WO2003016382A1 - Particle of crosslinked carboxylated polymer - Google Patents

Particle of crosslinked carboxylated polymer 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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Prior art keywords
containing polymer
carboxyl group
polymer particles
crosslinked
crosslinked carboxyl
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PCT/JP2002/007909
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French (fr)
Japanese (ja)
Inventor
Shigeki Hamamoto
Masatoyo Yoshinaka
Tomoki Kawakita
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Sumitomo Seika Chemicals Co., Ltd.
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Priority to JP2003521704A priority Critical patent/JPWO2003016382A1/en
Publication of WO2003016382A1 publication Critical patent/WO2003016382A1/en

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    • 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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Abstract

Particles of a crosslinked carboxylated polymer having a mean particle diameter of 20 to 800 µm which are obtained by: compression-molding a reaction product obtained by polymerizing an α,ß-unsaturated carboxylic acid with a compound having two or more ethylenically unsaturated groups in an inert solvent in the presence of a free-radical polymerization initiator; subsequently pulverizing the molding; and classifying the particles. The polymer particles are usable as, e.g., a thickener for cosmetics, moisturizing agent for poultices, or suspension stabilizer for emulsions or suspensions.

Description

明 細 書 架橋型カルボキシル基含有重合体粒子 技術分野  Description Crosslinked carboxyl-containing polymer particles Technical field
本発明は、 架橋型カルボキシル基含有重合体粒子に関する。 さらに詳しくは、 化粧品等の増粘剤、 パップ剤等の保湿剤、 乳化物や懸濁物等の懸濁安定剤等とし て好適に使用しうる架橋型カルボキシル基含有重合体粒子に関する。 背景技術  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. Background art
架橋型カルボキシル基含有重合体としては、 例えば、 アクリル酸等の ， β— 不飽和カルボン酸とポリアリルエーテルとの共重合体 （米国特許第 2 , 9 2 3 , 6 9 2号明細書） 、 ひ， ^—不飽和カルボン酸とへキサァリルトリメチレントリ スルホンとの共重合体 （米国特許第 2， 9 5 8 , 6 7 9号明細書） 、 ， β—不 飽和カルボン酸とリン酸トリアリルとの共重合体 （米国特許第 3， 4 2 6 , 0 0 4号明細書） 、 ， ^一不飽和カルボン酸とグリシジルメ夕クリレート等との共 重合体 （特開昭 5 8— 8 4 8 1 9号公報） 、 ァクリル酸等の ， ^—不飽和カル ボン酸とペン夕エリスリ トールァリルエーテルとの共重合体 （米国特許第 5 , 3 4 2， 9 1 1号明細書、 米国特許第 5， 6 6 3， 2 5 3号明細書および米国特許 第 4 , 9 9 6 , 2 7 4号明細書） 、 アクリル酸等の ， ^—不飽和カルボン酸と 、 （メタ） アクリル酸エステルとペンタエリスリ トールァリルエーテルとの共重 合体 （特公平 5 - 3 9 9 6 6号公報および特公昭 6 0— 1 2 3 6 1号公報） 等が 知られている。 これらの架橋型カルボキシル基含有重合体は、 水に分散、 膨潤さ せた後、 アルカリで中和して中和粘稠液とすることにより、 化粧品等の増粘剤、 パップ剤等の保湿剤、 乳化物や懸濁物等の懸濁安定剤等の用途に用いられている 前記架橋型カルボキシル基含有重合体をこれらの用途に使用するためには、 ま ず、 架橋型カルボキシル基含有重合体の均一な水分散液を調製し、 その後アル力 リで中和して中和粘稠液とする必要がある。 しかしながら、 前記架橋型カルボキ シル基含有重合体は、 通常、 微粉末であるため、 水に分散させる際に塊状物 （マ マコ） が生じやすい。 いったんママコが生成すると、 その表面にゲル状の層が形 成されるため、 その内部に水が浸透する速度が遅くなり、 均一な水分散液を得る ことが困難となるという欠点がある。 Examples of the crosslinked type carboxyl group-containing polymer include, for example, a copolymer of β-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), β-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. 58-84) No. 8,191), a copolymer of ^ -unsaturated carboxylic acid such as acrylic acid and pentaerythritol aryl ether (US Pat. No. 5,342,911, US Pat. Nos. 5,663,253 and U.S. Pat. Nos. 4,996,274), acrylic acid and the like; —Copolymer of unsaturated carboxylic acid, (meth) acrylate and pentaerythritol aryl ether (Japanese Patent Publication No. 5-39966 and Japanese Patent Publication No. 60-123636) Etc. are known. These 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. However, since 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. Once the mamako is formed, 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.
したがって、 架橋型カルボキシル基含有重合体の水分散液を調製する場合には 、 ママコの生成を防ぐために、 架橋型カルボキシル基含有重合体の粉末を水中に 高速攪拌下で徐々に添加するという生産効率が悪い操作を必要とし、 場合によつ てはママコの生成を防止するために特殊な溶解装置を必要とする。  Therefore, when preparing an aqueous dispersion of the crosslinked carboxyl group-containing polymer, 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 mamako. Require poor operation and, in some cases, require special dissolution equipment to prevent the formation of mamako.
また、 前記架橋型カルボキシル基含有重合体は、 微粉末でかつ帯電しやすいた め、 粉立ちが激しい。 したがって、 前記架橋型カルボキシル基含有重合体には、 取り扱いが難しいばかりでなく、 作業環境上好ましくないという欠点もある。 一方、 水への分散、 溶解性が改良された架橋型カルボキシル基含有重合体とし ては、 特殊な界面活性剤の存在下、 不活性溶媒中、 アクリル酸等の ， J5 -不飽 和カルボン酸とペン夕エリスリ トールァリルエーテルとを共重合させた共重合体 (特開平 6 — 1 9 9 9 6 9号公報） 、 析出重合中に水、 アルコール等の溶媒を添 加し、 析出してきた小粒子を顆粒状に造粒するか、 または析出重合させた後に、 水、 アルコール等の溶媒で造粒したポリ （メタ） アクリル酸またはその塩類 （特 開平 3— 8 9 4 5 8号公報） 等が知られている。  In addition, 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. On the other hand, as 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), in which a solvent such as water or an alcohol is added during precipitation polymerization to precipitate. Poly (meth) acrylic acid or its salts granulated with a solvent such as water or alcohol after granulation or precipitation polymerization of small particles (Japanese Patent Laid-Open Publication No. Hei 3-889458) Etc. are known.
しかしながら、 これら架橋型カルボキシル基含有重合体は、 水への分散性が改 善されているものの、 未だ十分であるとはいえない。 また、 架橋型カルボキシル 基含有重合体の水分散液が不均一である場合、 表面のなめらかさ、 増粘性および 透明性に優れた中和粘稠液を得るためには、 引き続き、 アルカリで中和して中和 粘稠液を得る際に、 長時間攪拌する必要があるため、 生産性に劣るという欠点が ある, 発明の開示 However, these 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
本発明の目的は、 水への分散性に優れ、 取り扱いが容易で、 その水分散液をァ ルカリで中和して得られる中和粘稠液が表面のなめらかさ、 増粘性および透明性 に優れた架橋型カルボキシル基含有重合体粒子を提供することにある。  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.
本発明は、 ， ^一不飽和カルボン酸類と、 エチレン性不飽和基を 2個以上有 する化合物とを、 不活性溶媒中で、 ラジカル重合開始剤の存在下、 重合させるこ とによって得られた生成物を圧縮成形後、 粉砕、 分級してなる、 中位粒子径が 2 0〜800 の架橋型カルボキシル基含有重合体粒子に関する。 発明を実施するための最良の形態  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. BEST MODE FOR CARRYING OUT THE INVENTION
本明細書にいう 「中位粒子径」 とは、 架橋型カルボキシル基含有重合体粒子を 篩で分級したときに各篩上に残っている架橋型カルボキシル基含有重合体粒子の 重量を順次積算して得られた積算重量が、 架橋型力ルボキシル基含有重合体粒子 の全重量の 50重量％に達したときの篩の目開きに相当する粒子径をいう。 より 具体的には、 J I S— Z 8 8 0 1— 1 982に規定された 7つの標準篩（目開き 8 5 0 m、 50 0 /m、 35 5 zm、 300 zm、 25 0 m、 1 8 0 /m、 1 0 6 ^m) および受け皿を用意し、 目開きの小さい篩から目開きの大きい篩を 順次積層し、 一番目開きの大きい篩に架橋型カルボキシル基含有重合体粒子 1 0 0 gを入れ、 ロータップ式篩振動器を用いて 1 0分間振動させ、 各篩上に残った 架橋型力ルポキシル基含有重合体粒子を秤量し、 順次積算して得られた積算重量 が架橋型カルボキシル基含有重合体粒子の全重量の 5 0重量％に達したときの篩 の目開きに相当する粒子径を次式により算出して求められた粒子径を中位粒子径 とする。 中位粒子径 （ m) = ( ) X (D-B) +B As used herein, 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. More specifically, 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
C-A  C-A
(式中、 Aは、 目開きの粗い篩から順次篩上に残った架橋型カルボキシル基含有 重合体粒子の重量を積算し、 積算重量が架橋型カルボキシル基含有重合体粒子の 全重量の 50重量％未満であり、 かつ 50重量％に最も近い篩までの積算値 （g ) である。 Bは、 Aの積算値を求めた時の篩の目開き （ zm) である。 Cは、 目 開きの粗レ、篩から順次篩上に残つた架橋型力ルポキシル基含有重合体粒子の重量 を積算し、 積算重量が、 架橋型カルボキシル基含有重合体粒子の全重量の 5 0重 量％以上であり、 かつ 5 0重量％に最も近い篩までの積算値 （g) である。 Dは 、 Cの積算値を求めた時の篩の目開き （ zm) である。 ）  (Where 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. % 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. And the integrated value (g) up to the sieve closest to 50% by weight. D is the sieve opening (zm) when the integrated value of C was determined.)
本発明の架橋型カルボキシル基含有重合体粒子の中位粒子径は、 20〜800 〃m、 好ましくは 1 0 0〜 70 0〃m、 より好ましくは 1 5 0〜600 amであ る。 架橋型カルボキシル基含有重合体粒子の中位粒子径が 20 zm未満の場合、 水への分散性が悪くなり、 表面のなめらかさ、 増粘性および透明性に優れた中和 粘稠液を得ようとする場合、 アルカリで中和する際に、 長時間攪拌する必要があ り、 さらに、 粉立ちが激しくなつて取り扱いにくくなる。 また、 架橋型カルボキ シル基含有重合体粒子の中位粒子径が 8 00 mを超える場合、 水への分散性は 良好であるが、 水との親和性が悪くなり、 アルカリで中和した中和粘稠液中に不 溶性のゲルが生成する。  The median particle size of the crosslinked carboxyl group-containing polymer particles of the present invention is 20 to 800 μm, preferably 100 to 700 μm, 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.
本発明の架橋型カルボキシル基含有重合体粒子の嵩密度は、 0. 2〜0. 6 g ZmL、 好ましくは 0. 25〜 6 gZmL、 より好ましくは 0. 3〜0. 5 5 gZmLであることが望ましい。 架橋型カルボキシル基含有重合体粒子の嵩密 度が 0. 2 gZmL未満の場合、 粉立ちが激しくなつて取り扱いにくくなるおそ れがある。 また、 嵩密度が 0. 6 g/mLを超える場合、 水に分散させる際に、 架橋型カルボキシル基含有重合体粒子が完全に分散するのに長時間を要するだけ でなく、 得られる中和粘稠液の表面のなめらかさが悪化するおそれがある。 ここで、 本明細書にいう 「嵩密度」 とは、 架橋型カルボキシル基含有重合体粒 子の重量と、 該重量の架橋型力ルボキシル基含有重合体粒子の容積との比をいう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.
。 より具体的には、 架橋型カルボキシル基含有重合体粒子 1 O gを 5 O m L容の 空のメスシリンダーの上部 5 c mの高さから 2 0秒間以内で投入した後、 架橋型 カルボキシル基含有重合体粒子の占める容積 （m L ) を測定し、 架橋型カルボキ シル基含有重合体粒子の重量 1 O gを、 架橋型カルボキシル基含有重合体粒子の 占める容積 （m L ) で除することにより算出した値をいう。 . More specifically, 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.
本発明で用いられる架橋型力ルポキシル基含有重合体は、 ot， ^—不飽和カル ボン酸類と、 エチレン性不飽和基を 2個以上有する化合物とを、 不活性溶媒中で 、 ラジ力ル重合開始剤の存在下で重合させることによつて製造することができる ο  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 ο
前記 ， ^一不飽和カルボン酸類としては、 特に限定されず、 例えば、 ァクリ ル酸、 メタクリル酸、 クロトン酸、 マレイン酸、 ィタコン酸、 フマル酸等の ， β一不飽和カルボン酸；ァクリル酸ラゥリル、 ァクリル酸ミリスチル、 アクリル 酸パルミチル、 アクリル酸ォレイル、 アクリル酸ステアリル、 アクリル酸ベへ二 ル、 メタクリル酸ラウリル、 メタクリル酸ミリスチル、 メタクリル酸パルミチル 、 メタクリル酸ォレイル、 メタクリル酸ステアリル、 メタクリル酸べへニル等の アルキル基の炭素数が 1 0〜3 0の ， ^—不飽和カルボン酸アルキルエステル 等が挙げられ、 これらは、 それぞれ単独で用いてもよく、 2種以上を併用しても よい。  The above-mentioned, ^ monounsaturated carboxylic acids are not particularly restricted but include, for example, β 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.
なお、 ， -不飽和カルボン酸は、 それ単独で用いてもよく、 アルキル基の 炭素数が 1 0〜3 0の α， —不飽和カルボン酸アルキルエステルとを併用して もよい。 中でも、 安価で入手が容易であり、 中和粘稠液の透明性に優れた架橋型 カルボキシル基含有重合体を得ることができることから、 ァクリル酸を単独で用 いるか、 またはアクリル酸とメタクリル酸ラウリルとの混合物を用いることが好 ましい。 a , —不飽和カルボン酸類の使用量は、 後述する不活性溶媒 1 0 0容量部に 対して 6〜2 5容量部、 好ましくは 8〜2 2容量部、 さらに好ましくは 1 3〜2 0容量部であることが望ましい。 α， ^一不飽和カルボン酸類の使用量が 6容量 部未満の場合、 得られる架橋型カルボキシル基含有重合体の中和粘稠液の透明性 が悪化するおそれがある。 また、 ， ^—不飽和カルボン酸類の使用量が 2 5容 量部を超える場合、 反応が進行するにつれ、 架橋型カルボキシル基含有重合体が 析出し均一に攪拌することが困難となり、 得られる架橋型カルボキシル基含有重 合体の中和粘稠液の表面のなめらかさが悪化するおそれがある。 The, -unsaturated carboxylic acid may be used alone or in combination with an α, -unsaturated carboxylic acid alkyl ester having an alkyl group having 10 to 30 carbon atoms. Above all, since it is possible to obtain a crosslinked carboxyl group-containing polymer which is inexpensive and easily obtainable and has excellent transparency of the neutralized viscous liquid, acrylic acid is used alone, or acrylic acid and lauryl methacrylate are used. It is preferred to use a mixture with a, —The amount of the unsaturated carboxylic acid used is 6 to 25 parts by volume, preferably 8 to 22 parts by volume, more preferably 13 to 20 parts by volume with respect to 100 parts by volume of the inert solvent described later. Part is desirable. When the amount of the α, ^ 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.
前記エチレン性不飽和基を 2個以上有する化合物としては、 特に限定されず、 例えば、 エチレングリコール、 プロピレングリコール、 ポリオキシエチレングリ コール、 ポリオキシプロピレングリコール、 グリセリン、 ポリグリセリン、 トリ メチロールプロパン、 ペン夕エリスリ トール、 サッカロ一ス、 ソルビトール等の ポリオールの 2置換以上のアクリル酸エステル類；前記ポリオールの 2置換以上 のメタクリル酸エステル類；前記ポリオールの 2置換以上のァリルエーテル類； フタル酸ジァリル、 リン酸トリアリル、 メタクリル酸ァリル、 テトラァリルォキ シェタン、 トリァリルシアヌレート、 アジピン酸ジビニル、 クロトン酸ビニル、 1， 5—へキサジェン、 ジビニルベンゼン等を挙げることができる。 中でも、 少 量で高い増粘性を有する中和粘稠液が得られ、 乳化物、 懸濁物等に高い懸濁安定 †生を付与することができることから、 ペンタエリスリ トールテトラァリルェ一テ ルおよびポリアリルサッカロースが好ましい。  The compound having two or more ethylenically unsaturated groups is not particularly limited. For example, ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, 2-substituted or more acrylates of polyols such as erythritol, saccharose, sorbitol, etc .; 2- or more-substituted methacrylates of the polyols; 2- or more-substituted aryl esters of the polyols; diaryl phthalate, triallyl phosphate Acrylyl methacrylate, tetraaryloxyshetane, triaryl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinylbenzene and the like. Above all, a small amount of a neutralized viscous liquid having a high viscosity can be obtained, and high suspension stability can be imparted to emulsions and suspensions. Therefore, pentaerythritol tetraaryl ether And polyallyl sucrose.
エチレン性不飽和基を 2個以上有する化合物の使用量は、 ， ^一不飽和カル ボン酸類 1 0 0重量部に対して、 0 . 1 5〜2重量部、 好ましくは 0 . 3〜 1 . 5重量部であることが望ましい。 ェチレン性不飽和基を 2個以上有する化合物の 使用量が 0 . 1 5重量部未満の場合、 得られる架橋型カルボキシル基含有重合体 の中和粘稠液の粘度が低下するおそれがある。 また、 エチレン性不飽和基を 2個 以上有する化合物の使用量が 2重量部を超える場合、 得られる架橋型カルボキシ ル基含有重合体の中和粘稠液中に不溶性のゲルが生成しやすくなるおそれがある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
0 0
前記ラジカル重合触媒としては特に限定されず、 例えば、 ， ' ーァゾビス イソブチロニトリル、 2 , 2 ' —ァゾビス一 2 , 4 —ジメチルバレロニトリル、 ジメチルー 2 , 2 ' ーァゾビスイソプチレート、 過酸化ベンゾィル、 ラウロイル パーォキサイド、 クメンハイドロパーォキサイド、 第三級ブチルハイドロパ一ォ キサイド等を挙げることができる。  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.
ラジカル重合触媒の使用量は、 /3—不飽和カルボン酸類 1 0 0重量部に対 して、 0 . 0 1〜0 . 4 5重量部、 好ましくは 0 . 0 1〜0 . 3 5重量部である ことが望ましい。 ラジカル重合触媒の使用量が 0 . 0 1重量部未満の場合、 反応 速度が遅くなるため経済的でなくなるおそれがある。 また、 ラジカル重合触媒の 使用量が 0 . 4 5重量部を超える場合、 得られる架橋型力ルポキシル基含有重合 体の中和粘稠液の表面のなめらかさが悪化するおそれがある。  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.
本明細書にいう 「不活性溶媒」 とは、 CL , /8—不飽和カルボン酸類およびェチ レン性不飽和基を 2個以上有する化合物を溶解するが、 得られる架橋型カルボキ シル基含有重合体を溶解しない溶媒をいう。  As used herein, the term "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.
不活性溶媒としては、 例えば、 ノルマルペンタン、 ノルマルへキサン、 イソへ キサン、 ノルマルヘプ夕ン、 ノルマルオクタン、 イソオクタン、 シクロペンタン 、 メチルシクロペンタン、 シクロへキサン、 メチルシクロへキサン、 ベンゼン、 トルエン、 キシレン、 クロ口ベンゼン、 エチレンジクロライド、 酢酸ェチル、 酢 酸イソプロピル、 メチルェチルケトン、 メチルイソプチルケトン等を挙げること ができる。 これらは単独で使用してもよく、 2種以上を併用してもよレ、。 中でも α  Examples of the inert solvent 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 α
net質が安定しており入手が容易である観点から、 エチレンジクロライドおよび ノルマルへキサンが好ましい。  Ethylene dichloride and normal hexane are preferred from the viewpoint of stable net quality and easy availability.
a , —不飽和カルボン酸類と、 エチレン性不飽和基を 2個以上有する化合物 とを反応させる際の雰囲気は、 例えば、 窒素ガス、 アルゴンガス等の不活性ガス 雰囲気であることが好ましい。 a, — 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.
反応温度は、 反応溶液の粘度上昇を抑制し、 得られる架橋型カルボキシル基含 有重合体の中和粘稠液の表面のなめらかさを向上させる観点から、 5 0〜9 0 °C 、 好ましくは 5 5〜7 5 °Cであることが望ましい。  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.
反応時間は、 反応温度によって異なるので一概には決定することができないが 、 通常、 2〜1 0時間である。  The reaction time differs depending on the reaction temperature and cannot be unconditionally determined, but is usually 2 to 10 hours.
反応終了後、 反応溶液を 8 0〜1 3 0 °Cに加熱し、 不活性溶媒を揮散除去する ことにより白色微粉末の架橋型カルボキシル基含有重合体を得ることができる。 加熱温度は、 8 0 °C未満の場合、 乾燥に長時間を要するおそれがあり、 1 3 0 °C を超える場合、 得られる架橋型カルボキシル基含有重合体の中和粘稠液の表面の なめらかさが悪化するおそれがある。  After completion of the reaction, 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.
かくして得られる架橋型カルボキシル基含有重合体を、 圧縮成形後、 粉砕、 分 級することにより、 本発明の架橋型カルボキシル基含有重合体粒子が得られる。 本発明の架橋型カルボキシル基含有重合体粒子の製造方法は、 1 1 0 °Cで 3時 間放置した後の減量 （以下、 「乾燥減量」 という） が 7重量％以下である架橋型 カルボキシル基含有重合体を圧縮成形後、 粉砕、 分級する工程を含んでいる。 か かる製造方法の具体例としては、 乾燥減量が 7重量％以下の架橋型カルボキシル 基含有重合体を適度な大きさに圧縮成形した後、 粉砕して所望の中位粒子径に分 級する方法等が挙げられる。  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.
前記圧縮成形する際に用いられる圧縮成形装置としては、 特に限定されず、 例 えば、 小型電動ポンプ油圧式プレス機、 ロールプレス式圧縮成形機、 押出成形機 等の一般に使用されている圧縮成形装置を使用することができる。  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.
圧縮成形する際の圧縮圧力は、 特に限定されず、 使用する成形機の機種、 架橋 型カルボキシル基含有重合体の組成、 乾燥減量、 圧縮温度等に応じて、 任意に設 定することができるが、 通常、 ゲージ圧で 9〜1 5 O M P a、 好ましくは 1 4〜 1 0 O M P aであることが望ましい。 圧縮圧力が 9 M P a未満の場合、 架橋型力 ルポキシル基含有重合体が十分に圧縮成形されず、 得られる圧縮成形体が脆くな り、 微粉含量が多くなるおそれがある。 また、 圧縮圧力が 1 5 0 M P aを超える 場合、 得られる架橋型カルボキシル基含有重合体粒子に、 ガラス状の親水性が悪 レ、部分が生成するおそれがある。 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.
圧縮成形された架橋型力ルポキシル基含有重合体の成形体の大きさおよび形状 は、 圧縮成形装置によって異なるが、 例えば、 小型電動ポンプ油圧式プレス機で は、 高さ 5 mm、 直径 2 5 mm程度の円柱状である。 また、 ロールプレス式圧縮 成形機では、 厚さ 1〜1 O mm程度の板状である。  The size and shape of the compression-molded cross-linked polymer of ropoxyl group-containing polymer vary depending on the compression molding equipment.For example, 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.
次に、 架橋型カルボキシル基含有重合体の圧縮成形体を粉砕する。  Next, the compression-molded body of the crosslinked carboxyl group-containing polymer is pulverized.
粉砕する際に用いられる粉砕装置としては、 特に限定されず、 例えば、 ピンミ ル型粉砕機、 ハンマ一ミル型粉砕機、 ジヱットミル型粉砕.機等の一般に使用され ている粉砕機を使用することができる。  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.
かくして粉砕し、 次いで、 所望の中位粒子径を有する粒子が得られるように、 所望の目開きの篩を用いて分級して粗粉を取り除くことにより、 本発明の架橋型 力ルポキシル基含有重合体粒子が得られる。  Thus, 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.
本発明の架橋型カルボキシル基含有重合体粒子は、 特定の中位粒子径を有する ため、 微粉末状の架橋型カルボキシル基含有重合体と比べママコが発生しにく く 、 水への分散性に優れ、 粉立ちが少なく作業性に優れている。 また、 本発明の架 橋型カルボキシル基含有重合体粒子を水に分散した後、 水酸化ナトリウム、 トリ エタノールアミン等のアルカリで中和することにより、 短時間で表面のなめらか さ、 増粘性および透明性に優れた中和粘稠液が得られる。 以下に、 実施例および比較例を挙げて本発明をさらに詳しく説明するが、 本発 明はこれら実施例のみに限定されるものではない。 実施例 1 攪拌機、 温度計、 窒素吹き込み管および冷却管を備えた 5 0 OmL容の四つ口 フラスコに、 アクリル酸 60 g (57. lmL) 、 ペン夕エリスリ トールテトラ ァリルエーテル 0. 48 g、 α, ' —ァゾビスイソブチロニトリル 0. 00 9 g、 エチレンジクロライド 3 75 g (30 OmL) を仕込んだ。 引き続き、 均一 に攪拌、 混合した後、 反応容器の上部空間、 原料および溶媒中に存在している酸 素を除去するために、 溶液中に窒素ガスを吹き込んだ。 次いで、 窒素雰囲気下、 70〜75でに保持して 3時間反応させた。 Since the crosslinked carboxyl group-containing polymer particles of the present invention have a specific median particle diameter, they are less susceptible to mamako and have better dispersibility in water than fine powdered crosslinked carboxyl group-containing polymers. Excellent, low dusting and excellent workability. In addition, after 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. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. 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, α, '— 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.
反応終了後、 生成したスラリーを 1 1 0°Cに加熱して、 エチレンジクロライド を留去し、 白色微粉末の架橋型カルボキシル基含有重合体 6 O gを得た。 得られ た架橋型力ルポキシル基含有重合体の中位粒子径は、 レーザー回折式粒度分布測 定装置 （株式会社島津製作所の商品名 S A L D— 200 0 J、 分散媒ノルマルへ キサン） で測定した結果 1 1 mであり、 また、 嵩密度は 0. 1 7 gZmLであ つ Tこ。  After the completion of the reaction, 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.
得られた架橋型カルボキシル基含有重合体 2 gを、 5mmx 25 mm øの型枠 内に敷き詰め、 小型電動ポンプ油圧式プレス機 （理研精機株式会社の商品名 C D M- 20) により 1 4. 7MPa (ゲージ圧） の圧縮圧力で圧縮成形し、 円柱型 の架橋型カルボキシル基含有重合体のタブレツト 2 gを得た。 このタブレツト 2 5個 （合計 50 g) を作製した。  2 g of the obtained cross-linked carboxyl group-containing polymer was spread in a 5 mm x 25 mm ø 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.
得られた架橋型カルボキシル基含有重合体のタブレツトを回転数が 7000 r mに設定されたピンミル型粉砕器 （ホソカワミクロン株式会社の商品名フアイ ンインパクトミル） に 1 gZ秒の速度で投入し、 粉砕した。 得られた粉砕物 5 0 gを目開き 1 0 0 0 mの篩で粗粉を取り除き、 本発明の架橋型カルボキシル基 含有重合体粒子 37. 5 gを得た。 得られた架橋型カルボキシル基含有重合体粒 子の中位粒子径は、 53 1 mであり、 嵩密度は 0. 3 8 g/mLであった。 実施例 2 実施例 1と同様の方法で得られた架橋型カルボキシル基含有重合体のタブレッ ト 25個 （合計 5 0 g) を回転数が 7000 r p mに設定されたピンミル型粉砕 器 （ホソカワミクロン株式会社の商品名ファインインパク トミル） に 1 gZ秒の 速度で投入し、 粉砕した。 得られた粉砕物 50 gを目開き 5 0 0 zmの篩で粗粉 を取り除き、 本発明の架橋型カルボキシル基含有重合体粒子 32. 4 gを得た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は、 225 amであ り、 嵩密度は 0. 34 gZmLであった。 実施例 3 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
実施例 1と同様の方法で得られた架橋型カルボキシル基含有重合体のタブレッ ト 25個 （50 g) を回転数が 7000 r pmに設定されたピンミル型粉砕器 （ ホソカワミクロン株式会社の商品名ファインインパクトミル） に 1 g/秒の速度 で投入し、 粉砕した。 得られた粉砕物 5 0 gを目開き 3 0 0 zmの篩で粗粉を取 り除き、 本発明の架橋型カルボキシル基含有重合体粒子 5. 8 gを得た。 得られ た架橋型カルボキシル基含有重合体粒子の中位粒子径は、 1 5 1 amであり、 嵩 密度は 0. 3 1 gZm であった。 実施例 4  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 4
実施例 1において、 圧縮圧力を 24. 5 MP a (ゲージ圧） に変更した以外は 、 実施例 1と同様にして、 本発明の架橋型カルボキシル基含有重合体粒子 36 g を得た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は 549 mであり、 嵩密度は 0. 44 gZmLであった。 実施例 5  In 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
実施例 1において、 圧縮圧力を 34. 3MP a (ゲージ圧） に変更した以外は 、 実施例 1と同様にして、 本発明の架橋型カルボキシル基含有重合体粒子 33 を得た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は 5 60 mであり、 嵩密度は 0. 4 8 gZmLであった。 実施例 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
実施例 1において、 圧縮圧力を 4 9 MP a (ゲージ圧） に変更した以外は、 実 施例 1と同様にして、 本発明の架橋型カルボキシル基含有重合体粒子 30 gを得 た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は 5 8 1 zmで あり、 嵩密度は 0. 52 g/mLであった。 実施例 7  In 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
実施例 1において、 圧縮圧力を 73. 5MPa (ゲージ圧） に変更した以外は 、 実施例 1と同様にして、 本発明の架橋型カルボキシル基含有重合体粒子 28 を得た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は 5 9 6 I mであり、 嵩密度は 0. 5 3 g/mLであった。 実施例 8  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 8
実施例 1において、 圧縮圧力を 9 8 MP a (ゲージ圧） に変更した以外は、 実 施例 1と同様にして、 本発明の架橋型カルボキシル基含有重合体粒子 25 gを得 た。 得られた架橋型カルボキシル基含有重合体粒子の中位粒子径は 60 9 «mで あり、 嵩密度は 0. 5 9 g/mLであった。 実施例 9  25 g of crosslinked carboxyl-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 98 MPa (gauge pressure). The median particle size of the obtained crosslinked carboxyl group-containing polymer particles was 609 m, and the bulk density was 0.59 g / mL. Example 9
攪拌機、 温度計、 窒素吹き込み管および冷却管を備えた 5 0 OmL容の四つ口 フラスコに、 アクリル酸 5 7. 6 g (54. 9m L) 、 メタクリル酸ラウリル 2 . 4 g (2. 8 mL) 、 ペン夕エリスリ トールテトラァリルエーテル 0. 30 g 、 , a' ーァゾビスイソプチロニトリル 0. 20 g、 ノルマルへキサン 275 . 0 g (4 1 0. 4mL) を仕込んだ。 引き続き、 均一に攪拌、 混合した後、 反 応容器の上部空間、 原料および溶媒中に存在している酸素を除去するために、 溶 液中に窒素ガスを吹き込んだ。 次いで、 窒素雰囲気下、 60〜6 5 °Cに保持して 4時間反応させた。 In a 50 OmL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and condenser, 57.6 g (54.9 mL) of acrylic acid and 2.4 g (2.8 g) of lauryl methacrylate were added. mL), Penyu erythritol tetraaryl ether 0.30 g, a'-azobisisobutyronitrile 0.20 g, normal hexane 275 .0 g (4.10.4 mL) was 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 reaction was carried out for 4 hours while maintaining the temperature at 60 to 65 ° C. under a nitrogen atmosphere.
反応終了後、 生成したスラリーを 9 0°Cに加熱して、 ノルマルへキサンを留去 し、 白色微粉末の架橋型カルボキシル基含有重合体 5 9 gを得た。 得られた架橋 型カルボキシル基含有重合体の中位粒子径は、 レーザ一回折式粒度分布測定装置 (株式会社島津製作所の商品名 SALD— 2000 J、 分散媒ノルマルへキサン ) で測定した結果、 1 7 ^mであり、 また、 嵩密度は 0. 1 3 gZmLであった 得られた架橋型カルボキシル基含有重合体を実施例 1 と同様に圧縮成形、 粉砕 、 分級して、 本発明の架橋型カルボキシル基含有重合体粒子 43 gを得た。 得ら れた架橋型カルボキシル基含有重合体粒子の中位粒子径は 40 9 であり、 嵩 密度は 0. 34 g/mLであった。 実施例 1 0  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). 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. Example 10
攪拌機、 温度計、 窒素吹き込み管および冷却管を備えた 5 0 OmL容の四つ口 フラスコに、 アクリル酸 5 7. 3 g (54. 6mL) 、 ポリアリルサッカロ一ス 0. 4 1 g、 ひ， a' ーァゾビスイソプチロニトリル 0. l g、 エチレンジクロ ライド 5 25 g (42 OmL) を仕込んだ。 引き続き、 均一に攪拌、 混合した後 、 反応容器の上部空間、 原料および溶媒中に存在している酸素を除去するために 、 溶液中に窒素ガスを吹き込んだ。 次いで、 窒素雰囲気下、 70〜75でに保持 して 3時間反応させた。  In a 50 OmL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube and cooling tube, 57.3 g (54.6 mL) of acrylic acid, 0.41 g of polyallyl saccharose, A, a'-azobisisobutyronitrile 0.1 g and ethylene dichloride 525 g (42 OmL) 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.
反応終了後、 生成したスラリーを 1 1 0°Cに加熱して、 エチレンジクロライド を留去し、 白色微粉末の架橋型カルボキシル基含有重合体 57 gを得た。 得られ た架橋型カルボキシル基含有重合体の中位粒子径は 1 5 mであり、 また、 嵩密 度は 0. 1 7 g/mLであった。 After the completion of the reaction, 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.
得られた架橋型カルボキシル基含有重合体を実施例 1と同様に圧縮成形、 粉砕 、 分級して、 本発明の架撟型カルボキシル基含有重合体粒子 4 1 gを得た。 得ら れた架橋型カルボキシル基含有重合体粒子の中位粒子径は、 5 09 であり、 嵩密度は 0. 39 g/mLであった。 比較例 1  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
実施例 4において、 架橋型カルボキシル基含有重合体の粉砕物を分級しない以 外は実施例 1と同様にして架橋型カルボキシル基含有重合体粒子 5 0 gを得た。 中位粒子径は 820〃mであり、 嵩密度は 0. 63 g/mLであった。 比較例 2  In 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 µm, and the bulk density was 0.63 g / mL. Comparative Example 2
攪拌機、 温度計、 窒素吹き込み管および冷却管を備えた 5 0 OmL容の四つ口 フラスコに、 アクリル酸 6 0 g ( 5 7. 1 mL) 、 ペン夕エリスリ トールテトラ ァリルエーテル 0. 48 g、 ， a' ーァゾビスイソブチロニトリル 0. 00 9 g、 エチレンジクロライド 375 g (30 OmL) を仕込んだ。 引き続き、 均一 に攪拌、 混合した後、 反応容器の上部空間、 原料および溶媒中に存在している酸 素を除去するために、 溶液中に窒素ガスを吹き込んだ。 次いで、 窒素雰囲気下、 70〜75 °Cに保持して 3時間反応させた。  In a 50 OmL four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, and cooling tube, 60 g (57. 1 mL) of acrylic acid, 0.48 g of pen-erythritol tetraaryl ether, a'azobisisobutyronitrile 0.009 g and ethylene dichloride 375 g (30 OmL) 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 ° C. for 3 hours under a nitrogen atmosphere.
反応終了後、 生成したスラリーを 1 1 0°Cに加熱して、 エチレンジクロライド を留去し、 白色微粉末の架橋型カルボキシル基含有重合体 6 0 gを得た。 得られ た架橋型カルボキシル基含有重合体の中位粒子径は、 レーザ一回折式粒度分布測 定装置 （株式会社島津製作所の商品名 SAL D_ 2000 J、 分散媒ノルマルへ キサン） で測定した結果、 1 1 /zmであり、 また、 嵩密度は 0. 1 7 g/mL-e あつ 7Z 比較例 3 After the completion of the reaction, 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
攪拌機、 温度計、 窒素吹き込み管および冷却管を備えた 5 0 OmL容の四つ口 フラスコに、 アクリル酸 60 g (5 7. 1 mL) 、 ペンタエリスリ トールテトラ ァリルエーテル 0. 48 g、 α, α' —ァゾビスイソブチロニトリル 0. 0 0 9 g、 エチレンジクロライド 375 g (3 0 OmL) を仕込んだ。 引き続き、 均一 に攪拌、 混合した後、 反応容器の上部空間、 原料および溶媒中に存在している酸 素を除去するために、 溶液中に窒素ガスを吹き込んだ。 次いで、 窒素雰囲気下、 70〜75 °Cに保持して 3時間反応させた。  In a 50 OmL four-necked flask equipped with a stirrer, thermometer, nitrogen injection tube and condenser, 60 g (57.1 mL) of acrylic acid, 0.48 g of pentaerythritol tetraaryl ether, α, α ' —0.09 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 ° C. for 3 hours under a nitrogen atmosphere.
反応終了後、 50°Cで、 エタノール 6 gとエチレンジクロライド 1 0 gの混合 溶媒を生成したスラリーに加え、 1 1 0°Cに加熱して、 エタノールとエチレンジ クロライドを留去し、 白色顆粒状の架橋型カルボキシル基含有重合体粒子 60 g を得た。 得られた白色顆粒状の架橋型カルボキシル基含有重合体粒子の中位粒子 径は 9 8 であり、 嵩密度は 0. 2 1 g/mLであった。  After completion of the reaction, a mixed solvent of ethanol 6 g and ethylene dichloride 10 g was added to the resulting slurry at 50 ° C, and the mixture was heated to 110 ° C to distill off ethanol and ethylene dichloride to give white granules. Thus, 60 g of crosslinked carboxyl group-containing polymer particles were obtained. The median particle size of the obtained white granular crosslinked carboxyl group-containing polymer particles was 98, and the bulk density was 0.21 g / mL.
〔架橋型力ルボキシル基含有重合体粒子の物性評価〕 (Evaluation of physical properties of crosslinked type ruboxyl group-containing polymer particles)
各実施例および各比較例で得られた架橋型力ルボキシル基含有重合体粒子の物 性を以下の方法に基づいて評価した。 その結果を表 1に示す。  The physical properties of the crosslinked type ruboxyl group-containing polymer particles obtained in each Example and each Comparative Example were evaluated based on the following methods. The results are shown in Table 1.
( 1 ) 分散性  (1) Dispersibility
1 L容のビーカ—にイオン交換水 4 8 3. 3 gを入れ、 4枚羽根パドル翼 （翼 径 5 Omm) を備えた攪拌機を用い、 毎分 500回転で攪拌しながら、 架橋型力 ルポキシル基含有重合体粒子 2. 5 を約1 0秒間かけて徐々に投入した。 投入 後 1 5分経過後攪拌を停止し、 ママコの生成の有無を目視にて評価した。  Add 43.3 g of ion-exchanged water to a 1 L beaker, and use a stirrer equipped with 4-blade paddle blades (blade diameter 5 Omm) while stirring at 500 revolutions per minute. The group-containing polymer particles 2.5 were gradually charged over about 10 seconds. After 15 minutes from the introduction, the stirring was stopped, and the presence or absence of formation of mamaco was visually evaluated.
(2) 中和粘稠液の表面のなめらかさ  (2) Smoothness of the surface of the neutralized viscous liquid
前記 （ 1 ) で得られた水分散液に 6重量％水酸化ナトリゥム水溶液 1 4. 2 g を加え、 C T F A (ザ'コスメティック ' トイレタリ 'アンド 'フラグランス ' アソシエーション） に準拠した攪拌翼で 1時間攪拌して架橋型カルボキシル基含 有重合体粒子の中和粘稠液を得た。 To the aqueous dispersion obtained in the above (1), 14.2 g of a 6% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred for 1 hour with a stirring blade conforming to CTFA (The 'Cosmetic'Toiletries' and 'Fragrance' Association). Stir to include cross-linked carboxyl groups A neutralized viscous liquid of polymer particles was obtained.
得られた架橋型カルボキシル基含有重合体粒子の中和粘稠液の表面を目視にて 評価した。 評価は男女 1 0人を評価パネラーとし、 中和粘稠液の表面のなめらか さについて良好であると感じた人数を集計し、 以下の評価基準に基づレ、て判定し た。 なお、 通常の場合、 以下の基準で B以上であれば、 表面のなめらかさに優れ ていると判断できる。  The surface of the neutralized viscous liquid of the obtained crosslinked carboxyl group-containing polymer particles was visually evaluated. For the evaluation, 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.
〔評価基準〕  〔Evaluation criteria〕
S ：中和粘稠液の表面がなめらかであると感じた人数が 1 0人  S: 10 people felt that the surface of the neutralized viscous liquid was smooth
A：中和粘稠液の表面がなめらかであると感じた人数が 8〜9人  A: 8-9 people felt that the surface of the neutralized viscous liquid was smooth
B ：中和粘稠液の表面がなめらかであると感じた人数が 5〜7人  B: 5 to 7 people felt that the surface of the neutralized viscous liquid was smooth
C ：中和粘稠液の表面がなめらかであると感じた人数が 4人以下  C: No more than 4 people felt that the surface of the neutralized viscous liquid was smooth
( 3 ) 粘度  (3) Viscosity
前記 （2 ) で得られた架橋型カルボキシル基含有重合体粒子の中和粘稠液を、 B型回転粘度計を用い、 口一夕一 N o . 7、 毎分 2 0回転、 温度 2 5 °Cの条件下 で測定した。 なお、 通常の場合、 2 5でにおける粘度が 4 2 0 0 O m P a ■ s以 上であれば粘度が高いと判断することができる。  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.
( 4 ) 透明性  (4) Transparency
前記 （2 ) で得られた架橋型カルボキシル基含有重合体粒子の中和粘稠液を 1 c m x 1 c mのセルに入れ、 4 2 5 n mの波長の光線の透過率を測定した。 なお 、 通常の場合、 透過率が 9 4 %以上であれば透明性に優れていると判断すること ができる。 表 1 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
Figure imgf000018_0001
表 1に示された結果から、 実施例 1 〜 1 0で得られた架橋型カルボキシル基含 有重合体粒子は、 水への分散性に優れているため、 その水分散液を、 アルカリで 中和して得られた中和粘稠液は、 表面のなめらかさ、 増粘性および透明性に優れ ていることがわかる。 以上説明したように、 本発明の架橋型カルボキシル基含有重合体粒子は、 特定 の中位粒子径を有するので、 水への分散性に優れ、 取り扱いが容易で、 その水分 散液をアル力リで中和して得られる中和粘稠液の表面のなめらかさ、 増粘性およ ぴ透明性に優れているという効果が発現される。
Figure imgf000018_0001
From the results shown in 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 効果 The effect of excellent transparency is exhibited.
また、 従来の微粉末の架橋型カルボキシル基重合体を用いた場合には、 水分散 液をアルカリで中和する際に、 長時間、 例えば、 1 0時間程度攪拌しないと表面 のなめらかさ、 増粘性および透明性に優れた中和粘稠液が得られない。 これに対 して、 本発明の架橋型カルボキシル基含有重合体粒子によれば、 特定の中位粒子 径を有するので、 均一な水分散液が容易に得られ、 アルカリで中和する際に、 短 時間、 例えば、 1時間程度攪拌するだけで、 表面のなめらかさ、 増粘性および透 明性に優れた中和粘稠液を得ることができる。 産業上の利用可能性  In addition, when a conventional fine powder of a cross-linked carboxyl group polymer is used, when the aqueous dispersion is neutralized with an alkali, the surface becomes smooth and increases without stirring for a long time, for example, about 10 hours. A neutralized viscous liquid having excellent viscosity and transparency cannot be obtained. On the other hand, according to the crosslinked carboxyl group-containing polymer particles of the present invention, since they have a specific median particle size, a uniform aqueous dispersion can be easily obtained, and when neutralized with an alkali, By stirring for a short period of time, for example, for about one hour, a neutralized viscous liquid excellent in surface smoothness, thickening and transparency can be obtained. Industrial applicability
本発明の架橋型カルボキシル基含有重合体粒子は、 化粧品等の増粘剤、 パップ 剤等の保湿剤、 乳化物や懸濁物等の懸濁安定剤等として好適に使用することがで きる。  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.

Claims

請求の範囲 The scope of the claims
1. a, ^一不飽和カルボン酸類と、 エチレン性不飽和基を 2個以上有する化 合物とを、 不活性溶媒中で、 ラジカル重合開始剤の存在下、 重合させることによ り得られる生成物を圧縮成形後、 粉砕、 分級してなる、 中位粒子径が 2 0〜8 0 0 zmの架橋型カルボキシル基含有重合体粒子。 1. Obtained by polymerizing a, ^ 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 Crosslinked carboxyl group-containing polymer particles having a median particle diameter of 20 to 800 zm, which are obtained by compression molding, pulverizing and classifying the product.
2. 嵩密度が、 0. 2〜0. 6 g/mLである請求項 1記載の架橋型カルボキ シル基含有重合体粒子。 2. The crosslinked carboxyl group-containing polymer particles according to claim 1, having a bulk density of 0.2 to 0.6 g / mL.
3. a, —不飽和カルボン酸類が、 アクリル酸またはアクリル酸とメタクリ ル酸ラウリルとの混合物である請求項 1記載の架橋型カルボキシル基含有重合体 粒子。 3. The crosslinked carboxyl group-containing polymer particle according to claim 1, wherein the a, —unsaturated carboxylic acid is acrylic acid or a mixture of acrylic acid and lauryl methacrylate.
4. エチレン性不飽和基を 2個以上有する化合物がペン夕エリスリ トールテト ラァリルエーテルまたはポリァリルサッ力ロースである請求項 1記載の架橋型力 ルボキシル基含有重合体粒子。 4. The crosslinked type ruboxyl group-containing polymer particle according to claim 1, wherein the compound having two or more ethylenically unsaturated groups is penyl erythritol tetralyl ether or polyarylsulfurose.
5. 乾燥減量が 7重量％以下の架橋型カルボキシル基含有重合体を圧縮成形後 、 粉砕、 分級する工程を含む請求項 1記載の架橋型カルボキシル基含有重合体粒 子の製造方法。 5. The method for producing crosslinked carboxyl group-containing polymer particles according to claim 1, comprising a step of compression-molding, pulverizing and classifying the crosslinked carboxyl group-containing polymer having a loss on drying of 7% by weight or less.
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