WO2010109582A1 - Porous hollow polymer particle, method for producing porous hollow polymer particle, fragrance material-carrying polymer particle, and method for producing fragrance material-carrying polymer particle - Google Patents

Abstract

Disclosed is a porous hollow polymer particle which excels in extended release of fragrance material, light diffusion, liquid absorption, sensibility, solvent resistance and mechanical strength. Also disclosed are a fragrance material-carrying polymer particle which can stably carry fragrance material, while having excellent extended release of the fragrance material; a method for producing a porous hollow polymer particle; and a method for producing a fragrance material-carrying polymer particle. The porous hollow polymer particle has a plurality of pores in the internal portion of the particle, and the outer surface and the inner surface of the particle are coated with a polyvinyl alcohol.

Description

Porous hollow polymer particle, method for producing porous hollow polymer particle, perfume-carrying polymer particle, and method for producing perfume-carrying polymer particle

The present invention relates to a porous hollow polymer particle excellent in sustained release property, light diffusibility, liquid absorbency, body sensibility, solvent resistance and mechanical strength of a fragrance. The present invention also relates to a perfume-carrying polymer particle that can stably carry a perfume and is excellent in sustained release of the perfume. Furthermore, it is related with the manufacturing method of this porous hollow polymer particle, and the manufacturing method of this fragrance | flavor carrying | support polymer particle.

Conventionally, hollow polymer particles having voids inside the particles have been used in a very wide range of fields for the purpose of reducing the weight of the material, making pores, and providing heat insulation, sound insulation, impact resistance, and the like.
The hollow polymer particles are known to scatter visible light due to a difference in refractive index between the resin layer and the internal void layer, and are used as a light diffusing agent. Such light diffusing agents are fluorescent, white light illumination covers, backlit translucent signs, displays, lighting, interior translucent partitions, as well as liquid crystal displays, liquid crystal television light diffusing sheets and light diffusing plates, It is used in many fields such as projectors and projection TV screens.

In particular, when used for a light diffusing sheet or a light diffusing plate, the light diffusing agent is required to have a high total light transmittance and an excellent light diffusibility. On the other hand, Patent Document 1 describes that a coating material excellent in opacity and whiteness can be obtained by using hollow polymer particles having a particle size of submicron as a light scattering agent. However, when conventional hollow polymer particles are used as a light diffusing agent, there is a problem that the luminance distribution varies due to the difference in angle with respect to the light exit surface. Further, there are problems in terms of solvent resistance and particle strength of the hollow polymer particles, and it has been difficult to ensure stable light scattering performance.

In addition, the hollow polymer particles are also used for paste compositions such as paints, inks, adhesives, etc. for the purpose of weight reduction, pore formation, heat insulation, sound insulation, impact resistance, etc. For example, Patent Document 2 discloses a method for forming a heat insulating coating film that can exhibit stable heat insulating performance over a long period of time by adding hollow polymer particles.
However, the conventional hollow polymer particles have a drawback that they are weak in solvent resistance and strength, and many of them are destroyed during the kneading process with the paint. Furthermore, the hollow polymer particles have a large buoyancy, and when blended in a solvent such as water or an organic solvent, it has been difficult to uniformly disperse them in the paint.

Conventionally, a sustained-release perfume carrying agent that maintains aroma by supporting various fragrances on a support and releasing the fragrances has been proposed. As such a sustained-release fragrance carrier, for example, in Patent Document 3, a fragrance is contained in a biodegradable resin having a predetermined molecular weight and made of a random or block copolymerized polyester by melt kneading, dipping, or the like. A perfume-containing sustained release biodegradable resin composition is disclosed. Patent Document 4 discloses a sustained-release fragrance in which a liquid fragrance and a hydrophobic substance are kneaded in the pores of a hydrophilic porous body and occluded in the pores.
Further, Patent Document 5 discloses sustained-release perfume-carrying resin particles in which liquid perfume is carried on the surface layer and / or supported resin particles having an OH group inside.
However, in the method of Patent Document 3, there is a problem that the release of the fragrance is extremely slow, or the fragrance existing inside is not released, and the release stops midway.
Further, even with the methods of Patent Document 4 and Patent Document 5, the amount of the fragrance carried is insufficient, or the fragrance cannot be released at a constant rate over a long period of time. There was a problem that it was reduced over time.
JP 05-170802 A JP 2004-000940 A Japanese Patent Laid-Open No. 11-106629 JP-A-10-17846 Japanese Patent Laid-Open No. 2003-15596

An object of this invention is to provide the porous hollow polymer particle which is excellent in the sustained release property of a fragrance | flavor, light diffusibility, liquid absorptivity, body sensibility, solvent resistance, and mechanical strength. It is another object of the present invention to provide a fragrance-carrying polymer particle that can stably carry a fragrance and has excellent sustained release of the fragrance. Furthermore, it aims at providing the manufacturing method of this porous hollow polymer particle, and the manufacturing method of this fragrance | flavor carrying | support polymer particle.

The present invention is a porous hollow polymer particle having a plurality of pores inside the particle, the outer surface of the particle and the inner surface of the particle being coated with polyvinyl alcohol.
Hereinafter, the present invention will be described in more detail.

The material of the particle main body of the porous hollow polymer particle of the present invention is not particularly limited, but a polymer obtained by polymerizing a monofunctional monomer or a polyfunctional monomer is preferable.

The monofunctional monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cumyl (meth) acrylate, cyclohexyl (meth) acrylate , Myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, alkyl (meth) acrylate such as isobornyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, glycidyl ( Polar group-containing (meth) acrylic monomers such as (meth) acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, p-alkyl Aromatic vinyl monomers such as styrene, vinyl esters such as vinyl acetate and vinyl propionate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, vinyl pyridine, 2-acryloyloxyethyl phthalic acid, itaconic acid, fumaric acid, ethylene, propylene Etc. These may be used alone or in combination of two or more.
Among these, highly transparent porous hollow polymer particles are obtained, and it is difficult to generate soot and ash during firing. Therefore, it is preferable to use an acrylic monomer, and more preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, (meta ) Acrylic acid.

The polyfunctional monomer is not particularly limited, and examples thereof include di (meth) acrylate, tri (meth) acrylate, diallyl compound, triallyl compound, and vinyl compound. These may be used alone or in combination of two or more.
Shrinkage of the porous hollow polymer particles obtained by using the polyfunctional monomer is suppressed, and the compression resistance is improved.

Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and trimethylolpropane. Examples include di (meth) acrylate.
Examples of the tri (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

Examples of the diallyl compound or triallyl compound include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, diallyl succinate, triallyl isocyanurate, and the like. It is done.
Examples of the divinyl compound include divinylbenzene and butadiene.

In the porous hollow polymer particle of the present invention, the outer surface of the particle and the inner surface of the particle are coated with polyvinyl alcohol. Thereby, the liquid absorptivity of the porous hollow polymer particles is greatly improved. In the present invention, the particle outer surface refers to the surface facing the outside of the porous hollow polymer particle, and the particle inner surface refers to a plurality of pores formed inside the porous hollow polymer particle. The surface that faces.

As the polyvinyl alcohol, it is preferable to use partially saponified polyvinyl alcohol.

The preferable lower limit of the saponification degree of the partially saponified polyvinyl alcohol is 68 mol%, and the preferable upper limit is 99 mol%. When the saponification degree is less than 68 mol%, it may be difficult to stably polymerize the polymerizable monomer. When the saponification degree exceeds 99 mol%, the polarity of the dispersion stabilizer becomes too high, The liquid absorptivity of the obtained porous hollow polymer particles may be lowered. A more preferred lower limit of the degree of saponification is 74 mol%, and a more preferred upper limit is 96 mol%.

The preferable lower limit of the average degree of polymerization of the polyvinyl alcohol is 200, and the preferable upper limit is 3000. When the average degree of polymerization is less than 200, the crosslink density of polyvinyl alcohol covering the outer surface of the particle and the inner surface of the particle becomes high, so that the liquid absorbency may be lowered. When the average degree of polymerization exceeds 3000, Polymerization may be difficult.

The porous hollow polymer particles of the present invention have a preferable lower limit of the average particle diameter of 10 μm and a preferable upper limit of 100 μm. When the average particle size is less than 10 μm, for example, when used as a light diffusing agent, a sufficient light diffusing effect cannot be obtained, and when used at the time of perfume, sufficient liquid absorptivity cannot be obtained. There is. When the average particle size exceeds 100 μm, sufficient body sensibility may not be improved. In addition, when used in perfume, sufficient fragrance effects may not be obtained. A more preferable lower limit of the average particle diameter is 15 μm, and a more preferable upper limit is 70 μm.

In the porous hollow polymer particles of the present invention, the preferable lower limit of the CV value of the particle diameter is 15%, and the preferable upper limit is 35%. By being within the above range, for example, when used in a light diffusing agent, a high light diffusion effect is obtained, and when used in a paste composition or the like, sufficient body sensibility and coating properties are obtained. If the CV value is less than 15%, the productivity may decrease, and if the CV value exceeds 35%, sufficient body sensibility and coatability may not be obtained. A more preferable lower limit of the CV value is 20%, and a more preferable upper limit is 35%.
In addition, in this specification, CV value is a numerical value calculated | required by following formula (1).
CV value of particle diameter (%) = (σ2 / Dn2) × 100 (1)
In formula (1), σ2 represents the standard deviation of the particle diameter, and Dn2 represents the number average particle diameter.

In the porous hollow polymer particles of the present invention, the preferable lower limit of the porosity is 20%, and the preferable upper limit is 80%. When the porosity is less than 20%, for example, when used for perfume-carrying polymer particles, the amount of perfume carried becomes insufficient, and when used for a light diffusing agent, a sufficient light diffusion effect cannot be obtained, Furthermore, when used in a paste composition or the like, liquid absorbency may not be obtained. When the porosity exceeds 80%, the strength at the time of handling may be insufficient and the particles may be destroyed. A more preferable lower limit of the porosity is 30%, and a more preferable upper limit is 70%.
In the present specification, the porosity is a percentage (%) of the volume of the hollow portion occupied in the entire volume of the porous hollow polymer particles. For example, an enclosed mercury pressure of 2000 kg using an AMCO Porosimeter 2000 is used. It can be measured under the condition of / cm ² .

The porous hollow polymer particles of the present invention preferably have a preferred lower limit of 1.0 of the ratio (D1 / D0) between the particle diameter D1 after immersion in a solvent at 25 ° C. for 24 hours and the particle diameter D0 before immersion. A preferred upper limit is 1.5. When the D1 / D0 is less than 1.0, for example, when used in a paste composition or the like, it may dissolve in a solvent and may not fully exhibit a desired function, and the D1 / D0 exceeds 1.5. In addition, since it swells too much in the solvent, the structure of the particles cannot be maintained when used in a paste composition or the like.
Examples of the solvent include alcohols such as methanol, ethanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylformaldehyde, tetrahydrofuran, toluene, xylene and ethanol / toluene mixed solvent = 50% / 50% is used.

In the porous hollow polymer particles of the present invention, the preferable upper limit of the average value of the ratio (d / D) of the pore diameter (d) to the outer diameter (D) is 0.3. When the above d / D exceeds 0.3, the number of pores present inside the particle decreases, and a sufficient light diffusion effect may not be obtained particularly when used as a light diffusing agent.
Note that the above d / D is determined in a direction parallel to the reference axis for 20 porous hollow polymer particles that are arbitrarily selected using an electron microscope with an axis in one arbitrary direction as a reference axis. The maximum value of the width is measured as the outer diameter, the pore diameter of the one having the largest pore width in the direction parallel to the reference axis is measured, and the measured outer diameter (D) and pore diameter (d) From the above, the pore diameter / outer diameter (d / D) is calculated. And it can obtain | require by calculating the arithmetic average of the pore diameter / outer diameter (d / D) of the measured 20 porous hollow polymer particles.

Since the porous hollow polymer particle of the present invention has high liquid absorbability, it can be suitably used as a perfume-carrying polymer particle carrying a perfume. The use as the perfume-carrying polymer particles will be described in detail later.

Since the porous hollow polymer particles of the present invention have excellent light diffusibility, the luminance distribution does not vary due to the difference in angle with respect to the light exit surface, and can correspond to any angle, A light diffusing agent having high particle strength and capable of ensuring stable light scattering performance is obtained. Therefore, the porous hollow polymer particles of the present invention can be used for light diffusing agents such as light diffusing agents for liquid crystals, matting agents, surface treatment agents, and additives for resin moldings.

In addition, since the porous hollow polymer particles of the present invention have high liquid absorbency, in the step of mixing the porous hollow polymer particles and the solvent, etc., the viscosity is low, and stirring and mixing are easy. In the coating step, since the solvent is absorbed inside the porous hollow polymer particles, the viscosity can be increased to a desired viscosity. Since the viscosity can be changed in each step as described above, the ink, paint, adhesive, matting agent, column filler, abrasive, fluidity control agent, water-based ink, water-based paint, coating agent, It can be used for paste composition applications such as filters.
Furthermore, using such liquid absorbency, diapers, napkins, agricultural and horticultural water retention agents, industrial water retention agents, hygroscopic agents, dehumidifying agents, building materials and other water absorption and oil absorption composition applications, sustained release It can be used for agricultural chemicals, medicines, antistatic agents and the like.
In addition, since the porous hollow polymer particles of the present invention have a high body sensation improving effect, cosmetics such as foundation, white powder, blusher, eye shadow, body powder, baby powder, pre-shave lotion, body lotion, lotion and the like were included. It can be used as a body sensitivity improving composition.
Especially, it is preferable to use the porous hollow polymer particle of this invention for a fragrance | flavor carrying | support polymer particle, a light-diffusion agent, and a paste composition.

The porous hollow polymer particles of the present invention include, for example, a step of mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution, the polymerizable monomer solution, and polyvinyl alcohol. And a dispersion stabilizer comprising the following: a step of adding a suspension to a polar solvent and suspending the dispersion stabilizer, and a step of polymerizing the polymerizable monomer. A method for producing such porous hollow polymer particles is also one aspect of the present invention.

In the method for producing porous hollow polymer particles of the present invention, first, a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer are mixed to prepare a polymerizable monomer solution.

As the polymerization monomer, for example, a monofunctional monomer or a polyfunctional monomer can be used. In addition, about the said monofunctional monomer and the said polyfunctional monomer, since it is the structure similar to the porous hollow polymer particle of this invention, the detailed description is abbreviate | omitted.

The organic solvent that does not react with the polymerizable monomer is appropriately selected from those that are not compatible with a polar solvent such as water as a polymerization medium, and the type is not particularly limited. For example, butane, pentane, hexane, heptane, Examples include cyclohexane, toluene, xylene, ethyl acetate, methyl chloride, methylene chloride, chloroform, carbon tetrachloride and the like.
If the amount of the organic solvent that does not react with the polymerizable monomer is too small, the porosity of the particles is low, and if it is too large, the porosity is too high and the strength of the particles is reduced. It is preferable to add 1 to 400 parts by weight with respect to parts, and more preferably 10 to 200 parts by weight.

In the method for producing porous hollow polymer particles of the present invention, the step of adding the polymerizable monomer solution and the dispersion stabilizer made of polyvinyl alcohol to a polar solvent and suspending the solution is then performed.

In this invention, the layer which consists of polyvinyl alcohol is formed in the porous porous polymer particle outer surface and particle | grain inner surface which are obtained by adding the dispersion stabilizer which consists of the said polyvinyl alcohol. As a result, the liquid absorptivity of the porous hollow polymer particles is improved, and the porous hollow polymer particles are not easily destroyed even when the porous hollow polymer particles are used, or in the mixing and molding processes.
In addition, since the formed layer is very thin, even when used as a light diffusing agent, the light diffusivity is not affected, and both the light diffusibility and the solvent resistance, durability, etc. are compatible. be able to.

If the amount of the polyvinyl alcohol added is too large or too small, the stability of the oil droplets of the polymerizable monomer solution is not sufficient, and particle aggregation occurs during the polymerization. The preferred lower limit is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the added amount of the polyvinyl alcohol is less than 0.1 parts by weight, a layer of polyvinyl alcohol is not formed on the outer surface and inner surface of the obtained porous hollow polymer particles, and the strength of the porous hollow polymer particles When the amount of the polyvinyl alcohol added exceeds 10 parts by weight, the polyvinyl alcohol layer becomes thick, which may impair the light diffusion effect and liquid absorbency.
A more preferred lower limit is 0.3 parts by weight, and a more preferred upper limit is 5 parts by weight.

The polar solvent is not particularly limited as long as it is incompatible with the polymerization monomer solution, and examples thereof include water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, and the like. It is preferable to use it.

In the method for producing porous hollow polymer particles of the present invention, the step of polymerizing the polymerizable monomer is then performed.

In the polymerization, a polymerization initiator is usually used. Examples of the polymerization initiator include compounds that generate oil-soluble free radicals that are compatible with the monomer solution for polymerization, such as benzoyl peroxide, lauroyl peroxide, dibutyl peroxydicarbonate, α-cumyl peroxyneodecano. Organic peroxides such as ate, azo initiators such as azobisisobutyronitrile, and redox initiators.

In the above polymerization, an inorganic salt or a water-soluble polymerization inhibitor may be added to the polar solvent in order to suppress the generation of new particles due to the polymerization occurring in a place other than the oil droplets of the polymerization monomer solution. The inorganic salt dissolves in a polar solvent, reduces the solubility of the monomer component for polymerization in the polar solvent, and functions to suppress polymerization in the polar solvent, such as sodium chloride, calcium chloride, sodium carbonate, etc. It is done. The water-soluble polymerization inhibitor is added for the purpose of suppressing polymerization in a polar solvent, and specific examples include sodium sulfite, sodium nitrite, copper chloride, iron chloride, titanium chloride, hydroquinone and the like. .

As a specific example of the method for producing the porous hollow polymer particles of the present invention, for example, the following method is preferable.
First, add water, a water-soluble polymer dispersion stabilizer, and an auxiliary stabilizer, pH adjuster, water-soluble polymerization inhibitor, etc., if necessary, to a container equipped with a stirrer and a thermometer. Prepare the charge. Next, a polymerization initiator is dissolved in advance in a polymerization monomer solution in which a polymerization monomer and an organic solvent that does not react with the polymerizable monomer are mixed and added to the initial charge, and then the polymerization initiator substantially acts. For example, a method of stirring for a predetermined time at a temperature at which the polymerization is not performed, raising the temperature to a temperature higher than the temperature at which the polymerization initiator acts, and continuing polymerization for a predetermined time may be used.
The polymerization monomer solution mixed with the polymerization monomer and the organic solvent that does not react with the polymerizable monomer may be added as it is to the initial charge, but it is added in a finely dispersed state in a dispersion medium in advance. It is preferable. Alternatively, a method may be used in which the monomer solution for polymerization is directly added to the initial charge and finely dispersed in the system by the action of mechanical stirring force.

As a method of finely dispersing in advance in a dispersion medium an organic solvent that does not react with the polymerization monomer and the polymerizable monomer, for example, a method using a mechanical disperser such as a homomixer or a biomixer, an ultrasonic homogenizer, or the like. Etc.
Since the particle diameter of the porous hollow polymer particles obtained as a result of the above polymerization depends on the oil droplet diameter of the polymerizable monomer solution finely dispersed in the dispersion medium, the type and amount of the dispersion stabilizer and the mechanical disperser The particle diameter of the porous hollow polymer particles can be easily controlled by the stirring force.

The temperature setting of the reaction system in the method for producing porous hollow polymer particles of the present invention varies depending on the composition and molecular weight of the polymerization monomer used, the type of polymerization initiator, the amount added, etc., but is usually in the range of 30 to 100 ° C. Done.
Additives added during or after the polymerization are not particularly limited, and examples include pH adjusters, anti-aging agents, antioxidants, and preservatives.

Further, when the polymerization is substantially completed, the pores of the porous hollow polymer particles remain in a state in which an organic solvent that does not react with the polymerizable monomer is included.
The encapsulated organic solvent can be removed as necessary by a method of blowing a gas such as steam, nitrogen, air or the like into a dispersion of particles obtained or a method of placing the system under reduced pressure.
In addition, the porous hollow polymer particles obtained by the production method of the present invention can be dried and used for powder applications.

The perfume-carrying polymer particles of the present invention are perfume-carrying polymer particles in which a perfume is carried on a porous hollow polymer particle having a plurality of pores inside the particle, and the porous hollow polymer particle has a particle outer surface and The inner surface of the particle is coated with polyvinyl alcohol.

The perfume-carrying polymer particles of the present invention can support a perfume stably by using the porous hollow polymer particles as a perfume support, and the amount of perfume supported can be made sufficient. . Moreover, it is excellent in the sustained release property of a fragrance | flavor, and it becomes possible to release a fragrance | flavor at a fixed speed over a long period of time.

In addition, about the said porous hollow polymer particle, since it is the structure similar to the porous hollow polymer particle of this invention, the detailed description is abbreviate | omitted.

The fragrance used in the present invention is preferably a liquid fragrance, and specifically, for example, fragrances such as cyclic ethers, ketones, alcohols, lactones, esters, aldehydes, plant natural fragrances, natural extracted essential oils. Synthetic fragrances, rose-like blended fragrances, cinnamon-like blended fragrances, citrus-like blended fragrances, and the like.

Examples of the fragrance of the cyclic ethers include hexamethylhexahydrocyclopentabenzopyran, rose euside and the like.
Examples of the fragrance of the ketones include α-isomethylionone.
Examples of the fragrances for the alcohols include dipyropylene glycol, cis-3-hexenol, linalool, and dihydrofarnesol.
Examples of the lactone fragrances include decalactone and γ-undecalactone.
Examples of the fragrance for the esters include geranyl acetate, isobornyl acetate, hexyl salicylate, and the like.
Examples of the fragrances of the aldehydes include citronellal, α-hexylcinnamic aldehyde, pt-butyl-α-methylhydrocinnamic aldehyde, and the like. These may be used alone or in combination of two or more.

Examples of the plant natural fragrances include hinokitiol, alumose, lemon, lime, orange terpene, rosemary, lavender, jasmine and the like. These may be used alone or in combination of two or more.

Examples of the natural extract essential oil include hiba oil, cypress oil, bamboo extract, mugwort extract, tung oil, cinnamon oil, camellia oil, eucalyptus oil, and the like. These may be used alone or in combination of two or more.

Examples of the synthetic fragrance include, for example, pinene, limonene, camphene, terbinolene, linanol, geraniol, citronellol, menthol, citral, vanillin, benzaldehyde ketone, carvone, menthone, benzophenone, coumarin, anisole, thymol, eugenol, anethole, benzoic acid, Examples thereof include cinnamic acid, hydrocinnamic acid, phenylacetic acid, ethyl acetate, geranyl acetate, and isoamyl propionate. These may be used alone or in combination of two or more.

Moreover, the following blended fragrances can be prepared by appropriately blending the above-mentioned various fragrances. In the parentheses below, the number of parts by weight is shown.

Examples of the rose-like blended fragrance include limonene (20), linalool (70), undecylenic aldehyde (30), citronellol (250), geraniol (200), phenylethyl alcohol (200), and hydroxycitronellol (20). , N-hexyl alcohol (40), t-2-hexenyl acetate (30), t-2-hexenol (60), ethyl caproate (30), phenylethylphenyl acetate (30), phenylethyl acetate ( 20) can be prepared.

For example, methyl dihydrojasmonate (20), γ-decalactone (20), α-ionone (50), benzyl alcohol (50), geraniol (80), linalool (250), cis- 3-hexenyl isovalerate (10), linalool oxide (80), nonyl aldehyde (20), n-hexyl alcohol (90), amyl propylate (160), ethyl caproate (30), cis-3-hexenol (100) and ethyl enanthate (40).

In addition, a geranium-like blended fragrance, a ylang-ylang-like blended fragrance, a cyclamen-like blended fragrance, a floral-like blended fragrance, a bineedle-like blended fragrance, a hiba oil-like blended fragrance, and the like can be used as a blended fragrance.

In the perfume-carrying polymer particles of the present invention, a filler, an antifoaming agent, a heat stabilizer, an antioxidant, an antistatic agent, an ultraviolet absorber, an antibacterial agent, an antifungal agent, a fluorescent agent, a dye, You may mix | blend a pigment etc.

The use and method of use of the fragrance-carrying polymer particles of the present invention are not particularly limited. For example, the method of using the fragrance-carrying polymer particles themselves of the present invention as a fragrance or the suspension of the fragrance-carrying polymer particles of the present invention Examples of the method include a method used as a dispersion, a method kneaded and used as a cream or paste, and a method used by spinning fibers. Moreover, it can use for the goods etc. which give aroma as a fashion coating film on molded objects, such as various films or tapes.
Furthermore, since the fragrance | flavor carrying | support polymer particle of this invention does not have stickiness etc. since a fragrance | flavor is carry | supported inside a particle | grain, it can be used conveniently also in cosmetics fields, such as a foundation.

The fragrance-carrying polymer particles of the present invention include, for example, a step of mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution, the polymerizable monomer solution, and polyvinyl alcohol. And a step of adding and suspending the dispersion stabilizer to a polar solvent, polymerizing the polymerizable monomer to produce porous hollow polymer particles, and supporting a fragrance on the porous hollow polymer particles. It can manufacture with the manufacturing method which has. Such a method for producing the perfume-carrying polymer particles is also one aspect of the present invention.

A step of mixing a polymerizable monomer in the perfume-carrying polymer particles of the present invention and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution, dispersion stability comprising the polymerizable monomer solution and polyvinyl alcohol The step of adding and suspending the agent in the polar solvent and the step of polymerizing the polymerizable monomer to produce the porous hollow polymer particles are the same as the porous hollow polymer particles of the present invention. Therefore, the detailed description is abbreviate | omitted.

The method for supporting the fragrance on the porous hollow polymer particles is not particularly limited, and for example, the method of mixing, dipping, etc. may be appropriately selected in consideration of the purpose of use of the final product, the form of use, the conditions of use, etc. Can do.

Examples of the mixing method include a method of mixing the porous hollow polymer particles and the fragrance using a mixer.
Examples of the mixer include a Nauter mixer (manufactured by Hosokawa Micron Corporation), a ribbon type mixer (manufactured by Tokuju Kogakusho Co., Ltd.), a V-type blender (manufactured by Dalton), a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and a Henschel mixer. (Mitsui Mining Co., Ltd.), Super Mixer (Kawata Co., Ltd.), Bench Kneader (Irie Trading Co., Ltd.) and the like.

Examples of the method by immersion include a method of immersing the porous hollow polymer particles in a container containing a fragrance. The time for immersing the porous hollow polymer particles, the amount of the fragrance used, and the like are not particularly limited, and are determined according to the degree of affinity between the fragrance used and the porous hollow polymer particles.
That is, when the porous hollow polymer particles are immersed, if the impregnation rate of the fragrance is slow, it is necessary to immerse the fragrance for a long time in order to obtain a desired fragrance. The immersion can be completed in a short time until a desired aroma is obtained.

In the step of supporting the fragrance on the porous hollow polymer particles, the amount of the polyvinyl alcohol added is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer. When the addition amount of the polyvinyl alcohol is less than 0.1 parts by weight, the strength, liquid absorbency, and solvent resistance of the porous hollow polymer particles may be lowered, and the addition amount of the polyvinyl alcohol is 10 parts by weight. If it exceeds 1, the polyvinyl alcohol layer becomes thick, which may impair the light diffusion effect and liquid absorbency. The minimum with more preferable addition amount of the said polyvinyl alcohol is 0.2 weight part, and a more preferable upper limit is 5 weight part.

According to the method for producing a porous hollow polymer particle of the present invention, it is possible to obtain a porous hollow polymer particle excellent in sustained-release perfume, light diffusibility, liquid absorbency, body sensibility, solvent resistance and mechanical strength. it can. Moreover, the fragrance | flavor carrying | support polymer particle which can carry | support a fragrance | flavor stably and is excellent in the sustained release property of a fragrance | flavor can be obtained. Furthermore, the manufacturing method of this porous hollow polymer particle and the manufacturing method of this fragrance | flavor carrying | support polymer particle can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(Preparation of porous hollow polymer particles)
50 parts by weight of methyl methacrylate and 30 parts by weight of isobutyl methacrylate as a monofunctional monomer, 20 parts by weight of trimethylolpropane triacrylate as a polyfunctional monomer, 100 parts by weight of cyclohexane as an organic solvent, and azobisisobutyronitrile as a polymerization initiator 25 parts by weight was mixed and stirred to prepare a monomer solution for polymerization.
Subsequently, 30 parts by weight of a 15% aqueous solution of partially saponified polyvinyl alcohol (saponification degree 88 mol%, average polymerization degree 2000) using 300 parts by weight of ion-exchanged water as a polar solvent was added, and the suspension was stirred with a homogenizer. Was prepared. On the other hand, in a 20 liter polymerization vessel equipped with a stirrer, jacket, reflux condenser and thermometer, the remaining ion-exchanged water and 0.25 parts by weight of sodium sulfite as a water-soluble polymerization inhibitor were added, and stirring was started. did. After depressurizing the inside of the polymerization vessel and deoxidizing the inside of the vessel, the pressure was returned to atmospheric pressure with nitrogen, the inside was made into a nitrogen atmosphere, and the suspension was put all at once into the polymerization tank. The temperature was raised to and polymerization was started. The polymerization was completed in 4 hours, and after a aging period of 1 hour, the polymerization tank was cooled to room temperature. The slurry was dehydrated with a centle, and then the organic filler was removed by vacuum drying to obtain porous hollow polymer particles.
The saponification degree of the partially saponified polyvinyl alcohol used was determined from the alkali consumption required for hydrolysis of the residual vinyl acetate structural unit. The average degree of polymerization of partially saponified polyvinyl alcohol was determined according to JIS K 6726.

The surface and cross section of the obtained porous hollow polymer particles were observed at a magnification of 1500 times using a scanning electron microscope (FE-SEM, manufactured by Hitachi, Ltd.) and photographed. FIG. 1 is a photograph of the surface of a porous hollow polymer particle, and FIG. 2 is a photograph of a particle cross section of the porous hollow polymer particle. As shown in FIG.1 and FIG.2, the particle | grain outer surface and particle | grain inner surface of the obtained porous hollow polymer particle were coat | covered with polyvinyl alcohol.

(Preparation of perfume-carrying polymer particles)
After weighing 1.000 g of the obtained porous hollow polymer particles, the porous hollow polymer particles were absorbed with a 0.05% aqueous solution of limonene, which is a fragrance, to obtain fragrance-carrying polymer particles by a method based on ASTM D1483. It was. The amount of fragrance absorbed was 0.800 g. The absorption amount of the fragrance was calculated by measuring the weight after absorption.

(Example 2)
Porous hollow polymer particles and perfume-carrying polymer particles were obtained in the same manner as in Example 1 except that partially saponified polyvinyl alcohol (saponification degree 81 mol%, polymerization degree 2000) was added.

(Example 3)
Porous hollow polymer particles and perfume-carrying polymer particles were obtained in the same manner as in Example 1 except that partially saponified polyvinyl alcohol (saponification degree 88 mol%, polymerization degree 500) was added.

(Comparative Example 1)
Instead of partially saponified polyvinyl alcohol, 45 parts by weight of a 20% aqueous solution of colloidal silica as a colloidal inorganic dispersion stabilizer, 0.45 parts by weight of polyvinylpyrrolidone as a dispersion stabilizer, 30 parts by weight of sodium chloride and 35% of hydrochloric acid Porous hollow polymer particles and perfume-carrying polymer particles were produced in the same manner as in Example 1 except that 0.3 part by weight of the aqueous solution was added.

(Comparative Example 2)
In Example 1 (Preparation of porous hollow polymer particles), polymer particles and perfume-carrying polymer particles were prepared in the same manner as in Example 1 except that 100 parts by weight of cyclohexane was not added as the organic solvent.

(Comparative Example 3)
After obtaining the polymer particles by the same method as in Comparative Example 2, the polymer particles and the limonene 0.05% aqueous solution were used in TEM50 (manufactured by Toshiba Machine Co., Ltd., co-directional twin-screw extruder). Perfume-carrying polymer particles were produced in the same manner as in Example 1 except that the perfume was absorbed by extrusion kneading.

(Evaluation)
The porous hollow polymer particles, polymer particles, and perfume-carrying polymer particles obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.

(1) The average particle diameter and CV value of the porous hollow polymer particles and the polymer particles. The obtained porous hollow polymer particles and polymer particles are volumetric using a laser diffraction particle size distribution meter (LA-910, manufactured by Horiba, Ltd.). The average particle size and CV value were measured.

(2) The average value of pore diameter / outer diameter (d / D) The porous hollow polymer particles obtained were obtained by using a transmission electron microscope (“JEM-1200EXII”, manufactured by JEOL Ltd.). The average value of the ratio of the pore diameter to the outer diameter of the particles was measured.

(3) Measurement of porosity of porous hollow polymer particles and polymer particles Measured under the condition of enclosed mercury pressure of 2000 kg / cm ² using Amos Porosimeter 2000, and the entire volume of porous hollow polymer particles and polymer particles The volume of the hollow part occupying was calculated.

(4) Particle size ratio before and after solvent immersion The obtained porous hollow polymer particles and polymer particles were immersed in methyl ethyl ketone for 24 hours at 25 ° C., and the particle size D1 before immersion and the particle size D0 before immersion were determined by the above laser. The ratio (D1 / D0) was calculated by measuring with a diffraction particle size distribution meter.

(5) Evaluation of Perfume Sustained Release Property The obtained perfume-supported polymer particles were transferred to a petri dish and the surface was flattened. )) Was used to measure the odor level. After the measurement, the petri dish was taken out of the polyethylene bag, put in an oven at 50 ° C., and the petri dish was taken out every 10 minutes, and the odor level was measured.
FIG. 3 shows a graph showing the change in odor level with respect to the heating time of the perfume-carrying polymer particles obtained in Example 1 and Comparative Example 1, and FIG. 4 shows the perfume-carrying obtained in Example 1 and Comparative Example 1. The graph showing the change of a relative value when the odor level at the time of the first measurement of a polymer particle is set to 100 is shown.
Table 1 shows the odor level (relative value) after 60 minutes of heating time with respect to the initial odor level (heating time 0 minutes).

Example 4
(Production of light diffusion sheet)
The light diffusing layer solution was prepared by stirring and mixing the following raw materials.
(binder)
Acrylic binder 20 parts by weight (solvent)
Toluene 40 parts by weight Methyl ethyl ketone 20 parts by weight (porous hollow polymer particles)
20 parts by weight of particles obtained in Example 1

The obtained light diffusing layer solution was applied to one side of a polyethylene terephthalate sheet, which was a transparent substrate layer, and then dried to obtain a light diffusing sheet.
The dry weight of the coating film was 16 g / m ² , and the thickness of the coating film after drying was 30 μm.

(Example 5)
A light diffusion sheet was obtained in the same manner as in Example 4 except that the particles obtained in Example 2 were used as the porous hollow polymer particles.

(Example 6)
A light diffusion sheet was obtained in the same manner as in Example 4 except that the particles obtained in Example 3 were used as the porous hollow polymer particles.

(Comparative Example 4)
A light diffusion sheet was obtained in the same manner as in Example 4 except that the particles obtained in Comparative Example 1 were used as the porous hollow polymer particles.

(Evaluation)
About the light-diffusion sheet obtained by the Example and the comparative example, it evaluated by the following method. The results are shown in Table 2.

(6) Measurement of transmittance The light diffusion sheet thus obtained was measured for total light transmittance and haze using a haze meter (Tokyo Denshoku Co., Ltd., “TC-H3PDK”, conforming to JIS K7105).
A product having a total light transmittance of 90% or more and a haze of 80% or more was judged as a non-defective product.

ADVANTAGE OF THE INVENTION According to this invention, the porous hollow polymer particle excellent in the sustained release property of a fragrance | flavor, light diffusibility, liquid absorptivity, body sensibility, solvent resistance, and mechanical strength can be provided. Further, it is possible to provide a fragrance-carrying polymer particle that can stably carry a fragrance and is excellent in sustained release of the fragrance. Furthermore, the manufacturing method of this porous hollow polymer particle and this fragrance | flavor carrying | support polymer particle can be provided.

4 is a SEM photograph obtained by photographing the surface of the porous hollow polymer particles obtained in Example 1. FIG. 2 is a SEM photograph taken of a cross section of porous hollow polymer particles obtained in Example 1. FIG. It is a graph which shows the change of the odor level with respect to the heating time in perfume sustained release evaluation. In perfume sustained release evaluation, it is a graph which shows the change of a relative value when the odor level at the time of the first measurement is set to 100.

Claims (6)

A porous hollow polymer particle having a plurality of pores inside the particle,
A porous hollow polymer particle, wherein the outer surface of the particle and the inner surface of the particle are coated with polyvinyl alcohol. 2. The porous hollow polymer particle according to claim 1, wherein the polyvinyl alcohol is a partially saponified polyvinyl alcohol. 3. The porous hollow polymer particle according to claim 1, wherein the average particle diameter is 10 to 100 μm, the CV value is 15 to 35%, and the porosity is 20 to 80%. A method for producing the porous hollow polymer particles according to claim 1, 2, or 3,
A step of mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution;
Adding and suspending the polymerizable monomer solution and a dispersion stabilizer made of polyvinyl alcohol in a polar solvent; and
A method for producing porous hollow polymer particles, comprising a step of polymerizing the polymerizable monomer. A perfume-supporting polymer particle obtained by supporting a perfume on a porous hollow polymer particle having a plurality of pores inside the particle,
A perfume-carrying polymer particle, wherein the porous hollow polymer particle has a particle outer surface and a particle inner surface coated with polyvinyl alcohol. A method for producing the perfume-carrying polymer particles according to claim 5,
A step of mixing a polymerizable monomer and an organic solvent that does not react with the polymerizable monomer to prepare a polymerizable monomer solution;
Adding and suspending the polymerizable monomer solution and a dispersion stabilizer made of polyvinyl alcohol in a polar solvent;
Polymerizing the polymerizable monomer to produce porous hollow polymer particles; and
A method for producing a perfume-carrying polymer particle, comprising a step of carrying a perfume on the porous hollow polymer particle.

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