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WO2003016382A1 - Particule de polymere carboxyle reticule - Google Patents

Particule de polymere carboxyle reticule Download PDF

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Publication number
WO2003016382A1
WO2003016382A1 PCT/JP2002/007909 JP0207909W WO03016382A1 WO 2003016382 A1 WO2003016382 A1 WO 2003016382A1 JP 0207909 W JP0207909 W JP 0207909W WO 03016382 A1 WO03016382 A1 WO 03016382A1
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WIPO (PCT)
Prior art keywords
containing polymer
carboxyl group
polymer particles
crosslinked
crosslinked carboxyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/007909
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English (en)
Japanese (ja)
Inventor
Shigeki Hamamoto
Masatoyo Yoshinaka
Tomoki Kawakita
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to JP2003521704A priority Critical patent/JPWO2003016382A1/ja
Publication of WO2003016382A1 publication Critical patent/WO2003016382A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J3/12—Powdering or granulating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to crosslinked carboxyl group-containing polymer particles. More specifically, the present invention relates to crosslinked carboxyl group-containing polymer particles which can be suitably used as a thickener for cosmetics and the like, a humectant such as a poultice, and a suspension stabilizer for emulsions and suspensions.
  • a thickener for cosmetics and the like a humectant such as a poultice
  • a suspension stabilizer for emulsions and suspensions.
  • crosslinked type carboxyl group-containing polymer examples include, for example, a copolymer of ⁇ -unsaturated carboxylic acid such as acrylic acid and polyallyl ether (US Pat. No. 2,922,692), (Ii) Copolymers of ⁇ -unsaturated carboxylic acids and hexarylarylmethylenetrisulfone (US Pat. No. 2,958,679), ⁇ -unsaturated carboxylic acids and phosphoric acid Copolymers with triallyl (U.S. Pat. No. 3,426,004), and copolymers of, ⁇ -unsaturated carboxylic acids with glycidylmethacrylate (Japanese Patent Application Laid-Open No.
  • crosslinked carboxyl group-containing polymers are dispersed and swelled in water, and then neutralized with an alkali to form a neutralized viscous liquid, thereby increasing the viscosity of cosmetics and humectants such as poultices.
  • Used for applications such as suspension stabilizers such as emulsions and suspensions
  • In order to use the cross-linked carboxyl group-containing polymer in these applications first prepare a uniform aqueous dispersion of the cross-linkable carboxyl group-containing polymer, and then neutralize with an alkali. It must be a viscous liquid.
  • the crosslinked carboxyl group-containing polymer is usually a fine powder, a lump (mamako) is likely to be generated when the polymer is dispersed in water.
  • a gel-like layer is formed on its surface, so that the speed at which water permeates into the inside decreases, and it is difficult to obtain a uniform aqueous dispersion.
  • the production efficiency is such that the crosslinked carboxyl group-containing polymer powder is gradually added to water under high-speed stirring in order to prevent the formation of mako. Require poor operation and, in some cases, require special dissolution equipment to prevent the formation of mako.
  • the cross-linked carboxyl group-containing polymer is a fine powder and is easily charged, so that powdering is severe. Therefore, the above-mentioned cross-linked carboxyl group-containing polymer has drawbacks in that it is not only difficult to handle but also unfavorable in working environment.
  • a cross-linked carboxyl group-containing polymer having improved dispersibility and solubility in water a J5-unsaturated carboxylic acid such as acrylic acid in an inert solvent in the presence of a special surfactant is used.
  • Japanese Unexamined Patent Publication (Kokai) No. 6-19969 Japanese Unexamined Patent Publication (Kokai) No. 6-19969
  • a solvent such as water or an alcohol is added during precipitation polymerization to precipitate.
  • cross-linked carboxyl group-containing polymers are not yet satisfactory, although their dispersibility in water is improved. If the aqueous dispersion of the cross-linked carboxyl group-containing polymer is not uniform, then neutralize with alkali in order to obtain a neutralized viscous liquid with excellent surface smoothness, thickening and transparency. To obtain a viscous liquid, it is necessary to stir for a long time. Yes, Disclosure of the Invention
  • An object of the present invention is to provide a neutralized viscous liquid which is excellent in dispersibility in water, is easy to handle, and is obtained by neutralizing the aqueous dispersion with alkali.
  • An object of the present invention is to provide excellent crosslinked carboxyl group-containing polymer particles.
  • the present invention was obtained by polymerizing, ⁇ monounsaturated carboxylic acids and a compound having two or more ethylenically unsaturated groups in an inert solvent in the presence of a radical polymerization initiator.
  • the present invention relates to crosslinked carboxyl group-containing polymer particles having a median particle diameter of 20 to 800, which are obtained by compression molding, pulverizing and classifying the product.
  • the term “medium particle size” refers to a value obtained by sequentially integrating the weight of the crosslinked carboxyl group-containing polymer particles remaining on each sieve when the crosslinked carboxyl group-containing polymer particles are classified by a sieve. When the integrated weight thus obtained reaches 50% by weight of the total weight of the crosslinked type ruboxyl group-containing polymer particles, the particle size corresponds to the mesh size of the sieve.
  • the seven standard sieves specified in JIS-Z8801-1982 (opening: 85 m, 500 m / m, 350 m, 300 m, 300 m, 250 m, 18 m 0 / m, 106 ⁇ m) and a tray are prepared, and a sieve with a small aperture and a sieve with a large aperture are sequentially laminated, and the crosslinked type carboxyl group-containing polymer particles 100 g, vibrate for 10 minutes using a low tap sieve vibrator, weigh the polymer particles containing cross-linked lipoxyl groups remaining on each sieve, and sequentially accumulate the total weight.
  • the median particle size determined by calculating the particle size corresponding to the opening of the sieve when it reaches 50% by weight of the total weight of the group-containing polymer particles by the following formula is defined as the median particle size.
  • Medium particle size (m) () X (DB) + B
  • A is the weight of the cross-linked carboxyl-containing polymer particles remaining on the sieve in order from the coarse-meshed sieve, and the integrated weight is 50 weight of the total weight of the cross-linked carboxyl-containing polymer particles.
  • % I is the integrated value (g) up to the sieve closest to 50% by weight, and B is the sieve opening (zm) when the integrated value of A was obtained.
  • the weight of the cross-linkable lipoxyl group-containing polymer particles remaining on the sieve in order from the coarse and the sieve is integrated, and the integrated weight is 50% by weight or more of the total weight of the cross-linked carboxyl group-containing polymer particles.
  • D is the sieve opening (zm) when the integrated value of C was determined.
  • the median particle size of the crosslinked carboxyl group-containing polymer particles of the present invention is 20 to 800 ⁇ m, preferably 100 to 700 ⁇ m, and more preferably 150 to 600 am. If the median particle diameter of the crosslinked carboxyl group-containing polymer particles is less than 20 zm, dispersibility in water will be poor, and a neutralized viscous liquid having excellent surface smoothness, thickening and transparency will be obtained. In this case, it is necessary to stir for a long time when neutralizing with an alkali, and furthermore, the powder becomes so violent that it becomes difficult to handle. When the median particle size of the crosslinked carboxyl group-containing polymer particles exceeds 800 m, the dispersibility in water is good, but the affinity with water becomes poor, and the neutralization with alkali An insoluble gel forms in the viscous liquid.
  • the bulk density of the crosslinked type carboxyl group-containing polymer particles of the present invention is 0.2 to 0.6 g ZmL, preferably 0.25 to 6 gZmL, more preferably 0.3 to 0.55 gZmL. Is desirable. If the bulk density of the cross-linked carboxyl group-containing polymer particles is less than 0.2 gZmL, the powder may become so violent that it may be difficult to handle. When the bulk density exceeds 0.6 g / mL, it takes not only long time to completely disperse the cross-linked carboxyl group-containing polymer particles when dispersing in water, but also the obtained neutralized viscosity. The smoothness of the surface of the dense liquid may be deteriorated. As used herein, the term “bulk density” refers to the ratio of the weight of the cross-linkable carboxyl group-containing polymer particles to the volume of the cross-linked cross-linked ruboxyl group-containing polymer particles.
  • the cross-linked carboxyl group-containing polymer particles After adding 1 Og of the cross-linked carboxyl group-containing polymer particles within 20 seconds from the height of 5 cm above the empty measuring cylinder having a capacity of 5 OmL, the cross-linked carboxyl group-containing polymer particles The volume (mL) occupied by the polymer particles is measured, and the weight (1 Og) of the crosslinked carboxyl group-containing polymer particles is divided by the volume (mL) occupied by the crosslinked carboxyl group-containing polymer particles. Refers to the calculated value.
  • the polymer having a crosslinked type lipoxyl group used in the present invention is obtained by radiating ot, ⁇ -unsaturated carboxylic acid and a compound having two or more ethylenically unsaturated groups in an inert solvent by radical polymerization. It can be produced by polymerizing in the presence of an initiator ⁇
  • ⁇ monounsaturated carboxylic acids are not particularly restricted but include, for example, ⁇ monounsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid; Myristyl acrylate, palmityl acrylate, oleyl acrylate, stearyl acrylate, behenyl acrylate, lauryl methacrylate, myristyl methacrylate, palmityl methacrylate, oleyl methacrylate, stearyl methacrylate, behenyl methacrylate, etc. And —-unsaturated carboxylic acid alkyl esters having 10 to 30 carbon atoms in the alkyl group. These may be used alone or in combination of two or more.
  • The, -unsaturated carboxylic acid may be used alone or in combination with an ⁇ , -unsaturated carboxylic acid alkyl ester having an alkyl group having 10 to 30 carbon atoms.
  • acrylic acid is used alone, or acrylic acid and lauryl methacrylate are used.
  • the amount of the ⁇ , ⁇ monounsaturated carboxylic acid used is less than 6 parts by volume, the transparency of the resulting neutralized viscous liquid of the crosslinked carboxyl group-containing polymer may be deteriorated. If the amount of the, ⁇ -unsaturated carboxylic acid exceeds 25 parts by volume, as the reaction proceeds, the cross-linked carboxyl group-containing polymer precipitates and it becomes difficult to stir uniformly, and the resulting cross-linked The surface smoothness of the neutralized viscous liquid of the type carboxyl group-containing polymer may deteriorate.
  • the compound having two or more ethylenically unsaturated groups is not particularly limited.
  • the amount of the compound having two or more ethylenically unsaturated groups used is 0.15 to 2 parts by weight, preferably 0.3 to 1.0 part by weight, based on 100 parts by weight of, ⁇ monounsaturated carboxylic acids. Desirably 5 parts by weight. If the amount of the compound having two or more ethylenically unsaturated groups is less than 0.15 parts by weight, the viscosity of the resulting neutralized viscous liquid of the crosslinked carboxyl group-containing polymer may be reduced. When the amount of the compound having two or more ethylenically unsaturated groups exceeds 2 parts by weight, the obtained cross-linked carboxy Insoluble gels in the neutralized viscous solution of the polymer containing
  • the radical polymerization catalyst is not particularly restricted but includes, for example, 'azobisisobutyronitrile, 2,2'-azobis-1,2,4-dimethylvaleronitrile, dimethyl-2,2'azobisisobutyrate, Benzoyl oxide, lauroyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide and the like can be mentioned.
  • the amount of the radical polymerization catalyst used is 0.01 to 0.45 parts by weight, preferably 0.01 to 0.35 parts by weight, per 100 parts by weight of the / 3-unsaturated carboxylic acid. It is desirable that If the amount of the radical polymerization catalyst used is less than 0.01 parts by weight, the reaction rate may be low, which may be uneconomical. If the amount of the radical polymerization catalyst used exceeds 0.45 parts by weight, the smoothness of the surface of the resulting neutralized viscous liquid of the crosslinkable lipoxyl group-containing polymer may be deteriorated.
  • inert solvent refers to a solvent which dissolves a CL, / 8-unsaturated carboxylic acid and a compound having two or more ethylenically unsaturated groups, and obtains a crosslinked carboxyl group-containing polymer obtained. A solvent that does not dissolve the coalescence.
  • inert solvent examples include normal pentane, normal hexane, isohexane, normal heptane, normal octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and chlorobenzene. Mouth benzene, ethylene dichloride, ethyl acetate, isopropyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used alone or in combination of two or more. Among them ⁇
  • Ethylene dichloride and normal hexane are preferred from the viewpoint of stable net quality and easy availability.
  • the atmosphere in which the unsaturated carboxylic acids are reacted with the compound having two or more ethylenically unsaturated groups is, for example, an inert gas such as nitrogen gas or argon gas. Preferably, it is an atmosphere.
  • the reaction temperature is preferably 50 to 90 ° C., and more preferably 50 to 90 ° C., from the viewpoint of suppressing the increase in the viscosity of the reaction solution and improving the smoothness of the surface of the neutralized viscous liquid of the obtained cross-linked carboxyl group-containing polymer. It is desirably 55 to 75 ° C.
  • the reaction time differs depending on the reaction temperature and cannot be unconditionally determined, but is usually 2 to 10 hours.
  • the reaction solution is heated to 80 to 130 ° C., and the inert solvent is volatilized and removed, whereby a white fine powder of a crosslinked type carboxyl group-containing polymer can be obtained. If the heating temperature is lower than 80 ° C, it may take a long time to dry. If the heating temperature is higher than 130 ° C, the surface of the obtained crosslinked carboxyl group-containing polymer neutralized viscous liquid is smooth. May deteriorate.
  • the crosslinked carboxyl group-containing polymer particles of the present invention can be obtained by subjecting the thus obtained crosslinked carboxyl group-containing polymer to compression molding, pulverization and classification.
  • the method for producing the crosslinked carboxyl group-containing polymer particles of the present invention is characterized in that the weight loss after leaving for 3 hours at 110 ° C. (hereinafter referred to as “drying loss”) is 7% by weight or less. It includes a step of pulverizing and classifying the polymer after compression molding.
  • a specific example of such a production method is a method in which a crosslinked carboxyl group-containing polymer having a loss on drying of 7% by weight or less is compression-molded to an appropriate size, and then pulverized to classify into a desired medium particle diameter. And the like.
  • the compression molding apparatus used in the compression molding is not particularly limited, and examples thereof include commonly used compression molding apparatuses such as a small electric pump hydraulic press machine, a roll press compression molding machine, and an extrusion molding machine. Can be used.
  • the compression pressure at the time of compression molding is not particularly limited, and can be arbitrarily set according to the type of molding machine to be used, the composition of the cross-linked carboxyl group-containing polymer, the loss on drying, the compression temperature, etc. Usually, it is desirable that the gauge pressure is 9 to 15 OMPa, preferably 14 to 10 OMPa. When the compression pressure is less than 9 MPa, the bridging force The ropoxyl group-containing polymer may not be sufficiently compression-molded, and the resulting compression-molded product may become brittle and the fine powder content may increase. If the compression pressure exceeds 150 MPa, the obtained crosslinked carboxyl group-containing polymer particles may have poor glassy hydrophilicity and may form a portion.
  • the size and shape of the compression-molded cross-linked polymer of ropoxyl group-containing polymer vary depending on the compression molding equipment.
  • a small electric pump hydraulic press machine has a height of 5 mm and a diameter of 25 mm. It has a columnar shape.
  • the roll press type compression molding machine has a plate shape with a thickness of about 1 to 1 Omm.
  • the crusher used for crushing is not particularly limited, and for example, a commonly used crusher such as a pin mill crusher, a hammer mill crusher, a jet mill crusher, etc. may be used. it can.
  • the mixture is crushed and then classified using a sieve having a desired aperture to remove coarse powder so as to obtain particles having a desired median particle diameter. Coalescing particles are obtained.
  • the crosslinked carboxyl group-containing polymer particles of the present invention have a specific median particle diameter, they are less susceptible to mako and have better dispersibility in water than fine powdered crosslinked carboxyl group-containing polymers. Excellent, low dusting and excellent workability.
  • the bridged carboxyl group-containing polymer particles of the present invention are dispersed in water and neutralized with an alkali such as sodium hydroxide or triethanolamine, the surface is smooth, thickened and transparent in a short time. A neutralized viscous liquid having excellent properties is obtained.
  • Example 1 In a 50 OmL four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and condenser, 60 g (57.mL) of acrylic acid, 0.48 g of pen-erythritol tetraaryl ether, ⁇ , '— 0.009 g of azobisisobutyronitrile and 375 g (30 OmL) of ethylene dichloride were charged. Subsequently, after uniformly stirring and mixing, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel, the raw materials and the solvent. Then, the mixture was reacted at 70 to 75 for 3 hours under a nitrogen atmosphere.
  • the resulting slurry was heated to 110 ° C. to distill off ethylene dichloride, thereby obtaining 6 O g of a crosslinked carboxyl group-containing polymer as fine white powder.
  • the median particle size of the obtained cross-linked lipoxyl group-containing polymer was measured with a laser diffraction particle size distribution analyzer (trade name: SALD-2000J, Shimadzu Corporation, normal hexane dispersion medium). It is 11 m, and the bulk density is 0.17 gZmL.
  • 2 g of the obtained cross-linked carboxyl group-containing polymer was spread in a 5 mm x 25 mm ⁇ formwork, and was operated at a pressure of 4.7 MPa with a small electric pump hydraulic press (trade name: CD M-20, manufactured by Riken Seiki Co., Ltd.). (Gauge pressure) to obtain 2 g of a tablet of a columnar crosslinked type carboxyl group-containing polymer. Twenty-five tablets (total 50 g) were prepared.
  • the obtained tablet of the crosslinked type carboxyl group-containing polymer was put into a pin mill type pulverizer (fine impact mill of Hosokawa Micron Co., Ltd.) set at a rotation speed of 7000 rm at a speed of 1 gZ second and pulverized. . From 50 g of the obtained pulverized product, coarse powder was removed with a sieve having an opening of 100 m to obtain 37.5 g of crosslinked carboxyl group-containing polymer particles of the present invention. The median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 531 m, and the bulk density was 0.38 g / mL.
  • Example 2 A pin mill type pulverizer (trade name of Hosokawa Micron Corporation) having 25 tablets (total 50 g) of the crosslinked carboxyl group-containing polymer obtained in the same manner as in Example 1 was set at a rotation speed of 7000 rpm. (Fine impact mill) at a speed of 1 gZ second and pulverized. From 50 g of the obtained pulverized product, coarse powder was removed with a sieve having an opening of 500 zm to obtain 32.4 g of crosslinked carboxyl group-containing polymer particles of the present invention. The median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 225 am, and the bulk density was 0.34 gZmL.
  • Example 3 A pin mill type pulverizer (trade name of Hosokawa Micron Corporation) having 25 tablets (total 50 g) of the crosslinked carboxyl group-containing polymer obtained in the same manner as in Example 1 was set at a rotation speed of 7000 rpm. (Fine impact mill) at
  • a pin mill type pulverizer (trade name: Hosokawa Micron Co., Ltd.) having 25 tablets (50 g) of the crosslinked carboxyl group-containing polymer obtained in the same manner as in Example 1 was set at a rotation speed of 7000 rpm. (Impact mill) at a rate of 1 g / sec and pulverized. From 50 g of the obtained pulverized product, coarse powder was removed with a sieve having an opening of 300 zm to obtain 5.8 g of crosslinked carboxyl group-containing polymer particles of the present invention. The median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 151 am, and the bulk density was 0.31 gZm.
  • Example 1 36 g of crosslinked carboxyl group-containing polymer particles of the present invention were obtained in the same manner as in Example 1 except that the compression pressure was changed to 24.5 MPa (gauge pressure).
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 549 m, and the bulk density was 0.44 gZmL.
  • Example 5
  • Example 6 In the same manner as in Example 1 except that the compression pressure was changed to 34.3 MPa (gauge pressure) in Example 1, the crosslinked carboxyl group-containing polymer particles 33 of the present invention were used. I got The median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 560 m, and the bulk density was 0.48 gZmL.
  • Example 6
  • Example 1 30 g of crosslinked carboxyl group-containing polymer particles of the present invention was obtained in the same manner as in Example 1, except that the compression pressure was changed to 49 MPa (gauge pressure).
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 581 zm, and the bulk density was 0.52 g / mL.
  • Example 7
  • Crosslinked carboxyl group-containing polymer particles 28 of the present invention were obtained in the same manner as in Example 1 except that the compression pressure was changed to 73.5 MPa (gauge pressure).
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 596 Im, and the bulk density was 0.53 g / mL.
  • Example 10 After completion of the reaction, the resulting slurry was heated to 90 ° C. to distill off normal hexane to obtain 59 g of a crosslinked carboxyl group-containing polymer as fine white powder.
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer was measured with a laser diffraction single particle size analyzer (trade name: SALD-2000J, Shimadzu Corporation, normal hexane dispersion medium).
  • SALD-2000J laser diffraction single particle size analyzer
  • the crosslinked type carboxyl group-containing polymer obtained was subjected to compression molding, pulverization and classification in the same manner as in Example 1 to obtain a crosslinked type of the present invention. 43 g of carboxyl group-containing polymer particles were obtained.
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 409, and the bulk density was 0.34 g / mL.
  • the resulting slurry was heated to 110 ° C. to distill off ethylene dichloride, thereby obtaining 57 g of a crosslinked carboxyl group-containing polymer as fine white powder.
  • the median particle size of the obtained cross-linked carboxyl group-containing polymer was 15 m.
  • the degree was 0.17 g / mL.
  • the obtained crosslinked type carboxyl group-containing polymer was subjected to compression molding, pulverization and classification in the same manner as in Example 1 to obtain 41 g of bridged carboxyl group-containing polymer particles of the present invention.
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 509, and the bulk density was 0.39 g / mL. Comparative Example 1
  • Example 4 50 g of crosslinked carboxyl group-containing polymer particles were obtained in the same manner as in Example 1, except that the pulverized product of the crosslinked carboxyl group-containing polymer was not classified.
  • the median particle size was 820 ⁇ m, and the bulk density was 0.63 g / mL. Comparative Example 2
  • the resulting slurry was heated to 110 ° C. to distill off ethylene dichloride, thereby obtaining 60 g of a crosslinked carboxyl group-containing polymer as fine white powder.
  • the median particle size of the obtained crosslinked carboxyl group-containing polymer was measured using a laser diffraction single-particle size distribution analyzer (trade name: SAL D_2000 J, Shimadzu Corporation, normal hexane). 11 / zm and bulk density 0.17 g / mL-e hot 7Z Comparative Example 3
  • the surface of the neutralized viscous liquid of the obtained crosslinked carboxyl group-containing polymer particles was visually evaluated.
  • 10 men and women were used as the evaluation panelists, and the number of people who felt that the surface of the neutralized viscous liquid was smooth was judged to be good, and judged based on the following evaluation criteria. In the normal case, if the value is B or more based on the following criteria, it can be determined that the surface is excellent in smoothness.
  • the neutralized viscous liquid of the crosslinked type carboxyl group-containing polymer particles obtained in the above (2) was subjected to mouth rotation at No. 7, 20 rotations per minute, temperature 25 using a B-type rotational viscometer. It was measured under ° C. In a normal case, if the viscosity at 25 is 4200 OmPas or more, it can be determined that the viscosity is high.
  • the neutralized viscous liquid of the crosslinked carboxyl group-containing polymer particles obtained in the above (2) was placed in a 1 cm ⁇ 1 cm cell, and the transmittance of light having a wavelength of 425 nm was measured. Note that, in a normal case, if the transmittance is 94% or more, it can be determined that the transparency is excellent. table 1
  • the cross-linked carboxyl group-containing polymer particles obtained in Examples 1 to 10 are excellent in dispersibility in water. It can be seen that the neutralized viscous liquid obtained by summing has excellent surface smoothness, thickening and transparency. As described above, the crosslinked carboxyl group-containing polymer particles of the present invention have a specific median particle diameter, so that they are excellent in dispersibility in water, easy to handle, and can be used to remove water dispersion. The surface of the neutralized viscous liquid obtained by neutralization with ⁇ The effect of excellent transparency is exhibited.
  • the crosslinked carboxyl group-containing polymer particles of the present invention can be suitably used as a thickener for cosmetics and the like, a humectant such as a poultice, a suspension stabilizer for emulsions and suspensions, and the like.

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  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des particules d'un polymère carboxylé réticulé, dont le diamètre particulaire moyen se situe entre 20 et 800 νm, que l'on obtient par moulage par compression d'un produit de réaction obtenu par polymérisation d'un acide carboxylique α,β insaturé avec un composé ayant au moins deux groupes insaturés éthyléniquement dans un solvant inerte, en présence d'un initiateur de polymérisation radicalaire; puis par pulvérisation du moulage; et par classement des particules. On peut utiliser les particules polymères comme, par exemple, un épaississant pour produits cosmétiques, un agent hydratant pour cataplasmes, ou un stabilisant de suspension pour émulsions ou suspensions.
PCT/JP2002/007909 2001-08-09 2002-08-02 Particule de polymere carboxyle reticule Ceased WO2003016382A1 (fr)

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JP2003521704A JPWO2003016382A1 (ja) 2001-08-09 2002-08-02 架橋型カルボキシル基含有重合体粒子

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JP2001241648 2001-08-09
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007058143A1 (fr) * 2005-11-21 2007-05-24 Sumitomo Seika Chemicals Co., Ltd. Copolymere hydrosoluble ayant un groupe carboxyle modifie par un alkyle
WO2007132673A1 (fr) 2006-05-12 2007-11-22 Sumitomo Seika Chemicals Co., Ltd. Procédé de production de particules de polymère carboxylé granulaire et particules ainsi produites
WO2009022532A1 (fr) * 2007-08-10 2009-02-19 Sumitomo Seika Chemicals Co., Ltd. Procédé de fabrication de particules granulaires de polymère carboxylé et particules granulaires de polymère carboxylé
US8304517B2 (en) 2007-06-19 2012-11-06 Sumitomo Seika Chemicals Co., Ltd. Method for producing granulated carboxyl group-containing polymer particle and granulated carboxyl group-containing polymer particle
US8309667B2 (en) 2005-11-14 2012-11-13 Sumitomo Seika Chemicals Co., Ltd. Water-soluble copolymer having alkyl-modified carboxyl groups
JP2016069439A (ja) * 2014-09-29 2016-05-09 株式会社日本触媒 新規架橋重合体およびその製造方法
WO2017164357A1 (fr) * 2016-03-25 2017-09-28 住友精化株式会社 Copolymère contenant un groupe carboxyle modifié par un alkyle
WO2023074719A1 (fr) * 2021-10-27 2023-05-04 住友精化株式会社 POLYMÈRE RÉTICULÉ DE COMPOSÉ ACIDE CARBOXYLIQUE α,β-INSATURÉ, ET APPLICATION ASSOCIÉE

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JPH06107720A (ja) * 1992-10-01 1994-04-19 Sumitomo Seika Chem Co Ltd 架橋型カルボキシル基含有重合体の製造方法
JPH06287311A (ja) * 1993-04-01 1994-10-11 Mitsubishi Rayon Co Ltd 粉粒状重合体の製造方法
JPH08143680A (ja) * 1994-11-22 1996-06-04 Mitsubishi Chem Corp 粒状吸水性樹脂の処理法
JPH10130324A (ja) * 1996-10-24 1998-05-19 Nippon Shokubai Co Ltd 吸水性樹脂の製造方法
JPH11349687A (ja) * 1998-04-07 1999-12-21 Nippon Shokubai Co Ltd 粒子状含水ゲル状重合体および吸水性樹脂の製造方法

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JPH06107720A (ja) * 1992-10-01 1994-04-19 Sumitomo Seika Chem Co Ltd 架橋型カルボキシル基含有重合体の製造方法
JPH06287311A (ja) * 1993-04-01 1994-10-11 Mitsubishi Rayon Co Ltd 粉粒状重合体の製造方法
JPH08143680A (ja) * 1994-11-22 1996-06-04 Mitsubishi Chem Corp 粒状吸水性樹脂の処理法
JPH10130324A (ja) * 1996-10-24 1998-05-19 Nippon Shokubai Co Ltd 吸水性樹脂の製造方法
JPH11349687A (ja) * 1998-04-07 1999-12-21 Nippon Shokubai Co Ltd 粒子状含水ゲル状重合体および吸水性樹脂の製造方法

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8309667B2 (en) 2005-11-14 2012-11-13 Sumitomo Seika Chemicals Co., Ltd. Water-soluble copolymer having alkyl-modified carboxyl groups
WO2007058143A1 (fr) * 2005-11-21 2007-05-24 Sumitomo Seika Chemicals Co., Ltd. Copolymere hydrosoluble ayant un groupe carboxyle modifie par un alkyle
US8067517B2 (en) 2005-11-21 2011-11-29 Sumitomo Seika Chemicals Co., Ltd. Water-soluble copolymer having alkyl-modified carboxyl groups
WO2007132673A1 (fr) 2006-05-12 2007-11-22 Sumitomo Seika Chemicals Co., Ltd. Procédé de production de particules de polymère carboxylé granulaire et particules ainsi produites
US7842779B2 (en) 2006-05-12 2010-11-30 Sumitomo Seika Chemicals Co., Ltd. Process for producing granular carboxylated-polymer particle and granular carboxylated-polymer particle
JP5271079B2 (ja) * 2006-05-12 2013-08-21 住友精化株式会社 顆粒状カルボキシル基含有重合体粒子の製造方法及び顆粒状カルボキシル基含有重合体粒子
KR101409564B1 (ko) * 2006-05-12 2014-06-19 스미또모 세이까 가부시키가이샤 과립상 카르복실기 함유 중합체 입자의 제조 방법 및 과립상 카르복실기 함유 중합체 입자
US8304517B2 (en) 2007-06-19 2012-11-06 Sumitomo Seika Chemicals Co., Ltd. Method for producing granulated carboxyl group-containing polymer particle and granulated carboxyl group-containing polymer particle
WO2009022532A1 (fr) * 2007-08-10 2009-02-19 Sumitomo Seika Chemicals Co., Ltd. Procédé de fabrication de particules granulaires de polymère carboxylé et particules granulaires de polymère carboxylé
JP2016069439A (ja) * 2014-09-29 2016-05-09 株式会社日本触媒 新規架橋重合体およびその製造方法
WO2017164357A1 (fr) * 2016-03-25 2017-09-28 住友精化株式会社 Copolymère contenant un groupe carboxyle modifié par un alkyle
WO2023074719A1 (fr) * 2021-10-27 2023-05-04 住友精化株式会社 POLYMÈRE RÉTICULÉ DE COMPOSÉ ACIDE CARBOXYLIQUE α,β-INSATURÉ, ET APPLICATION ASSOCIÉE

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