,000 to 5,000,000, more preferably 30,000 to 400,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC) analysis (solvent: DMF, pullulan equivalent, 25°C).

[0016] The pullulan used in the present invention may be any pullulan that satisfies the above-mentioned requirements and is obtained by purifying commercially available pullulan. Alternatively, a commercially available pullulan that has been desalted and purified in advance may be used after dehydration. For example, it is preferable to use pullulan (desalted and purified) manufactured by Hayashibara Co., Ltd., which is sold for use in cosmetics, after dehydration.

[0017] Component (b) is an isocyanate group-containing silicone and is represented by the following formula (1): [ka] In formula (1), R 1are each independently selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the fluorine-substituted alkyl group include a trifluoropropyl group, a nonafluorohexyl group, and a heptadecafluorodecyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Preferably, the alkyl group has 1 to 8 carbon atoms or a phenyl group, and more preferably a methyl group.

[0018] R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group. Among these, a methyl group, an ethyl group, or a phenyl group is preferred. n is an integer of 1 to 10, preferably an integer of 2 to 8, more preferably an integer of 3 to 6, and most preferably 3. a is an integer of 0 to 3, preferably 0, 1, or 2, and most preferably 0.

[0019] (b) Examples of the isocyanate group-containing silicone include compounds represented by the following formula: [ka]

[0020] The silicone-modified pullulan of the present invention is an addition reaction product of (a) pullulan and (b) an isocyanate group-containing silicone. The compounding ratio when adding reacting (a) pullulan with (b) an isocyanate group-containing silicone is preferably 500 to 800 parts by mass, more preferably 600 to 700 parts by mass, of the isocyanate group-containing silicone to 100 parts by mass of pullulan.

[0021] The addition reaction is preferably carried out in (c) an organic solvent. Examples of organic solvents include esters such as butyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethers such as dibutyl ether, tetrahydrofuran, and dioxane, and amides such as N,N-dimethylformamide and N-methylpyrrolidone. These may be used alone or in combination. The amount of (c) organic solvent may be adjusted as appropriate, but is preferably 1,000 to 10,000 parts by mass of organic solvent per 100 parts by mass of pullulan. It is preferable that the (c) organic solvent used in the present invention has a low water content. The water content in the organic solvent is preferably 5,000 ppm or less, and more preferably 1 to 1,000 ppm. A water content within this range is preferred because it can suppress the generation of by-products.

[0022] While the above addition reaction typically proceeds without a catalyst, the production method of the present invention preferably uses a catalyst. From the standpoints of catalytic activity and safety, organometallic compounds containing metal elements such as iron, bismuth, zirconium, titanium, aluminum, and copper are preferred as catalysts. Organometallic compound catalysts have higher catalytic activity than amine catalysts and can improve the silicone addition rate. This reduces the amount of impurities and provides silicone-modified pullulan with a glass transition temperature of 100 to 150°C. Examples of organometallic compounds include acetylacetone metal complexes such as aluminum acetylacetone, iron acetylacetone, copper acetylacetone, titanium acetylacetone, and zirconium acetylacetone, as well as bismuth carboxylate. Acetylacetone metal complexes are particularly preferred, with iron acetylacetone complex being particularly preferred. The amount of organometallic compound is preferably 0.0001 to 0.1 parts by mass, and more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of pullulan. In the production method of the present invention, the use of such organometallic compounds as catalysts increases the addition reaction rate and reduces the amount of impurities.

[0023] The addition reaction temperature is preferably 50 to 150°C. The reaction time may be selected appropriately. After the reaction is completed, the silicone-modified pullulan can be obtained by washing and drying. The silicone-modified pullulan obtained by the production method of the present invention is characterized by having a small amount of by-products. That is, the silicone-modified pullulan is characterized by having a calcium content of less than 100 ppm and a content of the urea group-containing silicone represented by the above formula (2) of less than 2,000 ppm. Preferably, the remaining amount of the raw material isocyanate group-containing silicone represented by the above formula (1) is less than 2,000 ppm.

[0024] The calcium content in the silicone-modified pullulan is less than 100 ppm, preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably 5 ppm or less. The lower limit is not particularly limited, and the lower the better, but it is, for example, 0.01 ppm or more. If the calcium content is above the upper limit, the appearance of the resulting composition becomes cloudy, and precipitates may form in the composition, impairing aesthetics. The calcium content may be measured by the above-mentioned method for measuring the calcium content in pullulan.

[0025] In the silicone-modified pullulan, the content of the urea group-containing silicone represented by the above formula (2) is less than 2,000 ppm, preferably 1,800 ppm or less, preferably 1,500 ppm or less, and more preferably 1,000 ppm or less. There is no particular lower limit, and the lower the better, it is, for example, 0.1 ppm or more, preferably 1 ppm or more. If the content is above the upper limit, the appearance may become cloudy and a precipitate may form over time. The urea group-containing silicone is difficult to remove by washing. The content of the urea group-containing silicone can be measured by gas chromatography.

[0026] Furthermore, the residual amount of the starting isocyanate group-containing silicone represented by the above formula (1) in the silicone-modified pullulan is preferably less than 2,000 ppm, preferably 1,800 ppm or less, more preferably 1,500 ppm or less, and even more preferably 1,000 ppm or less. The lower limit is not particularly limited, and the lower the better, but it is, for example, 0.1 ppm or more, preferably 1 ppm or more. If the residual amount is above the upper limit, there is a risk of precipitation in the composition over time. Furthermore, it is undesirable from a safety standpoint when blended into cosmetics. The residual amount of isocyanate group-containing silicone can be measured by headspace gas chromatography.

[0027] The silicone-modified pullulan of the present invention preferably has a glass transition temperature of 100 to 150°C, more preferably 110 to 140°C. A glass transition temperature within this range is preferable because it forms a strong and flexible film, which, when used in cosmetics, is gentle on the skin and has excellent durability. The glass transition temperature of the present invention is a value measured by dynamic viscoelasticity measurement.

[0028] The present invention further provides a composition containing the silicone-modified pullulan and various oils. (A) the silicone-modified pullulan: 20 to 50% by mass, and (B) One or more oils selected from silicone oils, hydrocarbon oils, and ester oils: 50 to 80% by mass The present invention provides a silicone-modified pullulan composition comprising:

[0029] In component (B), examples of silicone oils include low- to high-viscosity linear or branched organopolysiloxanes such as dimethylpolysiloxane, tristrimethylsiloxymethylsilane, caprylyl methicone, phenyltrimethicone, tetraquistrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane-methylphenylsiloxane copolymer. Alternatively, examples include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, and tetramethyltetraphenylcyclotetrasiloxane; amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxanes, pyrrolidonecarboxylic acid-modified organopolysiloxanes; silicone rubbers such as high-polymerization gummy dimethylpolysiloxanes, gummy amino-modified organopolysiloxanes, and gummy dimethylsiloxane-methylphenylsiloxane copolymers; and cyclic organopolysiloxane solutions of silicone gums and rubbers.

[0030] Examples of hydrocarbon oils include linear, branched, and volatile hydrocarbon oils, such as ozokerite, α-olefin oligomers, light isoparaffin, isododecane, isohexadecane, light liquid isoparaffin, squalane, synthetic squalane, vegetable squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, polyethylene-polypropylene wax, ethylene / propylene / styrene copolymer, butylene / propylene / styrene copolymer, liquid paraffin, liquid isoparaffin, pristane, polyisobutylene, hydrogenated polyisobutene, microcrystalline wax, and petrolatum. Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid.

[0031] Ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, Examples of suitable hydroxystearic acid esters include butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isononyl isononanoate, isotridecyl isononanoate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, 2-octyldodecyl N-lauroyl-L-glutamate, isopropyl lauroyl sarcosine, and diisostearyl malate. Examples of glyceride oils include acetoglyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tribehenate, glyceryl monostearate, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, and diglyceryl myristate isostearate.

[0032] The silicone-modified pullulan composition of the present invention preferably has a transparent appearance and a viscosity at 25°C of 50 to 200,000 mPa·s as measured by the rotational viscosimetry method described in the Quasi-drug Ingredients Standards 2006.

[0033] The silicone-modified pullulan composition preferably produces a white precipitate when mixed with 1.5 parts by mass of acetone containing 1 part by mass of a composition consisting of 30% by mass of the silicone-modified pullulan and 70% by mass of a hydrocarbon oil such as isododecane. If the composition dissolves without producing a white precipitate in the acetone mixing test, the composition's stability over time and its stability when incorporated into cosmetics and coatings may be impaired. The silicone-modified pullulan composition of the present invention is silicone-modified to have a glass transition temperature of 100 to 150°C, and therefore produces a white precipitate when mixed with acetone.

[0034] The silicone-modified pullulan composition of the present invention can be added to cosmetics. The amount of silicone-modified pullulan composition to be added is not particularly limited, but it is suitable to add it in the range of 0.05 to 20% by mass, preferably 0.1 to 10% by mass, of the total cosmetic.

[0035] Cosmetics optionally contain ingredients acceptable for cosmetics. Examples of the cosmetic include powders, oils, water-in-oil emulsions, oil-in-water emulsions, non-aqueous emulsions, and multiple emulsions such as W / O / W and O / W / O. Examples of cosmetics include skin care cosmetics such as lotions, milky lotions, creams, cleansers, packs, oily liquids, massage products, beauty serums, beauty oils, detergents, deodorants, hand creams, lip balms, and wrinkle concealers; makeup cosmetics such as makeup bases, concealers, face powders, powder foundations, liquid foundations, cream foundations, oily foundations, blushers, eye shadows, mascaras, eyeliners, eyebrow pencils, and lipsticks; hair cosmetics such as shampoos, rinses, treatments, and setting agents; antiperspirants; and UV protection cosmetic compositions such as sunscreen oils, sunscreen emulsions, and sunscreen creams. The cosmetic may be in a variety of forms, including liquid, emulsion, cream, solid, paste, gel, powder, pressed, multi-layered, mousse, spray, stick, and pencil form. [Example]

[0036] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, the pullulan used in Examples 1-2 is a desalted and purified cosmetic pullulan having a weight-average molecular weight of 200,000 manufactured by Hayashibara Co., Ltd. The pullulan used in Comparative Examples 1-2 is a non-desalted and purified pullulan product, Pullulan PF-20 manufactured by Hayashibara Co., Ltd., having a weight-average molecular weight of 200,000.

[0037] [Example 1] A 7,000 ml reactor was charged with 100 g of pullulan and 1,300 g of hexane, and the mixture was azeotropically dehydrated under reduced pressure at 80°C for 2 hours while stirring. The pullulan had a water content of 200 ppm and a calcium content of 10 ppm. 3,000 g of N-methylpyrrolidone and 0.03 g of acetylacetonate iron complex were added and dissolved by heating at 120°C. 560 g of the isocyanate-containing organopolysiloxane represented by formula (3) was added dropwise to the mixture. After stirring for 5 hours at 120°C, 2,600 g of N-methylpyrrolidone separated from the reaction solution was removed, and 2,300 g of hexane was added to the remaining resin and dissolved by stirring. 1,200 g of methanol was added and stirred, and the methanol layer was discarded. This washing procedure was repeated twice, followed by drying under reduced pressure at 80°C for 8 hours, yielding 525 g of silicone-modified pullulan. The silicone-modified pullulan had a glass transition temperature of 125°C. The calcium content in the obtained silicone-modified pullulan was less than 1 ppm, the content of the isocyanate group-containing organopolysiloxane represented by the following formula (3) was 200 ppm, and the content of the urea group-containing organopolysiloxane represented by the following formula (4) was 50 ppm. [ka] [ka]

[0038] 30 g of the silicone-modified pullulan and 70 g of isododecane were mixed and dissolved to obtain a pale yellow, transparent composition with a viscosity of 450 mPa·s. When 1 g of this composition was mixed with 1.5 g of acetone, a white precipitate was deposited. Furthermore, the appearance of this composition remained unchanged even after being stored at room temperature for one month.

[0039] [Example 2] A 5,000 ml reactor was charged with 100 g of pullulan and 400 g of hexane, and the mixture was subjected to azeotropic dehydration under reduced pressure at 80°C for 2 hours while stirring. The pullulan had a water content of 400 ppm and a calcium content of 10 ppm. 1,500 g of N-methylpyrrolidone and 0.05 g of bismuth carboxylate (product name: K-KAT XK-640, manufactured by KING INDUSTRY) were added and dissolved by heating at 120°C. 600 g of the isocyanate group-containing organopolysiloxane represented by formula (3) was added dropwise. After stirring and reacting for 5 hours at 120°C, 1,000 g of methyl ethyl ketone was added and dissolved by stirring. This solution was added to 3,000 g of methanol and stirred to precipitate the resin. The mixture was washed three times with 300 g of methanol and dried under reduced pressure at 80°C for 8 hours, yielding 600 g of resin. The silicone-modified pullulan obtained had a glass transition temperature of 118°C. The calcium content in the obtained silicone-modified pullulan was less than 1 ppm, the content of the isocyanate group-containing organopolysiloxane represented by the above formula (3) was 1,800 ppm, and the content of the urea group-containing organopolysiloxane represented by the above formula (4) was 1,500 ppm.

[0040] 30 g of the silicone-modified pullulan and 70 g of isododecane were mixed and dissolved to obtain a pale yellow, transparent composition with a viscosity of 750 mPa·s. When 1 g of this composition was mixed with 1.5 g of acetone, a white precipitate was deposited. Furthermore, the appearance of this composition remained unchanged even after being stored at room temperature for one month.

[0041] [Comparative Example 1] A 7,000 ml reactor was charged with 100 g of pullulan (water content: 3.5%, calcium content: 1,200 ppm). 3,000 g of N-methylpyrrolidone and 10 g of triethylamine were added and heated to 120°C for dissolution. 560 g of the isocyanate-containing organopolysiloxane represented by formula (3) was added dropwise. After stirring and reacting for 5 hours at 120°C, 1,800 g of N-methylpyrrolidone separated from the reaction solution was removed, and 2,300 g of hexane was added to the remaining resin and stirred for dissolution. 1,200 g of methanol was added and stirred, and the methanol layer was discarded. This washing procedure was repeated twice, followed by drying under reduced pressure at 80°C for 8 hours, yielding 470 g of resin. The resulting silicone-modified pullulan had a glass transition temperature of 155°C. The resulting silicone-modified pullulan had a calcium content of 700 ppm, a content of the isocyanate group-containing organopolysiloxane represented by the above formula (3) of 7,000 ppm, and a content of the urea group-containing organopolysiloxane represented by the above formula (4) of 8,000 ppm.

[0042] 30 g of the silicone-modified pullulan and 70 g of isododecane were mixed and dissolved to obtain a pale yellow, opaque composition with a viscosity of 1,400 mPa·s. When 1 g of this composition was mixed with 1.5 g of acetone, no white precipitate formed, resulting in a clear solution. Furthermore, this composition formed a white precipitate after one month at room temperature, indicating poor stability over time.

[0043] Comparative Example 2 A 7,000 ml reactor was charged with 100 g of pullulan dried at 110°C for 2 hours. The pullulan had a water content of 1.2% and a calcium content of 1,200 ppm. 3,000 g of N-methylpyrrolidone and 10 g of triethylamine were added and dissolved by heating at 120°C. 560 g of the isocyanate-containing organopolysiloxane represented by formula (3) was then added dropwise. After stirring for 5 hours at 120°C, 1,800 g of N-methylpyrrolidone separated from the reaction solution was removed, and 2,300 g of hexane was added to the remaining resin and dissolved by stirring. 1,200 g of methanol was added and stirred, and the methanol layer was discarded. This washing procedure was repeated twice, followed by drying under reduced pressure at 80°C for 8 hours, yielding 480 g of resin. The resulting silicone-modified pullulan had a glass transition temperature of 155°C. The resulting silicone-modified pullulan had a calcium content of 700 ppm, a content of the isocyanate group-containing organopolysiloxane represented by the above formula (3) of 6,000 ppm, and a content of the urea group-containing organopolysiloxane represented by the above formula (4) of 7,000 ppm.

[0044] 30 g of the silicone-modified pullulan and 70 g of isododecane were mixed and dissolved to obtain a pale yellow, opaque composition with a viscosity of 1,200 mPa·s. When 1 g of this composition was mixed with 1.5 g of acetone, no white precipitate formed, resulting in a clear solution. Furthermore, this composition formed a white precipitate after one month at room temperature, indicating poor stability over time.

[0045] The manufacturing method of the present invention can provide silicone-modified pullulan with a low content of impurities such as by-products. The composition containing the silicone-modified pullulan of the present invention has improved storage stability, and when incorporated into cosmetics, it does not cause a deterioration in the feel during use. Furthermore, its high safety and transparency make it suitable for addition to coating agents and paints.

Claims

1. A silicone-modified pullulan characterized by being an addition reaction product of the following components (a) and (b): (a) Pullulan having a moisture content of 1.0% by mass or less and a calcium content of less than 100 ppm (b) an isocyanate group-containing silicone represented by the following formula (1): 【Chemical 1】 (In the formula, R １ are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; R ２ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 10, and a is an integer of 0 to 3. the calcium content in the silicone-modified pullulan is less than 100 ppm; And the following formula (2) 【Chemistry 2】 (In the formula, R １ , R ２ , n, and a are as described above) The content of the urea group-containing silicone represented by the formula (I) is less than 2,000 ppm. The silicone-modified pullulan.

2. 2. The silicone-modified pullulan according to claim 1, which has a glass transition temperature of 100 to 150° C. as measured by dynamic viscoelasticity measurement.

3. 3. The silicone-modified pullulan according to claim 1, wherein the amount of the isocyanate group-containing silicone represented by formula (1) remaining in the silicone-modified pullulan is less than 2,000 ppm.

4. (A) 20 to 50% by mass of the silicone-modified pullulan according to any one of claims 1 to 3, and (B) One or more oils selected from silicone oils, hydrocarbon oils, and ester oils: 50 to 80% by mass A composition comprising:

5. The composition according to claim 4, having a viscosity of 50 to 200,000 mPa·s at 25°C as measured in accordance with JIS K7117-1:1999.

6. A cosmetic comprising the composition according to claim 4 or 5.

7. A method for producing silicone-modified pullulan, comprising: (a) pullulan having a moisture content of 1.0% by mass or less and a calcium content of less than 100 ppm; (b) an isocyanate group-containing silicone represented by the following formula (1): 【Chemistry 3】 (In the formula, R １ are each independently a group selected from an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; R ２ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, n is an integer of 1 to 10, and a is an integer of 0 to 3. and subjecting the silicone-modified pullulan to an addition reaction, The calcium content in the silicone-modified pullulan is less than 100 ppm, and the silicone-modified pullulan satisfies the following formula (2): 【Chemistry 4】 (In the formula, R １ , R ２ , n, and a are as described above) The above production method, wherein the content of the urea group-containing silicone represented by the formula (I) is less than 2,000 ppm.

8. The method according to claim 7, wherein the addition reaction is carried out in the presence of an organometallic compound.

9. The method according to claim 8, wherein the organometallic compound is an acetylacetone metal complex or a bismuth carboxylate.

10. The method according to any one of claims 7 to 9, wherein the blending amount of the component (b) is 500 to 700 parts by mass per 100 parts by mass of the component (a).

11. The method according to any one of claims 7 to 10, wherein the addition reaction is carried out in an organic solvent, and the amount of the organic solvent is 1,000 to 10,000 parts by mass per 100 parts by mass of the component (a).

12. The method according to any one of claims 7 to 11, wherein the amount of the isocyanate group-containing silicone represented by formula (1) remaining in the silicone-modified pullulan is less than 2,000 ppm.

13. The method according to any one of claims 7 to 12, wherein the silicone-modified pullulan has a glass transition temperature of 100 to 150°C as measured by dynamic viscoelasticity measurement.

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