CN104250328B - Acrylic resin particle and the external preparation using the acrylic resin particle - Google Patents
Acrylic resin particle and the external preparation using the acrylic resin particle Download PDFInfo
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- CN104250328B CN104250328B CN201310268457.6A CN201310268457A CN104250328B CN 104250328 B CN104250328 B CN 104250328B CN 201310268457 A CN201310268457 A CN 201310268457A CN 104250328 B CN104250328 B CN 104250328B
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Abstract
The present invention provides a kind of in the case of being used for external preparation, smooth use feeling can be brought to external preparation and the less acrylic resin particle of creak sense and the external preparation for including the acrylic resin particle.The acrylic resin particle of the present invention contains the acrylic resin using methyl methacrylate component as principal component, it is characterized in that, volume average particle size be 4~10 μm and pass through the particle surface that scanning electron microscope is observed regulation divide region memory the number of protuberance be 4~30.
Description
Technical field
External preparation the present invention relates to acrylic resin particle and using the acrylic resin particle.
Background technology
Conventional resin particle is except improving the slickness of the external preparations such as cosmetics or smooth sense of touch being assigned to external preparation
Beyond purpose, used with various purpose.Resin particle be using emulsion polymerization, suspension polymerization, seeded polymerization, point
Polymerization manufacture known to polymerization etc. is dissipated, spherical resin particle can be obtained.
Have disclosed in patent document 1 by using resin particle diameter as based on 0.1~100 μm (methyl) acrylate monomer into
Point resin particle, it is more than 50 DEG C, than the condition below the temperature of low 10 DEG C of the thermal decomposition initial temperature of the resin particle
Under, handled in alkaline aqueous medium, the content of remaining (methyl) acrylate monomer is the (first of below 20ppm
Base) acrylate resin beads, and describe since residual monomer is less and can be suitable in cosmetics.
But in the case that above-mentioned (methyl) acrylate resin beads are used for cosmetics, there are the following problems：
On skin smoothly smear cosmetics when smooth use feeling it is relatively low, and with resin particle rub each other when friction
Caused creak sense（キ シ ミ feel（Creaky））.
Patent document 1：Japanese Unexamined Patent Publication 11-322836 publications
The content of the invention
The present invention provides a kind of in the case of external preparation, smooth use feeling and creak sense can be brought to external preparation
（Creaky）Less acrylic resin particle and the external preparation using the acrylic resin particle.
The acrylic resin particle of the present invention is to contain the acrylic acid series using methyl methacrylate component as principal component
The acrylic resin particle of resin, it is characterised in that volume average particle size is 4~10 μm and passes through scanning electron microscope
The particle surface of observation regulation division region memory protuberance number be 4~30.
The acrylic resin of acrylic resin particle is formed using methyl methacrylate component as principal component.In addition,
" using methyl methacrylate component as principal component " refers to, in the monomer component for forming acrylic resin, methacrylic acid
The content of methacrylate compound is more than 50 weight %.
The acrylic resin of acrylic resin particle is formed, monomer component can be only methyl methacrylate,
Can also contain can be with the other monomers component of methyl methacrylate copolymer.
As can be not particularly limited with the monomer of methyl methacrylate copolymer, for example, can enumerate acrylic acid,
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl base
Ester, octadecyl acrylate, acrylic acid-2-ethyl caproite, tetrahydrofurfuryl acrylate, methacrylic acid, methacrylic acid second
Ester, propyl methacrylate, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, metering system
Sour n-octyl, lauryl methacrylate, methacrylic acid -2- ethylhexyls, stearyl methacrylate etc..This
Outside, can be used alone with the monomer of methyl methacrylate copolymer can also and with two or more.
Acrylic resin can be crosslinked.It is crosslinked by acrylic resin, obtained acrylic resin grain
Son has given play to the excellent effect being difficult to finish swelling.
For cross-linked acrylic acid system resin, as long as making methyl methacrylate and the starting monomer containing multi-functional monomer
It polymerize and manufactures acrylic resin particle.As multi-functional monomer, for example, it is preferable to be trimethylol propane trimethyl
The propylene such as acrylate, ethylene glycol dimethacrylate, dimethacrylate diethylene glycol (DEG) ester, dimethacrylate triethyleneglycol ester
The multi-functional monomer of acid system, is preferably ethylene glycol dimethacrylate.In addition, multi-functional monomer can be used alone and also may be used
With and with two or more.
The content of multi-functional monomer in starting monomer, due to obtaining being difficult to the acrylic resin grain to finish swelling
Son, therefore be preferably 1~15 parts by weight, more preferably 3~10 parts by weight are special relative to 100 parts by weight of methyl methacrylate
You Xuanwei not 5~10 parts by weight.
The volume average particle size of acrylic resin particle, contains the feelings in external preparation making acrylic resin particle
Under condition, the smooth use feeling of external preparation is improved, reduces creak sense when using external preparation, alternatively, reducing the coarse of external preparation
Sense, therefore 4~10 μm are limited to, it is preferably 6~10 μm, more preferably 6~8 μm.
The volume average particle size of acrylic resin particle is by Coulter Multisizer III（Beckman
Coulter company system measurement devices）Measure.Measure is issued using according to Beckman Coulter companies
MultisizerTMImplement in aperture after the correction of 3 user's manuals.
In addition, the selection in aperture suitably carries out in the following manner used in measure.That is, in the acrylic acid series tree of measure
Aperture of the selection with 50 μm of size in the case that the volume average particle size of the estimation of fat granule is 1~10 μm, in measure
The volume average particle size of the estimation of acrylic resin particle, which is more than selection in the case of 10 μm and less than 30 μm, has 100 μm
The aperture of size, is selected in the case where the volume average particle size of the estimation of acrylic resin particle is more than 30 μm and less than 90 μm
The aperture with 280 μm of size is selected, is more than 90 μm and 150 μm in the volume average particle size of the estimation of acrylic resin particle
Selection is with 400 μm aperture of size etc. in the case of below.Volume average particle size after measure is put down with the volume estimated
In the case of equal particle diameter difference, it is changed to after there is the aperture of appropriate size, is measured again.
In addition, in the case where selecting the aperture with 50 μm of size, electric current（Aperture current）It is set as -800, gain
（Gain）It is set as 4, in the case where selecting the aperture with 100 μm of size, electric current（Aperture current）Be set as -1600,
Gain is set as 2, in the case where selecting the aperture with 280 μm and 400 μm of size, electric current（Aperture current）Be set as-
3200th, gain is set as 1.
As measurement sample, contact mixer is utilized using by acrylic resin particle 0.1g（ヤ マ ト science strains
Formula commercial firm system, " TOUCHMIXER MT-31 "）And ultrasonic cleaner（ヴ ェ Le ヴ ォ ク リ ー ア societies of Co., Ltd. system,
“ULTRASONIC CLEANER VS-150”）It is dispersed in the nonionic surfactant water-soluble liquid 10mL of 0.1 weight % and forms
For the sample of dispersion liquid.Set in the determination part of Coulter Multisizer III and fill ISOTON（Registration mark）II
（Beckman Coulter company systems：Measure electrolyte）Beaker, while being slowly stirred in beaker, be added dropwise above-mentioned scattered
Liquid, after the reading alignment 5~10% of the densimeter of Coulter Multisizer III main body pictures, starts to measure.In measure
The degree not entered in beaker with bubble is slowly stirred, and terminates to measure at the time of 100,000 particles are measured.Acrylic resin
The volume average particle size of particle is the arithmetic average in the size distribution of the volume reference of 100,000 particles.
In the acrylic resin particle of the present invention, the regulation for the particle surface observed by scanning electron microscope is drawn
The number of existing protuberance is defined as 4~30 in subregion, is preferably 7~30, more preferably 10~30, especially
Preferably 10~20.
In the acrylic resin particle of the present invention, the regulation for the particle surface observed by scanning electron microscope is drawn
The number of existing protuberance is excessive or very few in subregion, rubbing when can all make the acrylic resin particle rub each other
Wipe resistance to become larger, acrylic resin particle is contained in external preparation and in the case of use, reduce the smooth of external preparation
Use feeling, creak sense during using external preparation become harsh feelings that are more, or increasing external preparation.
In the acrylic resin particle of the present invention, the regulation for the particle surface observed by scanning electron microscope is drawn
The number of existing protuberance is measured with following methods in subregion.First, method described above measure acrylic resin particle
Volume average particle size, random selection 10 has 0.8~1.2 times of volume average particle size from acrylic resin particle
The acrylic resin particle of particle diameter.For example, in the case that the volume average particle size of acrylic resin particle is 8 μm, at random
The acrylic resin particle that 10 particle diameters of selection are 6.4~9.6 μm.It will be averaged from acrylic resin particle with volume
The acrylic resin particle of 0.8~1.2 times of particle diameter of particle diameter as measure object be because,（1）Acrylic resin grain
The major part of son is included in 0.8~1.2 times of particle diameter of volume average particle size,（2）0.8~1.2 with volume average particle size
Times particle diameter acrylic resin particle acrylic resin particle is contained in external preparation and in use, can be outside left and right
With the smooth use feeling of agent, using external preparation when creak sense or external preparation harsh feeling.
Using scanning electron microscope to shoot the amplifications of the acrylic resin particle of 8000 times of multiplying power shooting selection
Photo.To each acrylic resin particle, the state can contact acrylic resin particle most is drawn in a manner of surrounding
The positive round C of most path.Draw 90% diameter of the diameter with positive round C and with the center identical with the center of positive round C
Measure circle D.Calculate the number of protuberance contained in measure circle D.The protrusion that will be measured in each acrylic resin particle
The arithmetic mean of instantaneous value of the number in portion as acrylic resin particle surface regulation division region memory protuberance number
Mesh.As measure object protuberance only calculate enter completely measure circle D in protuberance, even if some from measure justify
Except the protuberance that D exceeds can be from measure object.In addition, only by measure circle D in protuberance be set to measure object be because,
Due to the technical reason of scanning electron microscope, the acrylic resin particle fraction measured outside circle D will not be clear
Chu shoots, it is impossible to accurately calculates protuberance.
In addition, for the standard deviation of the frictional resistance in the acrylic resin particle of the present invention, due to more improving
The smooth use feeling of external preparation, more reduces creak sense when using external preparation, alternatively, more reducing the coarse of external preparation
Sense, therefore preferably below 0.022N, more preferably below 0.02N, particularly preferably 0.003N~0.02N.
The standard deviation of the frictional resistance of acrylic resin particle refers to the value of following method measure.
The making of first test film
First, length 100mm, width 50mm, the first acrylic panel of thickness 3mm are prepared, the one of the first acrylic panel
Two-sided tape is sticked in the entire surface in face（ニ チ バ Application society trade name " Na イ ス タ ッ Network NW-15SF "）（Process A）.
The funnel and funnel platform of apparent density analyzer are used on above-mentioned two-sided tape（According to JIS K5101-12-1）
After acrylic resin particle is carried out freely falling body on whole faces of two-sided tape, blown off with the compressed air of 0.05MPa
Unnecessary acrylic resin particle on the two-sided tape（Process B）.
Then, above-mentioned first acrylic panel is placed on flat glass plate.In addition, by length 100mm × width 50mm
The flat glass plate of flat rectangular shape and surface（500g）It is placed in the patch of the acrylic resin particle of the first acrylic panel
On conjunction face, apply the load of the dead weight based on glass plate to acrylic resin particle, stand 1 minute.Then, from the first propylene
After sour plate removes glass plate, the unnecessary acrylic resin on above-mentioned two-sided tape is blown off with the compressed air of 0.1MPa again
Particle（Process C）.
Then, using above-mentioned process B and process C as a circulation, two circulations is carried out, make the first test film.
The making of second test film
Length 30mm, width 20mm, thickness 3mm the second acrylic panel one side entire surface on stick two-sided tape
（ニ チ バ Application society trade name " Na イ ス タ ッ Network NW-15SF "）.All corners of second acrylic panel are chamfered（Step D）.
Then, using the funnel and funnel platform of apparent density analyzer（According to JIS K5101-12-1）In two-sided tape
After acrylic resin particle is carried out freely falling body in entire surface, blown off with the compressed air of 0.05Mpa on the two-sided tape
Unnecessary acrylic resin particle（Process E）.
Then, above-mentioned second acrylic panel is placed on flat glass plate.In addition, by other length 30mm × width
The flat glass plate of the flat rectangular shape of 20mm and surface（60g）It is placed in the acrylic resin particle of the second acrylic panel
On binding face, apply the load of the dead weight based on glass plate to acrylic resin particle, stand 1 minute.Then, from the two the third
After olefin(e) acid plate removes glass plate, the unnecessary acrylic acid series tree on above-mentioned two-sided tape is blown off with the compressed air of 0.1MPa again
Fat granule（Process F）.
Then, using above-mentioned operation E and process F as a circulation, two circulations is carried out, make the second test film.
Friction of the first test film and the second test film obtained in operation more than as acrylic resin particle
The measurement sample of the standard deviation of resistance.
Overlapping first examination of mode contacted each other with acrylic resin particle accompanying on these acrylic panels
Test piece and the second test film.Then, while load 100g is applied towards the first test film on the second test film, first is fixed
Make in the state of test film the second test film on the parallel direction in the surface relative to the first test film, in hauling speed
600mm/ minutes, mensuration distance 30mm, move under conditions of sample rate 1ms, carry out the measure of frictional resistance.
Then, after the measure of the measurement result of frictional resistance starts 0.5 second untill 2.999 seconds, rubbing for 1ms is often sampled
In the data for wiping resistance, the standard deviation of frictional resistance is tried to achieve.
To the different acrylic resin particles of haphazard selection, the measure of 3 above-mentioned frictional resistance is carried out, friction is hindered
Standard deviation of the arithmetic mean of instantaneous value of the standard deviation of power as the frictional resistance of acrylic resin particle.In addition, friction resistance
The measure of power can be used by Xin Dong science society with trade name " HEiDOn TRIBOGEAR TYPE：38 " commercially available surface propertys
Measuring machine.
Then, the manufacture method of the acrylic resin particle of the present invention is illustrated.The acrylic acid series tree of the present invention
Fat granule can be manufactured by known method, but due to being easily adjusted particle diameter, preferably manufacture propylene by suspension polymerisation
Sour resin beads.
The method that acrylic resin particle is manufactured by suspension polymerisation is illustrated.Make to include polymerization initiator and contain
There is the mixture of the starting monomer of methyl methacrylate（Oil phase）In aqueous medium（Water phase）In disperse after, hang starting monomer
Floating polymerization.
As the device for making oil phase be dispersed in water phase, it is not particularly limited, for example, microfluidizer can be enumerated
（マイクロフルイダイザー）, nano-dispersed machine（ナノマイザー）Deng high-pressure type dispersion machine, pass through um porous
Glass（MPG）Oil phase is pressed into aqueous medium by perforated membrane（Water phase）In device, possess have propeller impeller dispersion machine,
Mix machine, ultrasonic dispersing machine etc..
In the case of making the acrylic resin of composition acrylic resin particle crosslinked, as long as containing first as described above
Contain multi-functional monomer in the starting monomer of base methyl acrylate.In addition, forming the third of acrylic resin particle
In the case of containing other monomers component in olefin(e) acid system resin, can also suitably contain in starting monomer can be with metering system
The monomer of sour methyl esters copolymerization.
As aqueous medium, it is not particularly limited, for example, water, water and water-soluble organic media can be enumerated（Methanol, second
The lower alcohols such as alcohol（Carbon number is less than 5 alcohol））Blending agent.The dosage of aqueous medium, due to seeking acrylic acid series tree
The stabilisation of fat granule, therefore be preferably 100~1000 parts by weight relative to 100 parts by weight of starting monomer.
As polymerization initiator, as long as the polymerization of starting monomer can be triggered, it is not particularly limited, but it is small preferably using 10
When half life temperature be 40~80 DEG C of polymerization initiator, for example, benzoyl peroxide, lauroyl peroxide, t-butyl peroxy
The organic peroxides such as base 2 ethyl hexanoic acid ester；2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2- methylbutyronitriles), 2,2 '-
Azo system nitrile compounds such as azo two (2,4- methyl pentane nitriles) etc..Polymerization initiator can be used alone can also and with two kinds
More than.
The dosage of polymerization initiator, due to can successfully trigger the suspension polymerisation of starting monomer, relative to raw material
100 parts by weight of monomer, are preferably 0.01~2 parts by weight, more preferably 0.1~1 parts by weight.
Dispersion stabilizer can be contained in an aqueous medium.As dispersion stabilizer, can enumerate calcium phosphate, magnesium phosphate,
The phosphate such as aluminum phosphate, trbasic zinc phosphate；The pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate, zinc pyrophosphate；Calcium carbonate, carbon
Sour magnesium, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, cataloid etc. are difficult water-soluble
Inorganic compound；Water soluble polymer etc. as polyvinylpyrrolidone, polyvinyl alcohol.In these, divide using by acid
The dispersion stabilizer for solving and being dissolved in the water（For example, calcium carbonate, calcium phosphate, magnesium hydroxide, magnesium pyrophosphate, calcium pyrophosphate）When,
Dispersion stabilizer can be readily removable after polymerization process, therefore preferably.Also may be used in addition, dispersion stabilizer can be used alone
With and with two or more.
From the mobility for ensuring suspension while, the dispersed excellent side of the acrylic resin particle in suspension
Face considers that the dosage of dispersion stabilizer is preferably 0.5~15 parts by weight relative to 100 parts by weight of starting monomer.
In order to make dispersion liquid more stabilize in suspension polymerisation, surfactant can also be contained in an aqueous medium.
As surfactant, anion surfactant, nonionic surfactant and zwitterionic surfactant can be used
It is any.In addition, surfactant can be used alone can also and with two or more.
As anion surfactant, for example, enuatrol can be enumerated；The fatty acid oils such as potassium ricinoleate；Lauryl
The alkyl sulfate salt such as sodium sulphate, Texapon Special；The alkylbenzenesulfonates such as neopelex；Alkyl naphthalene sulfonic acid
Salt；Alkane sulfonate；The dialkyl sulfosuccinates such as dioctyl sodium sulphosuccinate；Alkenyl succinate（Di-potassium）；Alkane
Base phosphate ester salt；Naphthalene sulfonic acid-formaldehyde condensation product；Polyoxyethylene alkyl phenyl ether sulfuric acid, sodium laureth sulfate
Deng polyoxyethylene alkyl ether sulfate salt；Polyoxyethylene alkyl sulfate salt etc..
As nonionic surfactant, for example, can enumerate polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether,
Polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy sorbitan fatty acid ester, polyoxyethylene alkyl amine, fat
Fatty acid glyceride, ethoxy ethylene-epoxide propylene block copolymer etc..
As zwitterionic surfactant, lauryl dimethyl amine oxide, phosphate system surface-active can be enumerated
Agent, phosphite ester system surfactant etc..
From the mobility for ensuring suspension while, the dispersed excellent side of the acrylic resin particle in suspension
Face considers that the dosage of surfactant is preferably 0.001~0.1 parts by weight relative to 100 parts by weight of aqueous medium.
As described above, make the mixture containing starting monomer and polymerization initiator（Oil phase）It is dispersed in aqueous medium（Water phase）
In, make the polymerization of fluid drops of mixture, but the mixture containing starting monomer and polymerization initiator（Oil phase）A part dissolve in
In water phase, the starting monomer dissolved in water phase is utilized in the teat of acrylic resin particle surface is formed.
That is, acrylic resin particle of the invention, makes the mixture containing starting monomer and polymerization initiator（Oil phase）
Suspending drops polymerization and manufacture acrylic resin particle, on the other hand make to dissolve in aqueous medium（Water phase）In raw material list
Body polymerize and manufactures fine particle, and fine particle attachment integration is made on the surface of acrylic resin particle, is consequently formed prominent
Go out portion and manufacture the acrylic resin particle of the present invention.
In the case of containing multi-functional monomer in starting monomer, make the mixture containing starting monomer and polymerization initiator
（Oil phase）Suspending drops polymerization obtained from acrylic resin particle produce aggregation each other, therefore preferably contain in water phase
Water miscible polymerization inhibitor.The mutual Reasons for aggregation of acrylic resin particle do not find out clearly, but in starting monomer
During containing multi-functional monomer, the acrylic resin particle exhibit adhesiveness of generation, it is believed that due to the adhesiveness, acrylic acid series
Resin particle is assembled each other.Also, by containing water miscible polymerization inhibitor in water phase, suppress the acrylic acid series in generation
Resin particle exhibit adhesiveness, suppresses the mutual aggregation of acrylic resin particle.
As polymerization inhibitor, it is not particularly limited, for example, the nitrites such as sodium nitrite, sulfurous acid can be enumerated
Salt, hydroquinones, Vitamin C acids, water-soluble (vitamin) B class, citric acid, oxidoreductase etc., are preferably nitrites, more
Preferably sodium nitrite.In addition, polymerization inhibitor can be used alone can also and with two or more.
From the aspect of it can more effectively suppress the mutual aggregation of acrylic resin particle, the use of polymerization inhibitor
Amount is preferably 0.005~0.1 parts by weight relative to 100 parts by weight of aqueous medium, more preferably 0.005~0.05 parts by weight.
As long as the temperature of suspension polymerisation can polymerize starting monomer, it is not particularly limited, is preferably 30~110 DEG C,
More preferably 40~110 DEG C.When the time of suspension polymerisation is preferably 0.1~20 small, when being preferably 0.6~13 small.
From the acrylic resin particle that can be efficiently reduced from the aspect of contained levels of residual monomers,
It is preferred that polymerization temperature is divided into the first temperature province and the second temperature region than the first temperature province higher, starting monomer is set to exist
After first temperature province suspension polymerisation, make starting monomer in the further suspension polymerisation in second temperature region.
It is preferably 30~80 DEG C as the first temperature province, more preferably 40~70 DEG C.As second temperature region, need
It it is preferably 100~110 DEG C, more preferably 105~110 DEG C than the temperature of the first temperature province higher.
As described above, the suspension polymerization temperatures of starting monomer are divided into the first temperature province and second temperature region is hanged
Floating polymerization, carries out the poly- of starting monomer while thus polymerization initiator is slowly decomposed in the first temperature province of low temperature
Close, on the basis of the polymerization for carrying out starting monomer to a certain degree, in the second temperature region raising than the first temperature province higher
The polymerization speed of starting monomer, it is possible thereby to promote the polymerization of starting monomer, its result can reduce obtained acrylic acid series
Contained levels of residual monomers in resin particle.
The time of suspension polymerisation for the starting monomer in the first temperature province, since the polymerization of starting monomer can be made
Be sufficiently carried out, thus preferably 0.1~15 it is small when, more preferably 0.1~10 it is small when.For the raw material in second temperature region
The time of the suspension polymerisation of monomer, due to the levels of residual monomers that can be effectively reduced in obtained acrylic resin particle
With the levels of residual monomers in water phase, therefore preferably 0.5~10 it is small when, more preferably 0.5~7 it is small when.
The polymerisation conversion of the oil phase at the end of suspension polymerisation in first temperature province is 95% or so.Even if raw material list
In the case of containing multi-functional monomer in body, at the time of the suspension polymerisation in the first temperature province terminates also as described above, oil
The polymerisation conversion of phase is 95% or so, and the mutual aggregation of acrylic resin particle of generation does not produce, therefore in the second temperature
Before spending region progress suspension polymerisation, distintegrant is added in water phase, on the basis of decomposing the polymerization inhibitor dissolved in water phase,
Second temperature region further carries out the suspension polymerisation of starting monomer, carries out the polymerization of starting monomer in water phase and generates small grain
Son.
In addition, in the case of suspension polymerisation is not divided into the first temperature province and the progress suspension polymerisation of second temperature region,
When containing polymerization inhibitor in water phase, at the time of the polymerisation conversion of the starting monomer of oil phase becomes 90~95%, add in water phase
Add distintegrant, on the basis of decomposing the polymerization inhibitor dissolved in water phase, further carry out the suspension polymerisation of starting monomer, water
The polymerization of starting monomer is carried out in phase and generates fine particle.
For the volume average particle size of molecule, from can be in the acrylic acid that make the starting monomer of oil phase polymerize and generate
Easily adhere on the surface of resin beads it is integrated from the aspect of, be preferably 4~10 μm, more preferably 6~10 μm.This
Outside, the volume average particle size of fine particle can be with the situation of the measure of the volume average particle size of aforesaid propylene acid resin beads
Same method measure.
The distintegrant in water phase is added as decomposing polymerization inhibitor, is not particularly limited, for example, can be with
Enumerate sulfamic acid, ammonium chloride etc..
Amount for the distintegrant for adding the polymerization inhibitor in water phase, makes to gather due to that can not hinder suspension polymerisation
Close inhibitor effectively to decompose, therefore be preferably 100~2000 parts by weight, more preferably relative to 100 parts by weight of polymerization inhibitor
For 500~1000 parts by weight.
The major part of starting monomer is polymerize in above-mentioned suspension polymerisation, but in order to more reduce in acrylic resin particle
Contained residual monomer, preferably add in an aqueous medium on the basis of sodium hydroxide, the alkali compounds such as potassium hydroxide
Second temperature region further carries out suspension polymerisation.
By carrying out suspension polymerisation as described above, the suspension containing acrylic resin particle and fine particle can be obtained
Liquid.Acrylic resin particle and fine particle are separated by the suspension, carried out using cleaning solutions such as water one or many clear
Wash and be dehydrated.In addition, from the aspect of the cleaning performance of residual monomer etc. is higher, acrylic resin particle and fine particle
Cleaning can also use 50~70 DEG C of warm water.
As the method that acrylic resin particle and fine particle are separated by suspension, can enumerate using filter cloth by hanging
The method of supernatant liquid filtering, separation acrylic resin particle and fine particle.For the venting quality of filter cloth, due to by suspension not
Miss fine particle and can be together easily separated with acrylic resin particle, therefore preferably 50~120cm3/cm2/ point
Clock, more preferably 70~100cm3/cm2/ minute.
Then, it is dried while the mixture of stirring acrylic resin particle and fine particle until residual moisture
Reach relative to the total weight of acrylic resin particle and fine particle below 0.5 weight %.In the drying process, third
The surface of olefin(e) acid resin beads has fine particle attachment integration, can obtain in third of particle surface formed with protuberance
Olefin(e) acid resin beads.
From can make on the surface of acrylic resin particle fine particle effectively adhere to it is integrated from the aspect of, third
The drying temperature of the mixture of olefin(e) acid resin beads and fine particle is preferably 50~90 DEG C, more preferably 60~80 DEG C.Separately
Outside, when the drying time of the mixture of acrylic resin particle and fine particle is preferably 5~20 small, more preferably 10~20 is small
When.
Obtained acrylic resin particle is classified using general stage division as needed, so as to
To the acrylic resin particle that volume average particle size is 4~10 μm.
The acrylic resin particle obtained as described above can be adapted to containing being used in external preparation.As external preparation,
For example, external application pharmaceuticals or cosmetics etc. can be enumerated.As external application pharmaceuticals, as long as being suitable for skin, then do not limit especially
It is fixed, for example, cream, ointment, emulsion etc. can be enumerated.As cosmetics, for example, perfumed soap, shower cream, face cleaning can be enumerated
The cleanings such as cream, face cleaning scrub cream, toothpaste apply some make up；Face powder class, foundation cream, lipstick, lipstick, blush, eyebrow cosmetics, nail polish
Deng cosmetics of dressing up；Skin cream before shaving（プレシェーブローション）, the emollient such as skin cream；Talcum powder（ボデ
ィーパウダー）, baby talcum powder（ベビーパウダー）Deng body external preparation；Toner, emulsifiable paste, lotion, facial mask class,
Hair washing applies some make up, hair dye, hair cosmetic agent, armaticity cosmetics, baths, antiperspirant, sunscreen product, tanning products, shaves
With emulsifiable paste etc..
The mixed proportion of acrylic resin particle in external preparation, is not particularly limited, and is fitted according to the species of external preparation
Work as adjusting, but preferably generally 0.5~80 weight %, more preferably 2~30 weight %.In addition, acrylic resin particle
The place in advance such as surface conditioning agent, organic powder or inorganic particle of finish, silicone compounds and fluorine compounds etc. can also be utilized
Reason.
As finish, as long as the finish usually used in external preparation, for example, atoleine, spiny dogfish can be enumerated
The hydrocarbon ils such as alkane, vaseline, paraffin, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecenoic acid, epoxide
The higher fatty acids such as stearic acid, linoleic acid, lanolin fatty acid, synthetic fatty acid；Tricaprylin, didecyl acid propylene glycol
The ester oils such as ester, 2 ethyl hexanoic acid spermaceti alcohol ester, the different spermaceti alcohol ester of stearic acid；Beeswax, spermaceti, lanolin, Brazil wax, small candle
The wax class such as vegetable wax；The grease types such as Linseed oil, cottonseed oil, castor oil, egg oil, coconut oil；The gold such as zinc stearate, zinc laurate
Belong to soap；Higher alcohols such as cetanol, stearyl alcohol, oleyl alcohol etc..
Using the method for finish processing acrylic resin particle, it is not particularly limited, for example, in acrylic acid
Stirred after above-mentioned finish is added in resin beads using mixer etc., thus in the surface dope of acrylic resin particle
The dry method of agent；After dissolving by heating finish in the appropriate solvents such as ethanol, propyl alcohol, ethyl acetate, hexane, propylene is added in a solvent
Sour resin beads are mixed, and then, decompression removes or heating removes solvent, thus on the surface of acrylic resin particle
It is coated with wet method of finish etc..
As silicone compounds, as long as the silicone compounds usually used in external preparation, for example, two can be enumerated
Methyl polysiloxane, methylhydrogenpolysi,oxane, methyl phenyl silicone, acrylic acid-silicone-based graft polymers, organic silicone
Resin portion cross-linking type organopolysiloxane polymer etc..Method using silicone compounds processing acrylic resin particle does not have
It is particularly limited to, for example, illustrated dry or wet in the case of above-mentioned finish can be utilized.Alternatively, it is also possible to basis
Need to carry out baking processing, or catalysts etc. are properly added in the case of the silicone compounds with reactivity.
For fluorine compounds, as long as the fluorine compounds usually coordinated in external preparation, for example, can enumerate containing perfluor
The ester of alkyl, perfluoroalkyl silanes, perfluoropolyether, the polymer etc. with perfluor base.Utilize the side of fluorine compounds processing particle
Method is also not particularly limited, for example, illustrated dry or wet in the case of above-mentioned finish can be utilized.In addition, also may be used
To carry out baking processing as needed, or catalysts are properly added in the case of the silicone compounds with reactivity
Deng.
As organic powder, for example, nylon particle, crosslinked polystyrene particle, silicone resin particle, amino can be enumerated
The resin particles such as Ethyl formate particle, polyethylene particles, fluorine particle.
As inorganic particle, for example, iron oxide, ultramarine, Prussian blue, chromium oxide, chromium hydroxide, carbon black, manganese
Purple, titanium oxide, zinc oxide, talcum, kaolin, mica, calcium carbonate, magnesium carbonate, mica, alumina silicate, barium silicate, calcium silicates, silicon
Sour magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate hemihydrate（Bassanite）, calcium phosphate, hydroxyapatite, ceramic powders etc..
Organic powder or inorganic particle can be implemented to be surface-treated in advance.As surface treatment method, it can utilize and such as exist
Illustrated known process for treating surface in the case of finish.As long as in addition, do not damaging the acrylic resin of the present invention
The scope of the effect of particle, can also in external preparation according to purpose suitably coordinate it is general used in common additive.Make
For such component, for example, water, lower alcohol, grease and wax class, hydro carbons, higher fatty acids, higher alcohol, sterol, fat can be enumerated
It is fat acid esters, metallic soap, moisturizer, surfactant, high-molecular compound, color material raw material, spices, anticorrosion and bactericidal agent, anti-oxidant
Agent, ultra-violet absorber, other special compounding components etc..
As grease and wax class, for example, can enumerate avocado oil, apricot kernel oil, olive oil, cocoa butter, tallow, sesame oil,
Wheat-germ oil, safflower oil, missible oil wood fruit fat, turtle oil, camellia oil, persic oil, castor oil, grape-kernel oil, macadimia nut oil,
Ermine oil, egg oil, Japan tallow, coconut oil, rose hip oil, hydrogenated oil and fat, silicone oil, deep sea fish oil, Brazil wax, candelila wax,
Spermaceti, Jojoba Oil, lignite wax, beeswax, lanolin etc..
As hydro carbons, for example, atoleine, vaseline, paraffin, ceresin, microwax, saualane etc. can be enumerated.Make
For higher fatty acids, laurate, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecenoic acid, epoxide can be enumerated
Stearic acid, linoleic acid, lanolin fatty acid, synthetic fatty acid.
As higher alcohol, for example, laruyl alcohol, cetanol, 18 hexadecanols can be enumerated（セトステアリルアルコー
ル）, stearyl alcohol, oleyl alcohol, docosyl alcohol, lanolin alcohol, hydrogenation lanolin alcohol, hexyl decyl alcohol, octyl decanol, isooctadecanol, lotus lotus
Fragrant plant alcohol, decyl tetradecyl alcohol etc..
As sterol, for example, cholesterol, beta-cholestanol, plant cholesterol can be enumerated（フィトコレステロー
ル）Deng.As fatty acid ester, ethyl linoleate, isopropyl myristate, lanolin fatty isopropyl propionate, bay can be enumerated
The own ester of acid, myristic acid nutmeg alcohol ester, myristic acid spermaceti alcohol ester, myristic acid octyldodecyl, decyl oleate, oil
Sour octyldodecyl, dimethyl-octyl hexyl decyl ester, isooctyl acid spermaceti alcohol ester, palmitic acid last of the ten Heavenly stems ester, three myristic acid glycerine
Ester, three（Caprinoyl capric acid）Glyceride, two oleic acid propylene glycol esters, three glyceryl isostearates, three isooctyl acid glyceride, lactic acid whale
Ceryl alcohol ester, lactic acid myristyl alcohol ester, two isooctadecanol ester of malic acid, cholesterol isostearate, 12- hydroxy stearic acid cholesterol
Ring-type alcohol fatty acid ester such as ester etc..
As metallic soap, for example, zinc laurate, Zinc tetradecanoate, magnesium myristate, zinc palmitate, tristearin can be enumerated
Sour zinc, aluminum stearate, calcium stearate, magnesium stearate, zinc undecylenate etc..As moisturizer, can enumerate glycerine, propane diols,
1,3 butylene glycol, polyethylene glycol, dl- pyrrolidone sodium carboxylates, sodium lactate, D-sorbite, Sodium Hyaluronate, polyglycereol, xylose
Alcohol, maltitol etc..
As surfactant, for example, can enumerate higher fatty acids soap, higher alcohol sulfate, N- acyl glutamates,
The anion surfactants such as phosphate ester salt；The cationic surfactants such as amine salt, quaternary ammonium salt；Betaine type, amino acid pattern, miaow
The amphoteric surfactantes such as oxazoline type, lecithin；Glycerine monofatty ester, methyl glycol fatty acid ester, sorbitol anhydride fatty acid
The nonionic surfactants such as ester, sucrose fatty ester, fatty acid polyglycerol ester, ethylene oxide condensation product.
As high-molecular compound, for example, Arabic gum, bassora gum, guar gum, locust bean gum, thorn Chinese parasol tree can be enumerated
Glue, carragheen（アイリスモス）, Quinces Quince seed glue（クインスシード）, gelatin, shellac, rosin, casein etc. it is natural high
Molecular compound；Sodium carboxymethylcellulose, hydroxyethyl cellulose, methylcellulose, ethyl cellulose, mosanom, ester gum, nitro
The semi-synthetic high-molecular compound such as cellulose, hydroxypropyl cellulose, avicel cellulose；Polyvinyl alcohol, polyvinylpyrrolidone, gather
The synthetic macromolecular compounds such as sodium acrylate, carboxy vinyl polymer, polyvinyl methyl ether.
As color material raw material, for example, can enumerate iron oxide, ultramarine, Prussian blue, chromium oxide, chromium hydroxide, carbon black,
Manganese violet, titanium oxide, zinc oxide, talcum, kaolin, mica, calcium carbonate, magnesium carbonate, mica, alumina silicate, barium silicate, calcium silicates,
Magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate hemihydrate（Bassanite）, calcium phosphate, hydroxyapatite, the nothing such as ceramic powders
Machine pigment；Azo system, nitro system, nitrous base system, xanthene system, quinoline system, anthraquinoline system, indigo system, triphenylmenthane system, phthalocyanine
The tar dyestuffs such as system, pyrene system.In addition, the powder material such as powder material or color material raw material of high-molecular compound can also be real in advance
Apply surface treatment.
As the method for the surface treatment of color material raw material, known process for treating surface can be utilized, for example, being based on hydrocarbon
The finish processing of oil, ester oil, lanolin etc., based on dimethyl polysiloxane, methylhydrogenpolysi,oxane, methyl phenyl silicone
Deng silicone-treated, based on the ester containing perfluoroalkyl, perfluoroalkyl silanes, perfluoropolyether and polymer etc. with perfluoroalkyl
Fluorine compounds processing, based on 3- methacryloxypropyl trimethoxy silanes, 3- glycidoxypropyl group trimethoxies
The silane coupling agent processing of silane etc., based on three isostearoyl base titanate esters of isopropyl, isopropyl three（Dioctylphyrophosphoric acid ester）
The titanium coupling agent processing of titanate esters etc., metallic soap processing, the amino acid treatment based on acyl glutamic acid etc., based on hydrogenation lecithin
Deng lecithin processing, collagen processing, polyethylene processing, moisture retention processing, inorganic compound processing, mechanochemistry processing etc.
Processing method.
As spices, for example, anisaldehyde, benzyl acetate, geraniol etc. can be enumerated.As anticorrosion and bactericidal agent, for example, can
To enumerate methyl hydroxybenzoate, nipagin A, nipasol, benzene first hydroxylamine, benzyl ethoxy amine
（benzethonium）Deng.As antioxidant, for example, dibutyl hydroxy toluene, butylated hydroxy anisole can be enumerated, do not eaten
Sub- propyl propionate, tocopherol etc..
As ultra-violet absorber, for example, particulate titanium dioxide, particulate zinc oxide, ceric oxide particulate, particulate oxygen can be enumerated
Change inorganic system's ultra-violet absorbers such as iron, particulate oxide zirconium；Benzoic acid system, p-aminobenzoic acid system, ortho-aminobenzoic acid system, water
The organic system ultra-violet absorbers such as poplar acid system, cinnamic acid system, benzophenone series, dibenzoyl methane system.
As special compounding component, for example, can enumerate estradiol, oestrone, ethinylestradiol, cortisone, hydrogenation can
The steroids such as pine, metacortandracin；The vitamins such as vitamin A, vitamin B, vitamin C, vitamin E；Citric acid, tartaric acid, breast
The skin contraction material agent such as acid, aluminium chloride, alum, Alcloxa, p-phenolsulfonic acid's zinc, zinc sulfate；Cantharides tincture, capsicum
Tincture, ginger tincture, mud sandfly extract, garlic P.E, Hinokitiol, carpronium chloride, pentadecanoic acid glyceride, vitamin E, it is female swash
The hair growth promoting agents such as plain, photosensitive element；Whitening agents such as phosphoric acid-L-AA magnesium, kojic acid etc..
The acrylic resin particle of the present invention is formed as described above, therefore acrylic resin particle is contained outside
With the smooth use feeling in agent and in the case of use, improving external preparation, creak sense during almost without using external preparation is several
Without the harsh feeling of external preparation, the external preparation with excellent use feeling may be constructed.
Brief description of the drawings
Fig. 1 is the enlarged photograph of the acrylic resin particle obtained by embodiment 1.
Fig. 2 is the enlarged photograph of the acrylic resin particle obtained by embodiment 2.
Fig. 3 is the enlarged photograph of the acrylic resin particle obtained by comparative example 1.
Symbol description
C positive round
D measure circles
Embodiment
The present invention is described in more detail in the following, enumerating embodiment, but is not limited to the present embodiment.
（Embodiment 1）
Ion exchange water（Water phase）After 60 parts by weight of magnesium pyrophosphate manufactured with double decomposition are added in 2400 parts by weight, into
One step dissolves 0.72 parts by weight of NaLS.Prepare in methyl methacrylate（MMA）Make 2 in 1000 parts by weight,
The mixture that 2 '-azo two (2,4- methyl pentane nitriles), 5 parts by weight uniform dissolution forms（Oil phase）.Add in above-mentioned ion exchange water
After adding mixture, homomixer is used（プ ラ イ ミ Network ス Co. Ltd. systems trade name " TK ホ モ ミ キ サ ー "）With
8000rpm stirrings, hybrid ionic exchanged water about 10 minutes and make oil phase micro disperse in water phase, produce dispersion liquid.
Then, dispersion liquid is moved in the autoclave equipped with agitator arm and thermometer, 50 while being dispersed with stirring liquid
℃（First temperature province）Heat 5 it is small when carry out methyl methacrylate suspension polymerisation.
Then, neopelex is supplied to dispersion liquid（Purity：20 weight %）6 parts by weight are as surfactant
Afterwards, 105 DEG C are warming up to（Second temperature region）Heat 2 it is small when come continue to carry out suspension polymerisation.Then, by autoclave
Temperature be down to less than 50 DEG C after, in dispersion liquid supply 72 parts by weight of sodium hydroxide, dispersion liquid is warming up to again 105 DEG C after
It is continuous carry out suspension polymerisation 5 it is small when.Cool down obtained suspension, addition hydrochloric acid decomposes point until the pH of slurry as 2 or so
Dispersion stabilizer.
Prepare centrifugal dehydrator（コクサン societies trade name " H-122 "）.In the inner face of the rotating cylinder of centrifugal dehydrator（It is interior
Footpath 30cm）Arrange venting quality 90cm3/cm2The filter cloth of/minute（Fu Island カ Application バ ス society's trade names " T84 "）Afterwards, it is de- to centrifugation
Water dispenser supplies suspension, makes rotating cylinder with 2400rpm（With respect to centrifugal acceleration：1932G）Supply and go in rotating cylinder while rotation
20 liters of ionized water, while the acrylic resin particle in suspension and fine particle are filtered, centrifuged, to third
Olefin(e) acid resin beads and fine particle are cleaned using deionized water, are dehydrated.
Then, dewatered cake shape is supplied into cleaning autoclave（ケ ー キ shapes）Resin particle, further in autoclave
2400 parts by weight of interior supply water, neopelex（Purity：20 weight %）1.2 parts by weight, 24 parts by weight of disodium hydrogen phosphate
After 12 parts by weight of potassium dihydrogen phosphate, to being stirred in autoclave while is warming up to 90 DEG C, continue 5 it is small when after, by high pressure
It is cooled to room temperature in kettle.
Then, above-mentioned centrifugal dehydrator rotating cylinder inner face（Internal diameter 30cm）Arrange venting quality 90cm3/cm2/ minute
New filter cloth（Fu Island カ Application バ ス society's trade names " T84 "）Afterwards, suspension is supplied to centrifugal dehydrator, makes rotating cylinder with 2400rpm
（With respect to centrifugal acceleration：1932G）20 liters of deionized water is supplied while rotation into rotating cylinder, to the acrylic acid series in suspension
While resin particle and fine particle are filtered, centrifuged, acrylic resin particle and fine particle are utilized and gone
Ionized water is cleaned, is dehydrated.
In horizontal vacuum drying machine（Gan Zao Xing productions society system）The dewatered acrylic resin particle of interior supply and small grain
Son（1000 parts by weight of solid constituent）, while 60 DEG C of suction vacuum of sheath temperature, with 10rpm（The circumference of agitator arm front end
Speed：7.85m/ minute）It is dried while stirring acrylic resin particle and fine particle until moisture is opposite
Reach in the gross weight of acrylic resin particle and fine particle below 0.5 weight %.
Obtained acrylic resin particle is passed through the sieve of 400 mesh of mesh to be classified, obtain acrylic acid series
Resin particle.Using scanning electron microscope putting for obtained acrylic resin particles is shot to shoot 8000 times of multiplying power
Big photo is shown in Fig. 1.
（Embodiment 2）
Ion exchange water（Water phase）After 60 parts by weight of magnesium pyrophosphate manufactured with double decomposition are added in 2400 parts by weight, into
One step dissolves 0.72 parts by weight of NaLS and 0.24 parts by weight of sodium nitrite as water-soluble polymeric inhibitor.It is accurate
It is standby to contain methyl methacrylate（MMA）The raw material list of 50 parts by weight of 950 parts by weight and ethylene glycol dimethacrylate
Make (2,4- methyl pentane nitriles) 5 parts by weight of 2,2 '-azo two in body and that 3 parts by weight uniform dissolution of benzoyl peroxide forms is mixed
Compound（Oil phase）.After adding mixture in above-mentioned ion exchange water, homomixer is used（プ ラ イ ミ Network ス Co. Ltd. systems
Trade name " TK ホ モ ミ キ サ ー "）Stirred with 8000rpm, hybrid ionic exchanged water about 10 minutes and make oil phase micro- in water phase
It is scattered, produce dispersion liquid.
Then, dispersion liquid is moved in the autoclave equipped with agitator arm and thermometer, 50 while being dispersed with stirring liquid
℃（First temperature province）Heat 5 it is small when carry out the suspension polymerisation of methyl methacrylate and ethylene glycol dimethacrylate.
Then, neopelex is supplied to dispersion liquid（Purity：20 weight %）6 parts by weight are as surfactant
Afterwards, further for decomposition sodium nitrite supply 2.4 parts by weight of sulfamic acid.Then, dispersion liquid is warming up to 105 DEG C（Second
Temperature province）Heat 2 it is small when come continue to carry out suspension polymerisation.
Then, after the temperature in autoclave being down to less than 50 DEG C, 72 parts by weight of sodium hydroxide are supplied into dispersion liquid, will
Dispersion liquid be warming up to again 105 DEG C continue suspension polymerisation 5 it is small when.Obtained suspension is cooled down, addition hydrochloric acid is until slurry
The pH of material decomposes dispersion stabilizer as 2 or so.
Using method similarly to Example 1, by obtained suspension, to acrylic resin particle and fine particle
Filtered, centrifuged, after acrylic resin particle and fine particle are cleaned, are dehydrated using deionized water, into
Row is dry, classification, thus obtains acrylic resin particle.Shot using scanning electron microscope with shooting 8000 times of multiplying power
The enlarged photograph of obtained acrylic resin particle is shown in Fig. 2.
（Embodiment 3）
Ion exchange water（Water phase）Calcium phosphate slurry is added in 1200 parts by weight（Peaceful chemistry society trade name " TCP-
10U”）Further make 0.72 parts by weight of NaLS and the nitrous acid as water-soluble polymeric inhibitor after 1200 parts by weight
0.24 parts by weight of sodium dissolve.Prepare containing methyl methacrylate（MMA）900 parts by weight and ethylene glycol dimethacrylate
Make (the 2,4- methyl pentane nitriles of 2,2 '-azo two in the starting monomer of 100 parts by weight of ester）3 weight of 5 parts by weight and benzoyl peroxide
The mixture that amount part uniform dissolution forms（Oil phase）.After adding mixture in above-mentioned ion exchange water, homomixer is used（プ
ラ イ ミ Network ス Co. Ltd. systems trade name " TK ホ モ ミ キ サ ー "）Stirred with 8000rpm, hybrid ionic exchanged water about 10 minutes
And make oil phase micro disperse in water phase, produce dispersion liquid.
Then, dispersion liquid is moved in the autoclave equipped with agitator arm and thermometer, 50 while being dispersed with stirring liquid
℃（First temperature province）Heat 5 it is small when carry out the suspension polymerisation of methyl methacrylate and ethylene glycol dimethacrylate.
Then, neopelex is supplied to dispersion liquid（Purity：20 weight %）6 parts by weight are as surfactant
Afterwards, further for decomposition sodium nitrite supply 2.4 parts by weight of sulfamic acid.Then, dispersion liquid is warming up to 105 DEG C（Second
Temperature province）Heat 2 it is small when come continue to carry out suspension polymerisation.
Then, after the temperature in autoclave being down to less than 50 DEG C, 72 parts by weight of sodium hydroxide are supplied into dispersion liquid, will
Dispersion liquid be warming up to again 105 DEG C continue suspension polymerisation 5 it is small when.Obtained suspension is cooled down, addition hydrochloric acid is until slurry
The pH of material decomposes dispersion stabilizer as 2 or so.
Using method similarly to Example 1, by obtained suspension, to acrylic resin particle and fine particle
Filtered, centrifuged, after acrylic resin particle and fine particle are cleaned, are dehydrated using deionized water, into
Row is dry, classification, thus obtains acrylic resin particle.
（Comparative example 1）
Ion exchange water（Water phase）Polyvinylpyrrolidone is added in 2400 parts by weight（Japanese catalyst society trade name " K-
30”）After 24 parts by weight, further make anion surfactant（You societies trade name " ラ ピ ゾ ー Le A-80 "）0.72 weight
Measure part and 0.24 parts by weight of sodium nitrite as water-soluble polymeric inhibitor dissolve.Prepare containing methyl methacrylate
（MMA）Make 5 weight of lauroyl peroxide in the starting monomer of 100 parts by weight of 900 parts by weight and ethylene glycol dimethacrylate
The mixture that amount part uniform dissolution forms（Oil phase）.After adding mixture in above-mentioned ion exchange water, ion exchange water is used
Homomixer（プ ラ イ ミ Network ス Co. Ltd. systems trade name " TK ホ モ ミ キ サ ー "）Stirred with 8000rpm, mix about 10
Minute and make oil phase micro disperse in water phase, produce dispersion liquid.
Then, dispersion liquid is moved in the autoclave equipped with agitator arm and thermometer, 60 while being dispersed with stirring liquid
℃（First temperature province）Heat 5 it is small when carry out the suspension polymerisation of methyl methacrylate and ethylene glycol dimethacrylate.
Then, neopelex is supplied to dispersion liquid（Purity：20 weight %）6 parts by weight are as surfactant
Afterwards, dispersion liquid is warming up to 105 DEG C（Second temperature region）Heat 2 it is small when come continue to carry out suspension polymerisation.
Then, after the temperature in autoclave being down to less than 50 DEG C, 72 parts by weight of sodium hydroxide are supplied in dispersion liquid, will
Dispersion liquid be warming up to again 105 DEG C continue suspension polymerisation 5 it is small when.Obtained suspension is cooled down, addition hydrochloric acid is until slurry
The pH of material decomposes dispersion stabilizer as 2 or so.
Using method similarly to Example 1, by obtained suspension, acrylic resin particle is filtered,
Centrifuge, after acrylic resin particle is cleaned, is dehydrated using deionized water, be dried, be classified, thus obtain
Acrylic resin particle.Using scanning electron microscope obtained acrylic resins are shot to shoot 8000 times of multiplying power
The enlarged photograph of particle is shown in Fig. 3.
（Comparative example 2）
Ion exchange water（Water phase）Calcium phosphate slurry is added in 1200 parts by weight（Peaceful chemistry society trade name " TCP-
10U”）After 5000 parts by weight, further dissolve 0.72 parts by weight of NaLS.Preparation is containing methyl methacrylate
（MMA）Make (the 2,4- bis- of 2,2 '-azo two in the starting monomer of 100 parts by weight of 900 parts by weight and ethylene glycol dimethacrylate
Methyl valeronitrile) mixture that forms of 5 parts by weight and 3 parts by weight uniform dissolution of benzoyl peroxide（Oil phase）.Above-mentioned ion exchange
After adding mixture in water, ion exchange water uses homomixer（プ ラ イ ミ Network ス Co. Ltd. systems trade name " TK ホ モ ミ
キサー”）Stirred with 8000rpm, mix about 10 minutes and make oil phase micro disperse in water phase, produce dispersion liquid.
Then, dispersion liquid is moved in the autoclave equipped with agitator arm and thermometer, 50 while being dispersed with stirring liquid
℃（First temperature province）Heat 5 it is small when carry out the suspension polymerisation of methyl methacrylate and ethylene glycol dimethacrylate.
Then, neopelex is supplied to dispersion liquid（Purity：20 weight %）6 parts by weight are as surfactant
Afterwards, dispersion liquid is warming up to 105 DEG C（Second temperature region）Heat 2 it is small when come continue to carry out suspension polymerisation.
Then, after the temperature in autoclave being down to less than 50 DEG C, 72 parts by weight of sodium hydroxide are supplied in dispersion liquid, will
Dispersion liquid be warming up to again 105 DEG C continue suspension polymerisation 5 it is small when.Obtained suspension is cooled down, addition hydrochloric acid is until slurry
The pH of material decomposes dispersion stabilizer as 2 or so.
Using method similarly to Example 1, by obtained suspension, acrylic resin particle is filtered,
Centrifuge, after acrylic resin particle is cleaned, is dehydrated using deionized water, be dried, be classified, thus obtain
Acrylic resin particle.
To obtained acrylic resin particle, method described above measure volume average particle size, the regulation of particle surface
Divide region memory the number of protuberance and the standard deviation of frictional resistance, the results are shown in table 1.
（The making of foundation cream）
Use 15 parts by weight of Henschel mixer mixing acrylic resin particle, 21 parts by weight of sericite, muscovite 51
Parts by weight, 0.6 parts by weight of red iron oxide, 1 parts by weight of yellow iron oxide and 0.1 parts by weight of black iron oxide and produce mixing
Thing.
On the other hand, 1 parts by weight of Span-83 and 0.2 parts by weight mixed dissolution of preservative are made in 2- second
Dissolved matter is produced in 10 parts by weight of base caproic acid spermaceti alcohol ester.
After making said mixture and the uniform mixing of above-mentioned dissolved matter, after adding 0.1 parts by weight of spices and uniformly mixing, crush
And sieve, make foundation cream material.The foundation cream material is compressed shaping in metal ware and produces foundation cream.
Prepare the participant of 10 people.Each participant has carried out the behavior that obtained foundation cream is smeared in wrist, with big thumb
Refer to and forefinger is clamped the behavior of obtained foundation cream and the behavior of obtained foundation cream is rubbed with thumb and forefinger.
The creak sense of smooth use feeling, foundation cream of each participant for foundation cream, the harsh feeling of foundation cream and to the attached of skin
The property, carries out any evaluation of " good " or " poor " from sense organ.
Among 10 people participants, there are more than 9 situations for being evaluated as " good " to be set to " A ", there are 7~8 to be evaluated as " good "
Situation is set to " B ", has 5~6 situations for being evaluated as " good " to be set to " C ", has less than 4 situations for being evaluated as " good " to be set to " D "
To be evaluated.
The results are shown in table 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Volume average particle size（μm） | 8.2 | 7.9 | 8.5 | 8.8 | 8.4 |
| The number of protuberance（It is a） | 5 | 14 | 28 | 2 | 47 |
| The standard deviation (gf) of frictional resistance | 1.92 | 0.65 | 1.82 | 3.65 | 2.53 |
| The standard deviation (N) of frictional resistance | 0.0188 | 0.0064 | 0.0178 | 0.0358 | 0.0248 |
| Smooth use feeling | A | A | B | A | C |
| Creak sense | B | A | A | D | C |
| Harsh feeling | B | A | A | A | B |
| Adhesion | B | B | A | C | B |
Claims (4)
1. a kind of acrylic resin particle, containing the acrylic resin using methyl methacrylate component as principal component, its
It is characterized in that, the regulation for the particle surface that volume average particle size is observed for 4~10 μm and by scanning electron microscope divides
The number of existing protuberance is 4~30 in region,
" using methyl methacrylate component as principal component " refers to, in the monomer component for forming acrylic resin, methyl-prop
The content of e pioic acid methyl ester component is more than 50 weight %,
The acrylic resin particle manufactures as follows：Make the suspending drops of the mixture containing starting monomer and polymerization initiator
It polymerize and manufactures acrylic resin particle, on the other hand makes to dissolve in starting monomer polymerization in an aqueous medium and manufacture small
Particle, fine particle attachment integration is made on the surface of acrylic resin particle, is consequently formed protuberance.
2. acrylic resin particle according to claim 1, it is characterised in that acrylic resin is crosslinked.
3. acrylic resin particle according to claim 1, it is characterised in that the standard deviation of frictional resistance is
Below 0.022N.
4. a kind of external preparation, it is characterised in that contain the acrylic resin particle described in any one of claims 1 to 3.
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| CN103030731A (en) * | 2011-09-29 | 2013-04-10 | 积水化成品工业株式会社 | Resin particle and applications of same |
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