CN115551926A - Cellulose particles containing inorganic substance and method for producing same - Google Patents
Cellulose particles containing inorganic substance and method for producing same Download PDFInfo
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- CN115551926A CN115551926A CN202180034133.9A CN202180034133A CN115551926A CN 115551926 A CN115551926 A CN 115551926A CN 202180034133 A CN202180034133 A CN 202180034133A CN 115551926 A CN115551926 A CN 115551926A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The present invention provides an inorganic-coated cellulose particle, wherein the inorganic-coated cellulose particle contains an inorganic substance in a cellulose-containing cellulose particle, the mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2, and the average particle size of the inorganic-coated cellulose particle is 1 to 300 [ mu ] m. The present invention also provides a method for producing an inorganic substance-encapsulated cellulose particle, comprising mixing a cellulose acetate solution in which cellulose acetate is dissolved in an organic solvent with the inorganic substance so that the mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2 to obtain a resin mixture, suspending the resin mixture in water to prepare a suspension in which the inorganic substance-encapsulated cellulose acetate particle is dispersed in water, removing the organic solvent from the suspension, and saponifying the cellulose acetate particle to produce an inorganic substance-encapsulated cellulose particle in which the inorganic substance is encapsulated in the cellulose particle.
Description
Technical Field
The present invention relates to a cellulose particle containing an inorganic substance encapsulated therein and a method for producing the same.
This application claims priority based on Japanese patent application No. 2020-083983, filed on 12.5.2020, the contents of which are incorporated herein by reference.
Background
Particles such as acrylic beads, polystyrene beads, and polyurethane beads have been used for various products such as paints, plastics, adhesives, and cosmetics.
In recent years, problems of micro plastics in marine environments have been receiving much attention, and thus, demand for micron-sized cellulose particles using natural products as raw materials has been increasing.
As a method for producing cellulose particles, for example, a method described in patent document 1 is known. Patent document 1 describes the following methods (1) and (2).
Method (1): the method comprises cutting a cellulose ester filament produced by a dry spinning method using a solution of a cellulose ester in an organic solvent as a stock solution to prepare a chip (chip), heating and melting the chip in a medium to form spherical particles of the cellulose ester, and saponifying the spherical particles. Method (2): a solution of a cellulose ester in an organic solvent is used as a stock solution, the stock solution is suspended in a medium insoluble or slightly soluble in the organic solvent, the medium containing the suspended particles is heated to evaporate the organic solvent, spherical particles of the cellulose ester are formed, and the spherical particles are saponified.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication No. 55-40618
Disclosure of Invention
Problems to be solved by the invention
However, conventional cellulose particles have a problem of stability with time due to moisture absorption because they have a characteristic of easily absorbing moisture. Further, when cellulose particles are applied to products such as paints, plastics, adhesives, cosmetics, and the like, there are cases where defects occur due to moisture contained in the products.
The purpose of the present invention is to provide an inorganic substance-encapsulating cellulose particle having excellent low hygroscopicity and a method for producing the same.
Means for solving the problems
The invention comprises the following technical scheme.
[1] An inorganic-encapsulated cellulose particle characterized in that an inorganic substance is encapsulated in a cellulose particle comprising cellulose, the mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2, and the average particle diameter of the inorganic-encapsulated cellulose particle is 1 to 300 [ mu ] m.
[2] The cellulose particles containing an inorganic substance according to the above [1], which has a moisture absorption rate of 3% or less.
[3] The cellulose particles including an inorganic substance according to the above [1] or [2], wherein the refractive index of the inorganic substance is 1.43 to 2.00.
[4] The inorganic substance-encapsulating cellulose particle according to any one of the above [1] to [3], wherein the inorganic substance is surface-treated with at least one of a fatty acid and a silane compound.
[5] The inorganic substance-encapsulating cellulose particle according to any one of the above [1] to [4], wherein the mass ratio (inorganic substance/cellulose) is preferably 4/6 to 8/2, more preferably 6/4 to 8/2.
[6] The inorganic-encapsulated cellulose particles according to any one of the above [1] to [5], wherein the average particle diameter is preferably 1 to 150 μm, more preferably 1 to 100 μm.
[7] The cellulose particles including an inorganic substance according to any one of the above [1] to [6], wherein the inorganic substance is preferably at least one compound selected from the group consisting of calcium carbonate, calcium stearate, barium sulfate, talc, mica, kaolin, silica and alumina, more preferably at least one compound selected from the group consisting of calcium carbonate, calcium stearate, silica and talc, and still more preferably at least one compound selected from the group consisting of calcium carbonate and calcium stearate.
[8] A method for producing an inorganic-substance-encapsulating cellulose particle, characterized in that an inorganic-substance-encapsulating cellulose particle is produced by mixing a cellulose acetate solution in which cellulose acetate is dissolved in an organic solvent with the inorganic substance so that the mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2 to obtain a resin mixture, suspending the resin mixture in water to prepare a suspension in which the inorganic-substance-encapsulating cellulose acetate particle is dispersed in water, removing the organic solvent from the suspension, and saponifying the cellulose acetate particle.
[9] The method for producing inorganic-encapsulated cellulose particles according to the above [8], wherein the resin mixture is suspended in water in the presence of a suspension stabilizer and a surfactant.
[10] The method for producing inorganic-encapsulated cellulose particles according to the above [8] or [9], wherein the mass ratio (inorganic substance/cellulose) is preferably 4/6 to 8/2, more preferably 6/4 to 8/2.
[11] The method for producing an inorganic-encapsulated cellulose particle according to any one of the above [8] to [10], wherein the cellulose acetate solution and the inorganic substance are mixed so that the ratio of the inorganic substance to 100 parts by mass of the cellulose acetate is preferably 15 to 240 parts by mass, more preferably 40 to 240 parts by mass, and still more preferably 90 to 240 parts by mass.
[12] The method for producing cellulose particles containing an inorganic substance according to any one of [8] to [11], wherein the cellulose acetate is selected from monoacetylcellulose, diacetylcellulose, and triacetylcellulose.
[13] The method for producing inorganic-encapsulated cellulose particles according to any one of [8] to [12], wherein the organic solvent has an azeotropic point with water of 100 ℃ or lower at 1013 hPa.
[14] The method for producing inorganic-encapsulated cellulose particles according to any one of [8] to [13], wherein the organic solvent is preferably at least one solvent selected from the group consisting of: aromatic compounds such as toluene and benzene; ester compounds such as methyl acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone and methyl ethyl ketone; and saturated aliphatic hydrocarbons such as n-heptane, n-hexane, and n-octane.
[15] The method for producing inorganic-encapsulated cellulose particles according to any one of the above [8] to [14], wherein the resin mixture is suspended in water by suspending the resin mixture in an aqueous dispersion medium solution containing water, a suspension stabilizer and a surfactant.
Effects of the invention
According to the present invention, an inorganic substance-encapsulating cellulose particle having excellent low hygroscopicity and a method for producing the same can be provided.
Detailed Description
[ cellulose particles having an inorganic substance entrapped therein ]
The cellulose particles containing an inorganic substance of the present invention contain an inorganic substance in cellulose-containing cellulose particles. That is, the cellulose particles containing an inorganic substance therein contain cellulose and an inorganic substance. The cellulose particles containing an inorganic substance may further contain other components than cellulose and inorganic substances within a range not to impair the effects of the present invention. Examples of the other components include a trace amount of cellulose acetate, a suspension stabilizer, a surfactant, moisture, an organic filler, a pigment (inorganic substance is not included), a drug, and the like, but the other components are not limited to these examples.
In the present invention, "inorganic substance included" means that the inorganic substance is included in the interior of the cellulose particles. The inorganic substance may be contained in the entire cellulose particle, or a part of the inorganic substance may be exposed on the surface of the cellulose particle.
The state of "including an inorganic substance" can be confirmed by a method of visually observing the cross section of the particle or the surface of the particle with an optical microscope, a method of analyzing an image by a scanning electron microscope, or the like.
The "cellulose particle containing an inorganic substance" may be a particle in which a plurality of inorganic substance particles are contained in one cellulose particle, or may be a particle in which one inorganic substance particle is coated with cellulose. Further, a mixture of these forms of particles is also possible.
It should be noted that even when the cellulose particles including an inorganic substance and a small amount of cellulose particles not including an inorganic substance are mixed, the aggregate of the particles as a whole satisfies the requirements of the present invention and the effects of the present invention can be obtained, and the present invention is also included in the scope of the present invention. In this case, the amount of the cellulose particles not containing an inorganic substance is preferably 8% or less, and more preferably 5% or less.
The refractive index of the inorganic substance is preferably 1.43 to 2.00, more preferably 1.43 to 1.80, still more preferably 1.45 to 1.75, and particularly preferably 1.45 to 1.70. When the refractive index of the inorganic substance is within the above range, the transparency of the cellulose particles containing the inorganic substance can be maintained.
The refractive index of an inorganic substance was measured by irradiating the inorganic substance with sodium D-ray at 25 ℃ using an Abbe refractometer.
Examples of the inorganic substance having a refractive index within the above range include: calcium carbonate (refractive index: 1.50 to 1.69), calcium stearate (refractive index: 1.47), barium sulfate (refractive index: 1.64), talc (refractive index: 1.54 to 1.59), mica (refractive index: 1.53), kaolin (refractive index: 1.64), silica (refractive index: 1.44 to 1.50), alumina (refractive index: 1.76) and the like. Among these inorganic substances, calcium carbonate, calcium stearate, silica and talc are preferable, and calcium carbonate and calcium stearate are more preferable, from the viewpoint of easily maintaining the transparency of the cellulose particles encapsulating the inorganic substance.
The inorganic substance may be used alone or in combination of two or more.
The particle size of the inorganic substance is not particularly limited as long as the average particle size of the cellulose particles containing the inorganic substance is within the following range.
The inorganic substance is preferably surface-treated with at least one of a fatty acid and a silane compound (hereinafter, the fatty acid and the silane compound are also collectively referred to as "surface-treating agent"). When an inorganic substance is surface-treated with a surface treatment agent, the hydrophobicity of the surface of the inorganic substance is increased, and the inorganic substance is easily included in the following cellulose acetate particles.
In the present invention, "surface treatment" means that the surface of the inorganic substance is coated with a surface treatment agent.
The surface treatment agent includes fatty acids and silane compounds, and fatty acids are preferable from the viewpoint of easily encapsulating inorganic substances in cellulose acetate particles.
The surface treatment agent may be used alone or in combination of two or more.
The amount of the surface treatment agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 1 to 3 parts by mass, based on 100 parts by mass of the inorganic substance, in terms of the amount added.
Examples of the fatty acid include: saturated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and salts thereof; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, and ricinoleic acid, and salts thereof. Examples of the salt of a saturated fatty acid and an unsaturated fatty acid include: alkali metal salts and ammonium salts such as potassium salts and sodium salts.
Among these fatty acids, saturated fatty acids are preferable, and stearic acid is more preferable, from the viewpoint of facilitating inclusion of inorganic substances in the cellulose acetate particles.
One of the fatty acids may be used alone, or two or more of them may be used in combination.
Examples of the silane compound include: vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth) acryloyl group-containing silane coupling agents such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and 3- (meth) acryloyloxypropylmethyldiethoxysilane; amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane; epoxy group-containing silane coupling agents such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.
One kind of the silane compound may be used alone, or two or more kinds may be used in combination.
The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2, preferably 4/6 to 8/2, and more preferably 6/4 to 8/2. When the mass ratio is not less than the above lower limit, the low hygroscopicity of the cellulose particles containing an inorganic substance is improved. If the mass ratio is not less than the lower limit, the performance of the cellulose particles (wherein hygroscopicity is not included) can be more easily maintained.
The cellulose particles containing inorganic substances are generally spherical.
The average particle diameter of the inorganic substance-encapsulating cellulose particles is 1 to 300. Mu.m, preferably 1 to 150 μm, and more preferably 1 to 100. Mu.m. When the average particle diameter of the inorganic substance-encapsulating cellulose particles is within the above range, spherical inorganic substance-encapsulating cellulose particles tend to be easily produced.
The average particle diameter of the cellulose particles containing an inorganic substance is a volume-based average particle diameter (volume average particle diameter) measured by a laser diffraction particle size distribution meter. The average particle diameter is a median particle diameter (d 50).
The cellulose particles containing an inorganic substance of the present invention preferably have a moisture absorption rate of 3% or less, more preferably 2.5% or less, still more preferably 2% or less, and particularly preferably 1.5% or less, from the viewpoint of excellent low moisture absorption. The lower the moisture absorption rate, the more preferable it is, the lower the moisture absorption rate may be 0%.
The moisture absorption rate of the cellulose particles containing an inorganic substance can be determined as follows.
Cellulose particles (for example, 1g or more) containing an inorganic substance therein are dried at 110 ℃ for 15 hours, and then left in an environment with a humidity of 100% and a temperature of 85 ℃ to absorb moisture from the cellulose particles containing an inorganic substance therein. The inorganic substance-encapsulating cellulose particles were collected at the time when 2 hours had elapsed from the start of leaving, and the mass (W) of the inorganic substance-encapsulating cellulose particles after moisture absorption was measured 11 ). The inorganic substance-encapsulating cellulose particles whose mass was measured were dried at 110 ℃ for 2 hours, and the mass (W) of the dried inorganic substance-encapsulating cellulose particles was measured 12 ) The nonvolatile content (N) after 2 hours of moisture absorption was determined from the following formula (i) 1 ). Similarly, the inorganic substance-encapsulating cellulose particles were collected at the time when 168 hours had elapsed from the start of leaving, and the mass (W) of the inorganic substance-encapsulating cellulose particles after moisture absorption was measured 21 ). The inorganic substance-encapsulating cellulose particles whose mass was measured were dried at 110 ℃ for 2 hours, and the mass (W) of the inorganic substance-encapsulating cellulose particles after drying was measured 22 ) The nonvolatile content (N) after 168 hours of moisture absorption was determined from the following formula (ii) 2 ). The moisture absorption rate of the cellulose particles containing an inorganic substance was determined by the following formula (iii).
N 1 (mass%) = W 12 /W 11 ×100···(i)
N 2 (mass%) = W 22 /W 21 ×100···(ii)
Moisture absorption rate (%) = (N) 1 -N 2 )/N 2 ×100···(iii)
< method for producing cellulose particles containing inorganic substance >
An example of the method for producing cellulose particles containing an inorganic substance according to the present invention will be described below.
In the method for producing inorganic substance-encapsulated cellulose particles according to the present embodiment, a cellulose acetate solution in which cellulose acetate is dissolved in an organic solvent and an inorganic substance are mixed so that the mass ratio of the inorganic substance to cellulose (inorganic substance/cellulose) is 2/8 to 8/2 to obtain a resin mixture, the obtained resin mixture is suspended in water to prepare a suspension in which the inorganic substance-encapsulated cellulose acetate particles are dispersed in water, and the organic solvent is removed from the suspension to saponify the cellulose acetate particles, thereby producing inorganic substance-encapsulated cellulose particles in which the inorganic substance is encapsulated in the cellulose particles. After the cellulose acetate particles are saponified to produce inorganic substance-encapsulating cellulose particles, the inorganic substance-encapsulating cellulose particles can be dried by further removing water by solid-liquid separation.
The method for producing cellulose particles including an inorganic substance according to the present embodiment may be said to include the following steps (a) to (d), and may be said to further include the following step (e) in addition to the steps (a) to (d).
Step (a): and a step of mixing a cellulose acetate solution in which cellulose acetate is dissolved in an organic solvent with an inorganic substance to prepare a resin mixture.
A step (b): and a step of suspending the resin mixture in water to prepare a suspension in which the cellulose acetate particles containing an inorganic substance are dispersed in water.
A step (c): and removing the organic solvent from the suspension.
Step (d): and saponifying the cellulose acetate particles to obtain inorganic substance-containing cellulose particles in which the cellulose particles contain an inorganic substance.
A step (e): and (d) removing water from the saponified aqueous dispersion obtained in step (d) to dry the inorganic substance-encapsulated cellulose particles.
In the step (a), the cellulose acetate solution and the inorganic substance are mixed so that the mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) is 2/8 to 8/2, preferably 4/6 to 8/2, more preferably 6/4 to 8/2.
The cellulose acetate solution and the inorganic substance are preferably mixed so that the ratio of the inorganic substance is 15 to 240 parts by mass with respect to 100 parts by mass of cellulose acetate. The proportion of the inorganic substance is more preferably 40 to 240 parts by mass, and still more preferably 90 to 240 parts by mass, relative to 100 parts by mass of cellulose acetate.
In the step (b), the resin mixture obtained in the step (a) is suspended in water to prepare a suspension in which the cellulose acetate particles containing an inorganic substance are dispersed in water. Since cellulose acetate is dissolved in an organic solvent in the resin mixture, when the resin mixture is suspended in water, the resin mixture becomes an oil component and is dispersed in water to form oil droplets, thereby obtaining a suspension in which cellulose acetate particles containing an inorganic substance are dispersed in water.
In the cellulose acetate, the degree of substitution of acetyl groups, the acetylation rate, and the like are not particularly limited.
Examples of the cellulose acetate include: monoacetylcellulose, diacetylcellulose, triacetylcellulose, and the like.
The viscosity of the cellulose acetate solution is not particularly limited, but is preferably 500 to 300000 mPas, more preferably 2000 to 100000 mPas. Here, the viscosity is a value measured at a temperature of 25 ℃ using a BL type rotational viscometer (for example, "RB-85L" manufactured by Toyobo industries Co., ltd.).
The cellulose acetate may be used alone or in combination of two or more.
The organic solvent used in the step (a) is not particularly limited as long as it is a compound capable of dissolving cellulose acetate. However, the organic solvent is preferably an organic solvent having low solubility in water. The organic solvent is preferably an organic solvent having an azeotropic point with water of 100 ℃ or lower at 1013 hPa.
Examples of the organic solvent having an azeotropic point with water of 100 ℃ or lower at 1013hPa include: aromatic compounds such as toluene and benzene; ester compounds such as methyl acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone and methylethyl ester; saturated aliphatic hydrocarbons such as n-heptane, n-hexane, and n-octane.
One kind of the organic solvent may be used alone, or two or more kinds may be used in combination.
The concentration of the cellulose acetate solution is not particularly limited, but is preferably 4 to 40 mass%, more preferably 8 to 16 mass%.
In the method for producing cellulose particles containing an inorganic substance in accordance with the present embodiment, it is preferable that the resin mixture is suspended in water in the presence of a suspension stabilizer. The suspension stabilizer may be added in advance to water as a dispersion medium, for example. When the dispersion medium is water and further contains a suspension stabilizer, the suspension state tends to be stabilized, and the cellulose particles containing the inorganic substance can be produced more easily.
Examples of the suspension stabilizer include: cellulose-based water-soluble resins (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, etc.), polyvinyl alcohol, polyacrylates, polyethylene glycol, polyvinyl pyrrolidone, polyacrylamide, and phosphoric acid triesters. In the case where a cellulose-based water-soluble resin is used as the suspension stabilizer, it is removed together with water in the step (e), and therefore the inorganic substance/cellulose ratio of the finally obtained inorganic substance-encapsulating cellulose particles is not affected.
The suspension stabilizer may be used alone or in combination of two or more.
In the method for producing cellulose particles containing an inorganic substance according to the present embodiment, it is preferable that the resin mixture is suspended in water in the presence of a surfactant. The surfactant may be added to water as a dispersion medium in advance, for example. When the dispersion medium further contains a surfactant in water, the suspension state tends to be stabilized, and the cellulose particles containing inorganic substances can be produced more easily.
The surfactant is not particularly limited, and known anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used.
One kind of surfactant may be used alone, or two or more kinds may be used in combination.
In the step (b), it is preferable that: an aqueous dispersion medium solution is prepared in advance, and the resin mixture is suspended in the aqueous dispersion medium solution to obtain a suspension in which the cellulose acetate particles including the inorganic substance are dispersed in water. When the aqueous dispersion medium solution and the resin mixed solution are mixed, they may be stirred, for example, by a stirrer.
The aqueous dispersion medium preferably contains water, the suspension stabilizer and the surfactant.
The content of the suspension stabilizer in the aqueous dispersion medium solution is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, still more preferably 0.3 to 7 parts by mass, and particularly preferably 0.4 to 5 parts by mass, relative to 100 parts by mass of water. When the content of the suspension stabilizer is not less than the lower limit, the suspension state of the cellulose acetate particles and the inorganic substance in the production process is easily stabilized, and the cellulose particles containing the inorganic substance can be produced more easily. If the content of the suspension stabilizer is not more than the upper limit, the viscosity of the suspension does not become too high, and problems such as winding of the suspension around the shaft of the manufacturing machine do not easily occur, and granulation is easy.
The content of the surfactant in the aqueous dispersion medium solution is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, still more preferably 0.02 to 1.5 parts by mass, and particularly preferably 0.03 to 0.5 parts by mass, based on 100 parts by mass of water. When the content of the surfactant in the aqueous dispersion medium is not less than the lower limit, the suspension state of the cellulose acetate particles in the production process is easily stabilized, and the cellulose particles containing the inorganic substance can be produced more easily. When the content of the surfactant in the aqueous dispersion medium is not more than the upper limit, foaming of the suspension by stirring is less likely to occur, and cellulose particles including an inorganic substance are more easily produced.
In the step (c), the organic solvent is removed from the suspension. It is considered that the cellulose acetate particles containing the inorganic substance in the suspension and the organic solvent are dispersed in water as an oil component. Therefore, by removing the organic solvent from the suspension in the step (c), an aqueous dispersion in which the cellulose acetate particles containing the inorganic substance are dispersed in water can be obtained.
In the step (c), the organic solvent is preferably removed by heating the suspension in which the cellulose acetate particles containing the inorganic substance are dispersed to a temperature equal to or higher than the azeotropic point of the organic solvent and water. By heating to the azeotropic point of the organic solvent and water or higher in the step (c), the organic solvent can be sufficiently removed, and the amount of the organic solvent remaining in the cellulose particles can be reduced to an extremely low level. The heating temperature is preferably 100 ℃ or lower at 1013 hPa. Here, the cellulose acetate particles containing an inorganic substance are in the form of a slurry dispersed in water. When the heating temperature of the cellulose acetate particles is made to exceed 100 ℃, water is also volatilized together with the organic solvent and removed, and therefore there is a possibility that the cellulose acetate particles are fused with each other.
In the step (d), the inorganic substance-containing cellulose particles are produced by saponifying the inorganic substance-containing cellulose acetate particles to thereby produce inorganic substance-containing cellulose particles in which the inorganic substance is contained in the cellulose particles. The saponification reaction can be carried out, for example, by: an aqueous dispersion of cellulose acetate particles containing an inorganic substance dispersed in water is mixed with an alkaline compound and heated as necessary.
The basic compound used for saponification is not particularly limited, and examples thereof include: sodium hydroxide, potassium hydroxide, ammonia, triethylamine, and the like.
One kind of the basic compound may be used alone, or two or more kinds may be used in combination.
The reaction time of the saponification reaction is preferably 1.5 to 4 hours, more preferably 2 to 3 hours. When the reaction time of the saponification reaction is not less than the lower limit, deacetylation is easily sufficiently progressed, and acetic acid odor of the inorganic substance-containing cellulose particles is easily reduced. If the reaction time of the saponification reaction is not more than the upper limit, the time required for one production process can be shortened, and the production efficiency can be improved.
The reaction temperature of the saponification reaction is preferably 90 to 100 ℃, more preferably 93 to 98 ℃. When the reaction temperature of the saponification reaction is not lower than the lower limit value, deacetylation is easily sufficiently performed, and the acetic acid odor of the cellulose particles encapsulating the inorganic substance is easily reduced. If the reaction temperature of the saponification reaction is not higher than the upper limit, the reaction solution (aqueous dispersion of cellulose acetate particles containing an inorganic substance) tends not to be excessively heated, and the cellulose particles containing an inorganic substance can be produced more easily at a lower cost.
When the basic compound has a hydroxyl group, the amount of the hydroxyl group in the basic compound is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol%, based on 100 mol% of the acetyl group in the cellulose acetate. When the amount of the substance of the hydroxyl group in the basic compound is not less than the lower limit, the deacetylation is easily sufficiently advanced, and the acetic acid odor of the cellulose particles containing the inorganic substance is easily reduced. When the amount of the hydroxyl group in the basic compound is not more than the above upper limit, the alkali compound does not need to be used in excess, and the cellulose acetate particles containing an inorganic substance can be produced more easily at a lower cost.
In the step (e), water is removed from the saponified aqueous dispersion obtained in the step (d), and the cellulose particles containing the inorganic substance therein are dried. The method for removing water from the aqueous dispersion after saponification is not particularly limited, and for example, a method for removing water by solid-liquid separation is preferable. The time and temperature for the solid-liquid separation can be appropriately set according to the use of the cellulose particles containing the inorganic substance encapsulated therein.
The details and preferred embodiments of the inorganic-encapsulated cellulose particles obtained by the method for producing inorganic-encapsulated cellulose particles according to the present embodiment may be the same as those described in the above-mentioned "inorganic-encapsulated cellulose particles".
< Effect >
The inorganic substance-containing cellulose particles of the present invention described above contain an inorganic substance in the cellulose particles, and thus have excellent low hygroscopicity.
Further, according to the method for producing an inorganic substance-encapsulating cellulose particle of the present invention, an inorganic substance-encapsulating cellulose particle having excellent low hygroscopicity can be easily produced.
< use >
The inorganic substance-encapsulating cellulose particles according to the present invention can be used as microbeads for use in paints, plastics, adhesives, cosmetics, paper coating materials, fiber processing materials, writing instruments, fillers for markers, and the like.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following descriptions.
[ measurement method ]
< measurement of refractive index >
The refractive index of an inorganic substance was measured by irradiating the inorganic substance with sodium D rays in an environment of 25 ℃ using an abbe refractometer ("model 1T" manufactured by ATAGO co.
< measurement of volume average particle diameter >
The volume average particle diameter of the cellulose particles containing an inorganic substance was measured using a laser diffraction particle size distribution analyzer ("SALD 2100" manufactured by Shimadzu corporation).
< measurement of moisture absorption >
The moisture absorption rate of the cellulose particles containing an inorganic substance can be determined as follows.
The cellulose particles containing an inorganic substance encapsulated therein were dried at 110 ℃ for 15 hours, and then left to stand in an environment with a humidity of 100% and a temperature of 85 ℃ to absorb moisture. The inorganic substance-encapsulating cellulose particles were collected at a time when 2 hours had elapsed from the start of leaving, and the mass (W) of the inorganic substance-encapsulating cellulose particles after moisture absorption was measured 11 ). The inorganic substance-encapsulating cellulose particles whose mass was measured were dried at 110 ℃ for 2 hours, and the mass (W) of the inorganic substance-encapsulating cellulose particles after drying was measured 12 ) The nonvolatile content (N) after 2 hours of moisture absorption was determined from the following formula (i) 1 ). Similarly, the inorganic substance-encapsulating cellulose particles were collected at the time when 168 hours had elapsed since the start of the standing, and the mass (W) of the inorganic substance-encapsulating cellulose particles after moisture absorption was measured 21 ). The inorganic substance-encapsulating cellulose particles whose mass was measured were dried at 110 ℃ for 2 hours, and the mass (W) of the dried inorganic substance-encapsulating cellulose particles was measured 22 ) The nonvolatile content (N) after 168 hours of moisture absorption was determined from the following formula (ii) 2 ). The moisture absorption rate of the cellulose particles encapsulating the inorganic substance was determined by the following formula (iii).
N 1 (mass%) = W 12 /W 11 ×100···(i)
N 2 (mass%) = W 22 /W 21 ×100···(ii)
Moisture absorption rate (%) = (N) 1 -N 2 )/N 2 ×100···(iii)
[ example 1]
In a 2L separable flask equipped with a stirrer, 500g of water was charged, and 12g of hydroxypropylmethylcellulose (equivalent to 2.4 parts by mass relative to 100 parts by mass of water) and 0.5g of sodium lauryl sulfate (equivalent to 0.1 part by mass relative to 100 parts by mass of water) were dissolved to prepare an aqueous dispersion medium solution.
A2L separable flask equipped with a stirrer was additionally charged with 600g of ethyl acetate, and 90g of cellulose acetate (acetylation rate: 55%) was dissolved therein to prepare a cellulose acetate solution. The obtained cellulose acetate solution (690 g) and calcium carbonate (manufactured by Fimatec ltd., AFF-STF having a refractive index of about 1.7) 200g (corresponding to 222.2 parts by mass per 100 parts by mass of cellulose acetate) as an inorganic material, which was surface-treated with stearic acid, were mixed to prepare a resin mixture solution.
The resin mixture is added to the aqueous dispersion medium to prepare a suspension. Then, the suspension was heated to 90 ℃ while stirring at 300rpm of the stirrer, and the ethyl acetate was evaporated from the suspension by heating at 90 ℃ for 2 hours. Then, the temperature was raised to 95 ℃, 35g of sodium hydroxide was added thereto, and the mixture was held for 1.5 hours to remove acetyl groups from the cellulose acetate particles, thereby obtaining inorganic substance-encapsulated cellulose particles in which inorganic substances are encapsulated in the cellulose particles. Thus, a slurry in which the cellulose particles containing the inorganic substance are dispersed in water is obtained.
Next, the slurry was cooled to room temperature, and then solid-liquid separation was performed by filtration, and the recovered solid matter was sufficiently washed with water and then dried at 70 ℃ for 20 hours to obtain spherical inorganic substance-encapsulated cellulose particles.
The volume average particle diameter and the moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
[ example 2]
In the same manner as in example 1, an aqueous dispersion medium solution was prepared.
A2L separable flask equipped with a stirrer was further charged with 700g of ethyl acetate, and 90g of cellulose acetate (acetylation rate: 55%) was dissolved therein to prepare a cellulose acetate solution. The obtained cellulose acetate solution 790g and calcium carbonate (fmatec ltd., manufactured "AFF-STF", refractive index: about 1.7) 90g (corresponding to 100 parts by mass per 100 parts by mass of cellulose acetate) as an inorganic substance, which was surface-treated with stearic acid, were mixed to prepare a resin mixture.
A spherical cellulose particle including an inorganic substance was obtained in the same manner as in example 1, except that the obtained aqueous dispersion medium solution and the resin mixed solution were used.
The volume average particle diameter and moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
[ example 3]
In the same manner as in example 1, an aqueous dispersion medium solution was prepared.
A2L separable flask equipped with a stirrer was additionally charged with 750g of ethyl acetate, and 90g of cellulose acetate (acetylation rate: 55%) was dissolved therein to prepare a cellulose acetate solution. The obtained cellulose acetate solution 840g and calcium carbonate (fmatec ltd., manufactured "AFF-STF", refractive index: about 1.7) as an inorganic material, which was surface-treated with stearic acid, 40g (corresponding to 44.4 parts by mass per 100 parts by mass of cellulose acetate) were mixed to prepare a resin mixture.
A spherical inorganic substance-encapsulating cellulose particle was obtained in the same manner as in example 1, except that the obtained aqueous dispersion medium solution and the resin mixed solution were used.
The volume average particle diameter and the moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
[ example 4]
500g of water was charged into a 2L separable flask equipped with a stirrer, and 6g of polyvinyl alcohol (equivalent to 1.2 parts by mass relative to 100 parts by mass of water) and 0.5g of sodium lauryl sulfate (equivalent to 0.1 part by mass relative to 100 parts by mass of water) were dissolved therein to prepare an aqueous dispersion medium solution.
Separately, a resin mixture was prepared in the same manner as in example 1.
A spherical cellulose particle including an inorganic substance was obtained in the same manner as in example 1, except that the obtained aqueous dispersion medium solution and the resin mixed solution were used.
The volume average particle diameter and the moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
[ example 5]
500g of water was charged into a 2L separable flask equipped with a stirrer, and 3g of hydroxypropylmethylcellulose (equivalent to 0.6 part by mass relative to 100 parts by mass of water) and 0.2g of sodium lauryl sulfate (equivalent to 0.04 part by mass relative to 100 parts by mass of water) were dissolved therein to prepare an aqueous dispersion medium solution.
Separately, a resin mixture was prepared in the same manner as in example 1.
A spherical inorganic substance-encapsulating cellulose particle was obtained in the same manner as in example 1, except that the obtained aqueous dispersion medium solution and the resin mixed solution were used.
The volume average particle diameter and the moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
[ example 6]
In the same manner as in example 1, an aqueous dispersion medium solution was prepared.
A2L separable flask equipped with a stirrer was additionally charged with 750g of ethyl acetate, and 90g of cellulose acetate (acetylation rate: 55%) was dissolved therein to prepare a cellulose acetate solution. The obtained cellulose acetate solution 840g and inorganic substance using stearic acid surface treatment of calcium stearate ("Na chemical industry Co., ltd." calcium stearate ", refractive index: about 1.5) 30g (corresponding to 100 parts by weight of cellulose acetate is 33.3 parts by weight) were mixed to prepare a resin mixture.
A spherical inorganic substance-encapsulating cellulose particle was obtained in the same manner as in example 1, except that the obtained aqueous dispersion medium solution and the resin mixed solution were used.
The volume average particle diameter and the moisture absorption rate of the obtained inorganic substance-encapsulating cellulose particles were measured. The results are shown in Table 1. The mass ratio of the inorganic substance to the cellulose (inorganic substance/cellulose) in the inorganic substance-encapsulated cellulose particles is shown in table 1.
Comparative example 1
In a 2L separable flask equipped with a stirrer, 500g of water was charged, and 10g of hydroxypropylmethylcellulose (equivalent to 2 parts by mass with respect to 100 parts by mass of water) and 2g of sodium lauryl sulfate (equivalent to 0.4 part by mass with respect to 100 parts by mass of water) were dissolved to prepare an aqueous dispersion medium solution.
A2L separable flask equipped with a stirrer was additionally charged with 1000g of ethyl acetate, and 250g of cellulose acetate (acetylation rate: 55%) was dissolved therein to prepare a cellulose acetate solution. The cellulose acetate solution obtained is also referred to as a resin mixture solution in comparative example 1.
The aqueous dispersion medium solution is added to the cellulose acetate solution to prepare a suspension. Then, the suspension was heated to 90 ℃ while stirring at 300rpm of the stirrer, and the ethyl acetate was evaporated from the suspension by heating at 90 ℃ for 2 hours. Then, the temperature was raised to 95 ℃, 95g of sodium hydroxide was added thereto, and the mixture was held for 1.5 hours to remove acetyl groups from the cellulose acetate particles, thereby obtaining cellulose particles. Thus, a slurry having cellulose particles dispersed in water was obtained.
Then, the slurry was cooled to room temperature, and then solid-liquid separation was performed by filtration, and the recovered solid matter was sufficiently washed with water and then dried at 70 ℃ for 20 hours to obtain spherical cellulose particles.
The volume average particle diameter and the moisture absorption rate of the obtained cellulose particles were measured. The results are shown in Table 1.
[ Table 1]
Abbreviations in table 1 are as follows.
HPMC: hydroxypropyl methylcellulose.
PVA: polyvinyl alcohol.
As is clear from table 1, the cellulose particles encapsulating the inorganic substance obtained in each example had a low moisture absorption rate and were excellent in low moisture absorption.
On the other hand, cellulose particles not containing an inorganic substance had a high moisture absorption rate and were inferior to cellulose particles containing an inorganic substance obtained in each example in low moisture absorption.
Claims (6)
1. Cellulose particles containing an inorganic substance encapsulated therein, characterized in that the cellulose particles containing cellulose are encapsulated with an inorganic substance,
the mass ratio of the inorganic substance to the cellulose, i.e., inorganic substance/cellulose, is 2/8 to 8/2,
the average particle diameter of the inorganic substance-encapsulating cellulose particles is 1 to 300 [ mu ] m.
2. The cellulose particles containing an inorganic substance according to claim 1, having a moisture absorption rate of 3% or less.
3. The inorganic substance-encapsulating cellulose particle according to claim 1 or 2, wherein the refractive index of the inorganic substance is 1.43 to 2.00.
4. The inorganic substance-encapsulating cellulose particle according to any one of claims 1 to 3, wherein the inorganic substance is surface-treated with at least one of a fatty acid and a silane compound.
5. A method for producing an inorganic substance-containing cellulose particle, characterized in that the method for producing an inorganic substance-containing cellulose particle according to any one of claims 1 to 4,
mixing a cellulose acetate solution in which cellulose acetate is dissolved in an organic solvent with the inorganic substance so that the mass ratio of the inorganic substance to the cellulose, i.e., inorganic substance/cellulose, is 2/8 to 8/2 to obtain a resin mixture, suspending the resin mixture in water to prepare a suspension in which cellulose acetate particles containing the inorganic substance are dispersed in water,
removing the organic solvent from the suspension,
and saponifying the cellulose acetate particles to produce inorganic substance-containing cellulose particles in which the inorganic substance is contained in the cellulose particles.
6. The method for producing cellulose particles containing an inorganic substance according to claim 5, wherein the resin mixture is suspended in water in the presence of a suspension stabilizer and a surfactant.
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| JPH0730203B2 (en) * | 1986-09-27 | 1995-04-05 | ダイセル化学工業株式会社 | Method for producing cellulose particles |
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