CN105778008A - Polymer particles, and preparation method and application of polymer particles - Google Patents
Polymer particles, and preparation method and application of polymer particles Download PDFInfo
- Publication number
- CN105778008A CN105778008A CN201410836102.7A CN201410836102A CN105778008A CN 105778008 A CN105778008 A CN 105778008A CN 201410836102 A CN201410836102 A CN 201410836102A CN 105778008 A CN105778008 A CN 105778008A
- Authority
- CN
- China
- Prior art keywords
- monomer
- polymer particle
- methyl
- formula
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Optical Elements Other Than Lenses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides polymer particles, and a preparation method and an application of the polymer particles. The polymer particles can be uniformly disperses in dispersion liquid, and can fully agglomerate when the dispersion liquid is volatilized. The polymer particles provided by the invention comprise a hydroxyl-monomer-containing constituent unit represented by the following general formula (1) and/or general formula (2), a constituent unit from a monofunctional (methyl) acrylic monomer, a constituent unit from a monofunctional styrenic monomer, and a constituent unit from a crosslinking monomer. The polymer particles has a volume average particle size of below 5mum, and hydroxyl value of higher than 5.0mgKOH/g and lower than 15mgKOH/g.
Description
Technical field
The present invention relates to manufacture method of can be used as the polymer particle of parts raw material of the optics parts such as antiglare film, optical diffusion film etc., polymer particle and application thereof.
Background technology
Polymer particle is used in the wide spectrum of liquid crystal sept, chromatographic grade filler, diagnostic reagent etc..And, also serve as the optics parts such as light diffusing sheet, optical diffusion film, antiglare film for various device fields such as display devices.Such polymer particle, when being supplied to practical use, most can be scattered in the dispersion liquid in water, organic solvent equal solvent or in this dispersion liquid and then add the form such as coating of the resinous principles such as resin glue and use with polymer particle.
For in the optics parts of display device, for instance require to mirror to prevent function to antiglare film.Mirror and prevent function from being the micro concavo-convex scattering exterior light formed by polymer particle and realize.Especially, function is prevented in order to realize mirroring of high-quality, it is desirable to antiglare film generally forms uniform and fine concavo-convex.
Formed fine concavo-convex time, first in the dispersion liquid containing solvent and resin glue dispersed polymer particle and do not make it condense.Then dispersion liquid is applied in the surface of film base material etc., dries and make solvent volatilize.Thus, polymer particle is gathered on film base material, forms doubtful state of aggregation, thus forming micro concavo-convex.
As such particle, Patent Document 1 discloses a kind of self-coagulation particle.It addition, as the particle of excellent dispersion, Patent Document 2 discloses a kind of high-hydrophilic polymer particle, it is to be obtained by the seed particles absorbing polymer sex ethylene base class monomer post polymerization containing hydrophilic macromonomer.
Patent documentation 1: Japanese Unexamined Patent Publication 2013-231133 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-062389 publication
But, along with the high-precision refinement, thin layer of display device in recent years, the quality of the optical film such as antiglare film is also diversified, sometimes also can require to be dispersed in alcohols solvent to the particle for optical film.Therefore, it is intended that exploitation can be dispersed in alcohols solvent and sufficient particle after coating.
Summary of the invention
In view of this, it is an object of the invention to, it is provided that can polymer particle dispersed in dispersion liquid, that can fully condense when dispersion liquid volatilizees.
It addition, other purposes of the present invention are in that, it is provided that the manufacture method of described polymer particle, containing the optical film after the dispersion liquid of described polymer particle, Coating dispersions.
The present inventor is by making to include the various monomer polymerizations of the hydroxyl monomer of regulation, and makes the numerical value such as volume average particle size, hydroxyl value within the limits prescribed, thus completing the present invention solving described problem.
Heretofore described polymer particle, it is characterized in that, containing carrying out the Component units of the hydroxyl monomer shown in free following formula (1) and/or formula (2), from the Component units of simple function (methyl) acrylic monomer, monofunctional styrenic's monomer, Component units from cross-linkable monomer, volume average particle size is less than 5 μm, and hydroxyl value is more than 5.0mgKOH/g and below 15mgKOH/g.
Formula (1)
(in formula (1), R represents H or CH3, m represents the numeral of 0～50, and n represents the numeral of 0～50, is 0 during m and n difference).
Formula (2)
(in formula (2), R separately represents H or CH3, p represents the numeral of 1～50).
Therefore, heretofore described polymer particle is dispersed in dispersion liquid, fully condenses when dispersion liquid volatilizees.
The manufacture method of heretofore described polymer particle is to make vinyl monomer polymerization manufacture the polymer particle manufacture method of polymer particle, it is characterized in that, described vinyl monomer includes the hydroxyl monomer shown in following formula (1) and/or formula (2), simple function (methyl) acrylic monomer, monofunctional styrenic's monomer and cross-linkable monomer, relative to described vinyl monomer total amount, containing the described hydroxyl monomer of 3～15 weight %.
Formula (1)
(in formula (1), R represents H or CH3, m represents the numeral of 0～59, and n represents the numeral of 0～50, is 0 during m and n difference).
Formula (2)
(in formula (2), R separately represents H or CH3, p represents the numeral of 1～50).
Therefore, the polymer particle obtained by the manufacture method manufacture of heretofore described polymer particle is dispersed in dispersion liquid, fully condenses when dispersion liquid volatilizees.
Heretofore described dispersion liquid, it is characterised in that containing described polymer particle and binding agent, described polymer particle is disperseed as dispersate.
Therefore, heretofore described dispersion liquid, polymer particle is dispersed, and when coating the coating objects such as base material film and make it dry, polymer particle fully condenses.
Heretofore described optical film, it is characterised in that described dispersion liquid is coated and is formed on base material film.
Therefore, when heretofore described optical film is owing to making it dry after coating, polymer particle fully condenses, and is therefore formed uniform and fine concavo-convex.
The polymer particle of the present invention, the manufacture method of polymer particle, dispersion liquid and optical film, for instance when being used as to have the film of anti-glare, carry out scattering light by the micro concavo-convex formed by polymer particle, the excellent effect thereby serving to be possible to prevent to mirror etc..
Accompanying drawing explanation
Fig. 1 is the image of the polymer particle representing embodiment 1 dispersity in alcoholic solvent dispersion liquid.
Fig. 2 is the image of the polymer particle representing embodiment 1 dispersity in alcoholic solvent dispersion liquid.
Fig. 3 is the image of the polymer particle representing comparative example 2 dispersity in alcoholic solvent dispersion liquid.
Fig. 4 is the image of the polymer particle representing comparative example 2 dispersity in alcoholic solvent dispersion liquid.
Detailed description of the invention
For the present invention described further below.
[polymer particle]
The polymer particle of the present invention, for instance as optics such as diffuser plate, optical diffusion film, antiglare film with parts for field of display devices.The polymer particle of the present invention contain to come the hydroxyl monomer shown in free following formula (1) and/or following formula (2) Component units, from the Component units of simple function (methyl) acrylic monomer, the Component units from monofunctional styrenic's monomer, the vinyl monomer from cross-linkable monomer etc. Component units.
Formula (1)
(in formula (1), R represents H or CH3, m represents the numeral of 0～50, and n represents the numeral of 0～50, is 0 during m and n difference.It addition, m and n is preferably 1～30.)
Formula (2)
(in formula (2), R separately represents H or CH3, p represents the numeral of 1～50.Wherein p is preferably 1～30.)
In described monomer, as the commercially available product of the hydroxyl monomer shown in formula (1), " Block レ Application マ (registered trade mark) " series that Japan Oil Co produces can be for example there are.And then, in described " Block レ Application マ (registered trade mark) " series, (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH to the present invention preferably " Block レ Application マ (registered trade mark) 50PEP-300 "3, m is on average about 3.5, n and is on average about 2.5), " Block レ Application マ (registered trade mark) 70PEP-350B " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, m is on average about 5, n and is on average about 2), " Block レ Application マ (registered trade mark) PP-1000 " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, m 0, n is on average about 4～6), " Block レ Application マ (registered trade mark) PP-500 " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, m 0, n is on average about 9), " Block レ Application マ (registered trade mark) PP-800) " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, m 0, n is on average about 13), " Block レ Application マ (registered trade mark) PE-90 " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, it is 0 that m is on average about 2, n), " Block レ Application マ (registered trade mark) PE-200 " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, it is 0 that m is on average about 4.5, n), " Block レ Application マ (registered trade mark) PE-350 " (mixture that the multiple compounds shown in described formula (1) is constituted, R is CH3, it is 0 that m is on average about 8, n) etc..These individually can only use one, it is possible to combines two or more use.
As the commercially available product of hydroxyl monomer shown in formula (2), " プ ラ Network セ Le (registered trade mark) FM " series that Co., Ltd.'s ダ イ セ Le produces can be for example there are.In described " プ ラ Network セ Le (registered trade mark) FM " series, (compound shown in described formula (2), R is CH to the present invention preferably " プ ラ Network セ Le (registered trade mark) FM2D "3, p is 2), " プ ラ Network セ Le (registered trade mark) FM3 " (compound shown in described formula (2), R is CH3, p is 3) etc..These individually can only use one, it is possible to combines two or more use.
Simple function (methyl) acrylic monomer is to have ethylene unsaturated group (methyl) acrylic monomer.As simple function (methyl) acrylic monomer, (methyl) alkyl-acrylates etc. such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) lauryl acrylate, (methyl) octadecyl acrylate can be for example there are.It addition, in this specification, " (methyl) acrylate " means acrylate or methacrylate, " (methyl) acrylic acid " means acrylic or methacrylic acid.
Among above-mentioned simple function (methyl) acrylic monomer, if using the simple function that dissolubility is below 0.45 weight % (methyl) acrylic monomer to 25 DEG C of water, then the hydroxyl monomer shown in formula (1) is difficult to enter inside polymer particle, easily being present in top layer, therefore the viewpoint from alcohol dispersibility is preferred.
Specifically, can illustrate (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, wherein particularly preferably (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate.It addition, from the viewpoint of alcohol dispersibility, measure relative to simple function (methyl) acrylic monomer and the total of monofunctional styrenic's monomer, it is preferable that above-mentioned simple function (methyl) acrylic monomer containing 30～95 weight %.
It addition, in this manual, the dissolubility of water is measured in accordance with the following methods.
(assay method to the dissolubility of water)
With the weight ratio mixing water of 1:1 and simple function (methyl) acrylic monomer, stir 30 minutes at 25 DEG C.Use separatory funnel separation aqueous phase and oil phase, measure the amount (weight %) of simple function (methyl) acrylic monomer being dissolved in aqueous phase by high performance liquid chromatography (HPLC).
Monofunctional styrenic's monomer is the styrene monomer with an ethylene unsaturated group.As monofunctional styrenic's monomer, styrene, α-methyl styrene, vinyltoluene, vinyl xylene, ethyl vinyl benzene etc. can be for example there are.Wherein, from the viewpoint of alcohol dispersibility and polymerisation reactivity, it is preferable that styrene.
Cross-linkable monomer is the polyfunctional monomer with multiple ethylene unsaturated group, has the function as cross-linking agent.nullAs cross-linkable monomer，Trimethylolpropane trimethacrylate can be for example there are、Ethylene glycol dimethacrylate、Dimethacrylate、TEGDMA、Ten ethylene glycol dimethacrylates、Ten five ethylene glycol dimethylacrylates、50/100 ethylene glycol dimethacrylate (pentacontahectaethyleneglycoldimethacrylate)、1,3-butanediol dimethylacrylate、Allyl methacrylate、Trimethylol-propane trimethacrylate、Tetramethylol methane tetraacrylate etc. multifunctional (methyl) acrylic ester monomer，Divinylbenzene、Divinyl naphthalene、N,N-divinyl aniline、Divinyl ether、Divinyl sulfide、The divinyl base class monomers such as divinyl sulfonic acid.
With the polymer particle of the present invention that above-mentioned monomer is Component units, as Component units, it is preferable that the hydroxyl monomer containing 3～15 weight %, the cross-linkable monomer of 3～35 weight %.When hydroxyl monomer is less than 3 weight %, the dispersibility in the hydrophilic organic solvents such as alcohols solvent is not enough, and the operability of coating is likely to decrease, and during higher than 15 weight %, above-mentioned dispersibility becomes superfluous, is coated with, can not get desired state of aggregation after drying.When cross-linkable monomer is less than 3 weight %, the degree of cross linking step-down of resin particle, its result resin particle is mixed with binding agent after as dispersion liquid be coated with time, it is possible to resin particle is swelling and causes the viscosity of dispersion liquid to rise, cause coating operability reduce.It addition, when cross-linkable monomer is higher than 35 weight %, effect is not correspondingly made available raising with the consumption that makes of above-mentioned cross-linkable monomer, it is possible to increase production cost.
It addition, it is less than 5 μm that the polymer particle of the present invention is synthesized into volume average particle size.Further, volume average particle size can be measured by such as Coulter-counter method.
About polymer particle, by making volume average particle size be less than 5 μm, when being coated and dry and be processed as thin film, form preferred protuberance with suitable quantity cohesion.And, by making particle diameter be more than 1 μm and less than 5 μm, preferred protuberance can be formed.
It addition, when the volume average particle size of polymer particle is more than 5 μm, for instance when using as the antiglare film on display device surface, the protuberance formed due to polymer particle coalescing is precipitous, causes excessive scattering exterior light, and display surface likely can become to turn white.And, when the volume average particle size of polymer particle is less than 1 μm, for instance as display device surface antiglare film use time, due to polymer particle coalescing formed protuberance become smooth, can not fully scattering exterior light, it is possible to cannot suppress mirroring to display surface.
The particle diameter coefficient of variation (CV) of above-mentioned polymer particle, it is preferred to less than 15%.Thus, when using the polymer beads period of the day from 11 p.m. to 1 a.m in the optics such as antiglare film, optical diffusion film, the optical characteristics such as anti-glare and light diffusing of optics can be improved.
It addition, it is more than 5.0mgKOH/g and below 15mgKOH/g that the polymer particle of the present invention is synthesized into its hydroxyl value.Further, hydroxyl value such as can be measured by hydroxyl value quantitative analysis method (JISK0070).
It is 5.0～15mgKOH/g by making the hydroxyl value of polymer particle, when being distributed in the hydrophilic organic solvents such as alcohols solvent together with binding agent, can appropriateness be scattered in hydrophilic organic solvent.That is, the polymer particle of the present invention, it is possible to dispersed without condensing, and when making it be coated with and drying, excessively dispersion will not be caused to cause that cohesion is bad.
By dispersed in hydrophilic organic solvent, when forming the optical films such as such as antiglare film, the uniform thin film being speckless can be formed.It addition, by preventing cohesion bad, can be formed fine concavo-convex, the exterior light such as the light that scattering external fluorescent lamps sends and prevent from mirroring, improve anti-glare.
Further, polymer particle is less than 5 μm by making volume average particle size, when being coated and dry and be processed into thin film, forms preferred protuberance with suitable quantity cohesion.
Further, when the volume average particle size of polymer particle more than 5 μm when, for instance when using as the antiglare film on display device surface, polymer particle coalescing and the protuberance that formed becomes precipitous, therefore excessive scattering exterior light, display surface likely can become to turn white.
The Component units from each monomer in polymer particle qualitatively and quantitatively, can be confirmed by gas chromatogram, liquid chromatograph, infrared spectrophotometer (IR), nuclear magnetic resonance method (NMR) decile analysis method.Further, the weight ratio of each monomer in monomer mixture is roughly the same with the weight ratio from the Component units of each monomer in polymer particle.
[manufacture method of polymer particle]
Manufacture method with regard to the polymer particle of the present invention illustrates below.The polymer particle of the present invention, it is preferable that manufactured by seeding polymerization.Manufactured by seeding polymerization, it is possible to suppress the deviation of particle diameter.By suppressing the deviation of particle diameter, when as the optical film such as antiglare film, optical diffusion film, it is possible to improve the optical characteristics such as anti-glare, light diffusing.But, the manufacture of the polymer particle of the present invention, it is not necessary to be necessarily limited to seeding polymerization, it is also possible to undertaken by polymerizations such as emulsion polymerization, suspension polymerisations.
Seeding polymerization is to use by the monomers such as vinyl monomer are polymerized the method that seed (kind) particle that the polymer obtained constitutes is polymerized, make seed particles specifically, the seed particles making other monomer absorption obtain in manufacture in an aqueous medium, makes to absorb a kind of method of the monomer polymerization within seed particles.
In seeding polymerization, in the emulsion (suspension) containing seeding polymerization monomer, aqueous medium and surfactant, first add seed particles.
As seeding polymerization monomer, vinyl monomer can be for example there are, for instance the mixture etc. of simple function (methyl) acrylic monomer, monofunctional styrenic's monomer, simple function (methyl) acrylic monomer and monofunctional styrenic's monomer.
As aqueous medium, the mixture etc. of lower alcohol (alcohol of carbon number less than 5), water and the lower alcohols such as water, methanol, ethanol can be for example there are.
The arbitrary surfaces activating agent of anion surfactant, cationic surfactant, nonionic surfactant and amphoteric surfactant can be used as above-mentioned surfactant.
As described anion surfactant, enuatrol can be for example there are, the fatty acid soaps such as Oleum Ricini potash soap, sodium lauryl sulphate, the alkyl sulfate salt such as ammonium lauryl sulfate, the alkylbenzenesulfonates such as dodecylbenzene sodium sulfonate, alkylnaphthalene sulfonate, alkylsulfonate, two (2-ethylhexyl) sodium sulfosuccinate, the dialkyl sulfosuccinates such as dioctyl sodium sulphosuccinate, alkenyl succinate (two calcium salts), alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene alkyl phenyl ether sulfuric acid, the polyoxyethylene alkyl ether sulfate salts such as sodium laureth sulfate, polyoxyethylene alkyl sulfate etc..
As described nonionic surfactant, the polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether can be for example there are, the polyoxyethylene alkyl phenyl ethers such as NONIN HS 240, polyoxyethylene styrene phenyl ether, the polyoxyalkylene alkyl such as the polyoxyalkylene tridecyl ester of the carbon number more than 3 of thiazolinyl, polyoxyethylene fatty acid ester, the polyoxyethylene sorbitan carboxylic esters such as sorbitan carboxylic esters, mono laurate polyoxyethylene sorbitol acid anhydride, polyoxyethylene alkyl amine, fatty acid glyceride, POLOXAMER etc..
As above-mentioned cationic surfactant, the alkylamine salts such as lauryl amine acetate, stearyl amine acetate can be for example there are, the quaternary ammonium salt etc. such as lauryl trimethyl ammonium chloride.
As above-mentioned amphoteric surfactant, lauryl dimethyl amine oxide, phosphate ester surfactant, phosphorous acid esters surfactant etc. can be for example there are.Above-mentioned surfactant can be used alone one, it is possible to combines two or more use.
Surfactant in seeding polymerization make consumption, relative to seeding polymerization monomer 100 weight portion, it is preferable that in the scope of 0.01～5 weight portion.When surfactant makes consumption less than above-mentioned scope, it is possible to polymerization stability step-down.It addition, when surfactant uses higher than above-mentioned scope, the cost of surfactant raises.
The emulsion added is manufactured by known method.Such as, monomer and surfactant are added in aqueous medium, disperse with fine down equipment such as homogenizer, ultrasonic processor, ultra micron gasifying devices (Na ノ マ イ ザ), obtain emulsion.As above-mentioned aqueous medium, water or water and the mixture of organic solvent (such as lower alcohol (alcohol of carbon number less than 5)) can be used.
Seed particles, it is possible to be directly appended in emulsion, it is also possible to add in emulsion with the form being distributed in aqueous medium.After seeding polymerization seed particles adds emulsion to, seeding polymerization monomer is absorbed by seed particles.This absorption generally can carry out through 1～12 hour stirring and emulsifying liquid under room temperature (about 20 DEG C).It addition, in order to promote that seeding polymerization monomer is absorbed by seed particles, emulsion can be heated to about 30～50 DEG C.
Seed particles is swelling by absorption monomer.The seeding polymerization monomer absorbed and the mixed proportion of seed particles are, relative to seed particles 1 weight portion, in the monomer of the absorption scope preferably in 5～300 weight portions, it is preferred that in the scope of 100～250 weight portions.When the mixed proportion of the seeding polymerization monomer absorbed is less than above-mentioned scope, the increase of the particle diameter that polymerization brings diminishes, and manufactures efficiency and reduces.On the other hand, when the mixed proportion of the seeding polymerization monomer absorbed is higher than above-mentioned scope, seeding polymerization monomer can not be absorbed by seed particles completely, individually carries out suspension polymerisation in an aqueous medium, it is possible to generates the abnormal little polymer particle of particle diameter.Further, seeding polymerization monomer is to whether the absorption of seed particles terminates, it is possible to confirmed that by observation by light microscope the expansion of particle diameter judges.
Therefore, by being polymerized the monomer absorbed by seed particles, the polymer particle of the present invention can be obtained.And, it is also possible to repeatedly repeat to make the step of the monomer polymerization absorbed by seed particles, obtain the polymer particle of the present invention.
The seeding polymerization monomer being polymerized, can be added as needed on polymerization initiator.After polymerization initiator can be mixed in the monomer being polymerized, the mixture obtained is scattered in aqueous medium, it is possible to polymerization initiator and the seeding polymerization monomer being polymerized are scattered in aqueous medium respectively and they are mixed.The size droplet diameter of the seeding polymerization monomer existed in the emulsion obtained is preferably smaller than the particle diameter of seed particles, because so monomer can be effectively absorbed by seed particles.
nullAs polymerization initiator，There is no particular limitation，Benzoyl peroxide can be for example there are、Lauroyl peroxide、O-chloro benzoyl peroxide、O-methoxyl group benzoyl peroxide、3,5,5-trimethyl acetyl base peroxide、Peroxidating (2 ethyl hexanoic acid) tert-butyl ester、The organic peroxides such as di-t-butyl peroxide，2,2 '-azobis isobutyronitrile、2,2 '-azo double; two (2,4-methyl pentane nitrile)、2,2 '-azo double; two (2,3-nitrile dimethyl)、2,2 '-azo double; two (2-methylbutyronitrile)、2,2 '-azo double; two (2,3,3-trimethylbutyronitrile)、2,2 '-azo double; two (2-isopropyl butyronitrile)、1,1 '-azo double; two (hexamethylene-1-nitrile)、2,Double; two (the 4-methoxyl group-2 of 2 '-azo,4-methyl pentane nitrile)、(2-carbamoyl azo) isopropyl cyanide ((2-カ Le バ モ イ Le ア ゾ) イ ソ Block チ ロ ニ ト リ Le)、4,4 '-azo double; two (4-cyanopentanoic acid)、Dimethyl-2,The azo-compounds etc. such as 2 '-azobisisobutylonitrile acid esters.Relative to monomer 100 weight portion, in the polymerization initiator scope preferably in 0.1～1.0 weight portion.
The polymerization temperature of above-mentioned seeding polymerization, suitably can determine according to the kind of the kind of the seeding polymerization monomer being polymerized and the polymerization initiator used as required.The polymerization temperature of seeding polymerization, is preferably 25～110 DEG C specifically, more preferably 50～100 DEG C.It addition, the polymerization time of seeding polymerization, it is preferred to 1～12 hour.The polyreaction of seeding polymerization, can carry out under noble gas (such as nitrogen) atmosphere being inertia to polymerization.Further, after the polyreaction of seeding polymerization is fully absorbed by seed particles preferably in the monomer being polymerized and the polymerization initiator that uses as required, heat up and carry out.
In above-mentioned seeding polymerization, in order to improve the dispersion stabilization of polymer particle, macromolecular dispersion stabilizer can be added in polymerization reaction system.As described macromolecular dispersion stabilizer, polyvinyl alcohol, polycarboxylic acids, cellulose family (hydroxyethyl cellulose, carboxymethyl cellulose etc.), polyvinylpyrrolidone etc. can be for example there are.Alternatively, it is also possible to and with mineral-type water-soluble high-molecular compounds such as above-mentioned macromolecular dispersion stabilizer and sodium tripolyphosphates.In these macromolecular dispersion stabilizers, it is preferable that polyvinyl alcohol and polyvinylpyrrolidone.Relative to seeding polymerization monomer 100 weight portion, in the addition of the above-mentioned macromolecular dispersion stabilizer scope preferably in 1～10 weight portion.
Additionally, in order to suppress the generation of the emulsified particle (polymer particle that particle diameter is too small) in the aqueous medium in above-mentioned polyreaction, the water miscible polymerization inhibitors such as the nitrites such as sodium nitrite, sulfites, hydroquinones, Vitamin C acids, aqueous vitamin B class, citric acid, oxidoreductase can be added in an aqueous medium.Relative to vinyl monomer 100 weight portion, in the addition of the above-mentioned polymerization inhibitor scope preferably in 0.02～0.2 weight portion.
The polymer particle so obtained by the seeding polymerization monomer absorbed by seed particles is polymerized is performing centrifugal separation on as required removing aqueous medium after polymerization terminates, after cleaning with water and/or solvent, and dry, separation.The method that the polymer particle obtained by seeding polymerization is separated from aqueous medium, be not particularly limited, can for example there are with spray dryer be representative spray drying method, drum dryer be representative the method being attached to heated cylinder and dry method, freeze-drying etc..
Further, for being polymerized the polymerization of seeding polymerization monomer for obtaining seed particles, it does not have limit especially, dispersin polymerization, emulsion polymerization, emulsifier-free emulsion polymerization, seeding polymerization, suspension polymerisation etc. can be used.In order to obtain the substantially uniform polymer particle of particle diameter by seeding polymerization, it is necessary to use the substantially uniform seed particles of particle diameter at the very start, make these seed particles grow into much the same.The substantially uniform seed particles of particle diameter as raw material, it is possible to manufactured by vinyl monomers such as polymerization monofunctional polymerizable (methyl) acrylic monomer, monofunctional styrenic's monomer such as emulsifier-free emulsion polymerization (emulsion not using surfactant is polymerized) and dispersin polymerizations.Accordingly, as the polymerization for obtaining seed particles, it is preferable that emulsion polymerization, emulsifier-free emulsion polymerization, seeding polymerization and dispersin polymerization.
For obtaining in the polymerization of seed particles, use polymerization initiator also according to needs.As described polymerization initiator; the persulfuric acid salts such as persulfuric acid calcium, Ammonium persulfate., sodium peroxydisulfate can be for example there are; benzoyl peroxide, lauroyl peroxide, o-chloro benzoyl peroxide, o-methoxyl group benzoyl peroxide, 3; 5; 5-trimethyl acetyl base peroxide, peroxidating (2 ethyl hexanoic acid) organic peroxide such as the tert-butyl ester, di-tert-butyl peroxide, 2; 2 '-azobis isobutyronitrile, 1; the double; two cyclohexanenitrile of 1 '-azo, 2; the azo compounds such as 2 '-azo double; two (2,4-methyl pentane nitrile).Above-mentioned polymerization initiator make consumption, relative to seeding polymerization monomer 100 weight portion used for obtaining seed particles, it is preferable that in the scope of 0.1～3 weight portion.The increase and decrease of consumption is made, the weight average molecular weight of the seed particles that scalable is obtained according to above-mentioned polymerization initiator.
For obtaining in the polymerization of seed particles, in order to regulate the weight average molecular weight of the seed particles obtained, molecular weight regulator can be used.As described molecular weight regulator, the thio-alcohol such as n octylmercaptan, tertiary lauryl mercaptan, α-methylstyrenedimer, γ-terpenes such as terpinene, cinene, the halogenated hydrocarbon such as chloroform, carbon tetrachloride etc. can be used.By the increase and decrease making consumption of above-mentioned molecular weight regulator, the weight average molecular weight of the seed particles that scalable is obtained.
The polymer particle of the present invention is suitable for the optics of the optical film such as antiglare film, optical diffusion film, it addition, be suitable for mixing with binding agent being used as dispersion liquid.
[manufacture method of optical film]
Next the polymer particle just using the present invention manufactures the method for optics parts and illustrates.Here, the optical films such as manufacture antiglare film are illustrated as the example of optics parts.During the optical film of the present invention manufactures, use the dispersion liquid that the dispersates such as the polymer particle of the present invention are scattered in the disperse medium such as binding agent the present invention obtained.Specifically, the dispersates such as polymer particle are scattered in the disperse medium such as binding agent the coating dispersion liquid obtained and coat on film base material so that it is be dry, thus being formed as film on film base material.
As binding agent, according to the characteristic that the transparency, polymer beads molecular dispersivity, light resistance, moisture-proof and thermostability etc. require, as long as can using in this field, then there is no particular limitation.As binding agent, (methyl) acrylic resin can be for example there are, (methyl) acrylic acid-polyurethane resinoid, polyurethane based resin, polyvinyl chloride resin, Vingon resinoid, tripolycyanamide resinoid, styrene resin, alkyd based resin, phenolic resin, epoxylite, polyester resin, the silicone resins such as alkyl polysiloxane resinoid, (methyl) acrylic acid-silicone resin, silicone-ol acid resin, silicone-polyurethane resinoid, the modified silicone resins such as silicone-polyester resin, polyvinylidene fluoride, the resin glue of the fluoro resinoids etc. such as fluoroolefin vinylic-ether polymer.
Resin glue, from the viewpoint of improve the durability of coating dispersion liquid, it is preferable that can be formed the curable resin of cross-linked structure by cross-linking reaction.Curable resin can solidify under various conditions of cure.The curable resin difference according to curing type, is divided into the kinds such as the ionizing radiation curable resin such as uv curing resin, electronic beam curing resin, thermosetting resin, wet (temperature) curable resin.
As thermosetting resin, can for example there are be made up of acrylic polyol and isocyanate prepolymer heat-curable urethane resinoid, phenolic resin, urea melamine, epoxy resin, unsaturated polyester resin, silicone resin etc..
As ionizing radiation curable resin, multifunctional (methyl) acrylate of polyhydric alcohol multifunctional (methyl) acrylate etc. can be for example there are, by diisocyanate, polyhydric alcohol with have the multifunctional polyurethane acrylate resin etc. that (methyl) acrylate etc. of hydroxyl is synthetically derived.
As ionizing radiation curable resin, except these, it be also possible to use and there are the polyether resin of esters of acrylic acid functional group, polyester resin, epoxy resin, alkyd resin, spiral shell acetal (ス ピ ロ ア セ タ Le) resin, polybutadiene, the many olefine resins of polymercaptan etc..
As resin glue, except above-mentioned curable resin, it be also possible to use thermoplastic resin.As thermoplastic resin, acetylcellulose can be for example there are, NC Nitroncellulose, acetyl group butyl cellulose, ethyl cellulose, the cellulose derivatives such as methylcellulose, the homopolymer of vinyl acetate and copolymer, the homopolymer of ethlyene dichloride and copolymer, the vinyl group resin such as the homopolymer of vinylidene chloride and copolymer, polyvinyl formal, the acetal resins such as polyvinyl butyral resin, the homopolymer of acrylate and copolymer, (methyl) acrylic resins such as the homopolymer of methacrylate and copolymer, polystyrene resin, polyamide, linear polyester resin, polycarbonate resin etc..
It addition, as binding agent, except above-mentioned resin glue, it is possible to use the rubber-like binding agent such as synthetic rubber, natural rubber, and mineral-type binding agent etc..As rubber-like resin glue, ethylene-propylene copolymer rubber, polybutadiene rubber, SBR styrene butadiene rubbers, acrylonitrile-butadiene rubber etc. can be for example there are.
Above-mentioned coating dispersion liquid also can contain organic solvent further.When being coated with above-mentioned coating dispersion liquid on the base materials such as film base material described later, as long as owing to making coating dispersion liquid that the coating of base material is become easy containing above-mentioned organic solvent, then there is no particular limitation.nullAs above-mentioned organic solvent，Toluene can be used、The aromatic solvents such as dimethylbenzene，Methanol、Ethanol、Normal propyl alcohol、Isopropanol、N-butyl alcohol、Isobutanol、The alcohols solvents such as propylene glycol monomethyl ether，Ethyl acetate、The esters solvents such as butyl acetate，Acetone、Butanone、Methyl iso-butyl ketone (MIBK)、Ketocyclopentane、The ketones solvents such as Ketohexamethylene，2-methyl cellosolve、Cellosolvo、Butoxy ethanol、Glycol dimethyl ether、Ethylene glycol diethyl ether、Diglycol dimethyl ether、The dihydroxylic alcohols ethers such as propylene glycol monomethyl ether，2-methoxyethyl acetate、2-ethoxyethyl acetate (Cellosolveacetate)、2-butoxy ethyl acetate、The glycol ether esters such as methyl proxitol acetate，Chloroform、Dichloromethane、Chloroform、The chloro kind solvents such as tetrachloromethane，Oxolane、Diethyl ether、1,4-dioxane、1,The ether solvents such as 3-dioxolanes，N-Methyl pyrrolidone、Dimethylformamide、Dimethyl sulfoxide、The amide solvents etc. such as dimethyl acetylamide.These organic solvents, can be used alone one, it is possible to mixes two or more use.Wherein, consider from the polymer particle uniformly dispersed and dried coherency dispersion liquid, it is preferable that the alcohols solvent of carbon number less than 5, it is preferred that methanol, ethanol, propanol.
Film base material preferably clear base material.As transparent film base material; the polyester polymers such as use polyethylene terephthalate (PET), PEN can be for example there are; the cellulosic polymers such as diacetyl cellulose, tri acetyl cellulose (TAC); polycarbonate polymer, the film of the polymer such as (methyl) acrylic polymer such as polymethyl methacrylate class.Additionally, as transparent film base material, also the use styrenic polymer such as polystyrene, acrylonitritrile-styrene resin can be for example there are, polyethylene, polypropylene, polyolefin containing ring-type or bornylene structure, the olefin polymers such as ethylene-propylene copolymer, vinyl chloride polymer, the film of the polymer such as acylamide polymer such as nylon, aromatic polyamide.And, as transparent film base material, it is possible to for example there are the film etc. of the polymer of the mixture etc. of sub-acylamide polymer, sulfone base polymer, polyether sulfone polymer, polyether-ether-ketone polymer, polyphenylene sulfide base polymer, vinyl alcohol polymer, vinylidene chloride base polymer, vinyl butyral base polymer, aryl nitrone polymer, polyformaldehyde base polymer, epoxide polymer, these polymer.As above-mentioned film base material, it is particularly preferred to use the less film base material of birefringence.It addition, the film of the easy adhesive layer arranging (methyl) acrylic resin, copolyester resinoid, polyurethane based resin, styrene-maleic acid grafted polyester resin, acrylic acid-grafted polyester resin etc. further to these films can also use as above-mentioned film base material.
The thickness of film base material can suitably be determined, but in general from the viewpoint of the operability such as intensity, process, thin layer etc. in 10～500 μ m, it is preferable that in 20～300 μ m, more preferably in 30～200 μ m.It addition, the additives such as UV absorbent, infrared absorbent, antistatic additive, adjustable refractive index agent, reinforcing agent also can be added in film base material.
As the method coated by coating dispersion liquid on film base material, the known coating processes such as stick coating method (バ U テ ィ Application グ), insert coating method, spin-coating method, reverse coating (リ バ ス U テ ィ Application グ), mould coating (ダ イ U テ ィ Application グ), spraying process, rolling method, intaglio plate coating, nick version coating, lip mould coating, air-knife coating method, dip coating can be for example there are.
The optical film of the present invention so constituted, owing to being that the coating dispersion liquid of polymer particle by the present invention excellent containing dispersion stabilization is coated and obtained on base material, therefore, in the film entirety formed by described coating, can be stablized and the uniform optical characteristics such as light diffusing, anti-glare.Therefore, the optical film of the present invention has high-quality stability.
[embodiment]
The present invention will be described below by way of embodiments and comparative examples, but the present invention is not limited to these.First, to following example and comparative example, the volume average particle size assay method of seed particles, the hydroxy value measuring method of polymer particle and the alcoholic solvent distributed test illustrating to use in the manufacture of the volume average particle size of polymer particle and the assay method of the particle diameter coefficient of variation, polymer particle.
{ volume average particle size of polymer particle and the assay method of the particle diameter coefficient of variation }
The volume average particle size of polymer particle coulter counter III (Beckman Ku Erte Co., Ltd. determinator) measures.The aperture (Aperture) by the calculating instrument TM3 users' guidebook correction of Beckman Ku Erte Co., Ltd. distribution is used to be measured.
Further, the aperture measured it is used for according to the appropriately sized selection measuring particle.When selection has 50 μm of apertures, electric current (aperture current) is set as-800, and gain (Gain) is set as 4.
As test sample, by touch blender (ヤ マ ト science Co., Ltd. system, " TOUCHMIXERMT-31 ") and ultrasonic cleaner (Co., Ltd.'s ヴ ェ Le ヴ ォ Network リ ア system, " ULTRASONICCLEANERVS-150 ") polymer particle 0.1g is scattered in the nonionic surfactant water-soluble liquid of 0.1 weight %, use as dispersion.Mensuration is slowly stirred, it is to avoid in beaker, introduce bubble, terminates to measure at the time point measuring 100,000 polymer particles.The volume average particle size of polymer particle is the arithmetic mean of instantaneous value in the particle size distribution of the volume reference of 100,000 particles.
The particle diameter coefficient of variation (CV value) of polymer particle is calculated by following mathematical expression and obtains.
The particle diameter coefficient of variation of polymer particle=(volume average particle size of the volume reference particle size distribution standard deviation ÷ polymer particle of polymer particle) × 100
{ assay method of the volume average particle size of the seed particles used in the manufacture of polymer particle }
The mensuration of the volume average particle size of the seed particles used in the manufacture of polymer particle is undertaken by laser diffraction/scattering formula particle size distribution device (Beckman Ku Erte Co., Ltd.'s system " LS13320 ") and universal liquid sample module (ユ ニ バ サ Le リ キ ッ De サ Application プ Le モ ジ ュ Le).
Specifically, by touch blender (big and science Co., Ltd. system, " TOUCHMIXERMT-31 ") and ultrasonic cleaner (Co., Ltd.'s ヴ ェ Le ヴ ォ Network リ ア system, " ULTRASONICCLEANERVS-150 ") seed particles dispersion liquid 0.1g is scattered in 0.1 weight % nonionic surfactant aqueous solution 10ml, use as dispersion.
Universal liquid sample block carries out pump circulation, thus in the state disperseing above-mentioned seed particles, and carry out under the state starting ultrasound unit (ULMULTRASONICMODULE), calculate the volume average particle size (arithmetic average diameter in the particle size distribution of volume reference) of seed particles.Condition determination is as described below.
Medium=water
Medium refraction index=1.333
Solid refractive index=seed particles refractive index (1.495)
PIDS relative concentration: about 40～55%
{ the hydroxy value measuring method of polymer particle }
The hydroxy value measuring of polymer particle carries out according to hydroxyl value quantitative analysis method (JISK0070-1992).It is following step specifically.
< hydroxy value measuring acid value measuring method " JISK0070 " >
The flat bottom beaker of 200mL adds 2g sample and 20mL pyridine solvent, after at room temperature stirring makes it disperse in 1 hour, adds 3 phenolphthalein reagents, with 0.5mol/L potassium hydroxide-ethanol solution titration, become aubergine for terminal with color.Carry out blank assay by same method, calculate according to the following formula and obtain acid number.Mensuration performs twice at, with its meansigma methods for acid number.
< acid number calculating formula >
Acid number (mgKOH/g)=(V1-V0) × f × 0.1 × 56.11 ÷ S
Wherein
S: sample quality (g)
V0: the amount (mL) of the 0.1mol/L potassium hydroxide-ethanol solution needed in blank assay .... blank titration amount (mL)
V1: the amount (mL) of the 0.1mol/L potassium hydroxide-ethanol solution needed in this test .... sample drop is quantitatively (mL)
The factor of f:0.1mol/L potassium hydroxide-ethanol solution ... 1.0
< analyzes method step >
After adding 2g sample and 3mL acetylation reagent in 200mL flat bottom beaker, stirring makes it fuse, and is subsequently adding 20mL pyridine solution, after stirring 10 minutes, makes it react 1 hour in 110 DEG C of oil baths.Stir 10 minutes in vibrating machine afterwards, add 1mL distilled water after letting cool, then make it react 10 minutes in 105 DEG C of oil baths.Be subsequently adding 3 phenolphthalein reagents, with 0.5mol/L potassium hydroxide-ethanol solution titration, with color become aubergine time for terminal.Carry out blank assay by same method, calculate hydroxyl value according to the following formula.Mensuration performs twice at, with meansigma methods for hydroxyl value.
< hydroxyl value calculating formula >
Hydroxyl value (mgKOH/g)=(V0-V1) × f × 0.5 × 56.11 ÷ S+ acid number
Wherein
S: sample quality (g)
V0: the amount (mL) of the 0.5mol/L potassium hydroxide-ethanol solution needed in blank assay .... blank titration amount (mL)
V1: the amount (mL) of the 0.5mol/L potassium hydroxide-ethanol solution needed in this test .... sample drop is quantitatively (mL)
The factor of f:0.5mol/L potassium hydroxide-ethanol solution ... 1.0
{ alcoholic solvent distributed test }
Alcoholic solvent distributed test, the plastics ointment jar of 10mL capacity weighs 0.1g particle and 5g methanol or isopropanol as alcoholic solvent, stir 3 minutes with stirring deaeration machine (あ わ と り Taro (registered trade mark) AR-100: Co., Ltd. シ Application キ society system).Stirring drips 1 dispersion liquid with glass pipette to glass plate, from top covered after terminating.Then, observe dispersity with digit microscope VHX (Co., Ltd. キ エ Application ス society system) and carry out implementation evaluation test.Result according to the observation, methanol and be judged to " ◎ " when can disperse in isopropanol, any one party is judged to "○" during dispersion, when both can not disperse, is judged to "×".
{ the manufacture example 1} of seed particles
In the delivery flask having blender, thermometer and reflux condenser, add the water 3000g as aqueous medium, methyl methacrylate 500g as simple function (methyl) acrylic monomer, n octylmercaptan 5g as molecular weight regulator, it is replaced into nitrogen by inside delivery flask while content in stirring delivery flask, the interior temperature of delivery flask is warming up to 70 DEG C.Then, in delivery flask, temperature is maintained at 70 DEG C, adds as, after the potassium peroxydisulfate 2.5g of polymerization initiator, obtaining emulsion through 12 hours polyreactions in delivery flask content.In the emulsion obtained, the solid content (polymethyl methacrylate particle) containing 14 weight %, its solid content is volume average particle size is 0.45 μm, and weight average molecular weight is the spherical shape particle (seed particles) of 15000.With the emulsion containing this spherical shape particle for seed particles dispersion, in the embodiment of polymer particle described later, comparative example.
{ the manufacture example 2} of seed particles
In the delivery flask having blender, thermometer and reflux condenser, add as the water 600g of aqueous medium, seed particles manufacture example 1 in the emulsion 70g, the methyl methacrylate 100g as simple function (methyl) acrylic monomer and the n octylmercaptan 1.0g as molecular weight regulator that obtain, stirring the space metathesis in delivery flask with blender while the content in delivery flask is nitrogen, and the interior temperature of delivery flask is warming up to 70 DEG C.Then, while in maintenance delivery flask, temperature is 70 DEG C, add as, after the potassium peroxydisulfate 0.5g of polymerization initiator, keeping carrying out polyreaction through 8 hours under the state that in delivery flask, temperature is 70 DEG C.Thus obtain seed particles dispersion.The seed particles dispersion obtained contains the solid content of 14 weight %, and this solid content is made up of spherical shape particle (seed particles) that volume average particle size is 1.01 μm.
{ embodiment 1: the manufacture example of polymer particle }
In the 5L reactor having blender and thermometer, add the styrene 300g as monofunctional styrenic's monomer, n-BMA (to the dissolubility of water be 0.04 weight % at 25 DEG C) 350g as simple function (methyl) acrylic monomer, ethylene glycol dimethacrylate 300g as cross-linkable monomer, poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark) 50PEP-300 " as the hydroxyl monomer shown in described formula (1), Japan Oil Co's system, the mixture that multiple compounds shown in described formula (1) is constituted, R=CH3, m average out to 3.5, n average out to 2.5) 50g, as the 2 of polymerization initiator, 2 '-azobis isobutyronitrile 8g also obtains monomer mixture after being mutually dissolved.In advance the polyoxethylene octylphenyl phenol ether 10g as nonionic surfactant is dissolved in 990g ion exchange water and obtains aqueous surfactant solution 1000g, by obtained monomer mixture and the mixing of this aqueous surfactant solution, put into high speed emulsion dispersion machine (trade name " ホ モ ミ Network サ MARK II 2.5 type ", プ ラ イ ミ Network ス Co., Ltd. system) process 10 minutes under 10000rpm, obtain emulsion.This emulsion adds above-mentioned seed particles and manufactures the seed particles dispersion 24g (solid content 3.4g) that volume average particle size is 0.45 μm obtained in example 1, stir 3 hours at 30 DEG C, obtain dispersion.This dispersion adds polyvinyl alcohol (the Nippon Synthetic Chemical Industry Co., Ltd's system as macromolecular dispersion stabilizer, trade name " go セ ノ Le (registered trade mark) GH-17 ") 4 weight % aqueous solution 2000g and as the sodium nitrite 0.6g of polymerization inhibitor, stirring 5 hours at 70 DEG C afterwards, then at 105 DEG C, stirring carries out polyreaction in 2.5 hours.By the dispersion liquid pressing filter dehydration after polymerization, with after warm water cleaning, vacuum drying 24 hours at 70 DEG C, obtain the polymer particle A being made up of crosslinking (methyl) acrylicstyrene copolymer resins.
{ embodiment 2: the manufacture example of polymer particle }
nullUsing the styrene 80g as monofunctional styrenic's monomer、Methyl methacrylate (to the dissolubility of water be 1.72 weight %s at 25 DEG C) 700g as simple function (methyl) acrylic monomer、Divinylbenzene 120g as cross-linkable monomer、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark 50PEP-300 " as the hydroxyl monomer shown in described formula (1)，Japan Oil Co's system) 100g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm that obtains will be manufactured in example 1 as seed particles dispersion in above-mentioned seed particles，In addition carry out similarly to Example 1，Obtain polymer particle B.
{ embodiment 3: the manufacture example of polymer particle }
nullUsing the styrene 240g as monofunctional styrenic's monomer、Methyl methacrylate 320g as simple function (methyl) acrylic monomer、Divinylbenzene 300g as cross-linkable monomer、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark 50PEP-300 " as the hydroxyl monomer shown in described formula (1)，Japan Oil Co's system) 100g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm that obtains will be manufactured in example 1 as seed particles dispersion in above-mentioned seed particles，In addition carry out similarly to Example 1，Obtain polymer particle C.
{ embodiment 4: the manufacture example of polymer particle }
nullUsing the styrene 510g as monofunctional styrenic's monomer、N-BMA 320g as simple function (methyl) acrylic monomer、Divinylbenzene 120g as cross-linkable monomer、Lactone-modified hydroxyethyl meth acrylate (trade name " プ ラ Network セ Le (registered trade mark) FM2D " as the hydroxyl monomer shown in described formula (2)，ダ イ セ Le KCC system，The material of P=2 in described formula (2)) 50g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g is mutually dissolved and obtains monomer mixture，The seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm that obtains will be manufactured in example 1 as seed particles dispersion in above-mentioned seed particles，Carry out similarly to Example 1 in addition obtaining polymer particle D.
{ embodiment 5: the manufacture example of polymer particle }
Using as the styrene 80g of styrene monomer, the n-BMA 700g as (methyl) acrylic monomer, the divinylbenzene 120g as cross-linkable monomer, poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark) 50PEP-300 " as the hydroxyl monomer shown in described formula (1), Japan Oil Co's system, the mixture that multiple compounds shown in described formula (1) is constituted, R1=CH3、R2=C2H5、R3=C3H6, R4=H, m average out to 3.5, n average out to 2.5) 100g, as the 2 of polymerization initiator, 2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved, using manufacturing the seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm obtained in example 1 as seed particles dispersion in above-mentioned seed particles, carry out similarly to Example 1 in addition obtaining polymer particle E.
{ embodiment 6: the manufacture example of polymer particle }
nullUsing the styrene 420g as monofunctional styrenic's monomer、Methyl methacrylate 230g as simple function (methyl) acrylic monomer、Divinylbenzene 300g as cross-linkable monomer、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark) 50PEP-300 " as the hydroxyl monomer shown in described formula (1)，Japan Oil Co's system) 50g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 107g (solid content 15.0g) that volume average particle size is 1.01 μm that obtains will be manufactured in example 2 as seed particles dispersion in above-mentioned seed particles，Carry out similarly to Example 1 in addition obtaining polymer particle F.
{ comparative example 1: the comparative example of polymer particle }
nullUsing the styrene 300g as monofunctional styrenic's monomer、Methyl methacrylate 230g as simple function (methyl) acrylic monomer、Ethylene glycol dimethacrylate 300g as cross-linkable monomer、Lactone-modified hydroxyethyl meth acrylate (trade name " プ ラ Network セ Le FM2D (registered trade mark) " as hydroxyl monomer shown in described formula (2)，ダ イ セ Le KCC system，The material of n=2 in described formula (2)) 50g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 107g (solid content 15.0g) that volume average particle size is 1.01 μm that obtains will be manufactured in example 2 as seed particles dispersion in above-mentioned seed particles，Carry out similarly to Example 1 in addition obtaining polymer particle G.
{ comparative example 2: the comparative example of polymer particle }
Using the styrene 200g of monofunctional styrenic's monomer, the methyl methacrylate 500g as simple function (methyl) acrylic monomer, the ethylene glycol dimethacrylate 300g as cross-linkable monomer, as the 2 of polymerization initiator, 2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved, using manufacturing the seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm obtained in example 1 as seed particles dispersion in above-mentioned seed particles, carry out similarly to Example 1 in addition obtaining polymer particle H.
{ comparative example 3: the comparative example of polymer particle }
nullUsing the styrene 200g as monofunctional styrenic's monomer、Methyl methacrylate 400g as simple function (methyl) acrylic monomer、Ethylene glycol dimethacrylate 200g as cross-linkable monomer、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark) 50PEP-300 " as the hydroxyl monomer shown in described formula (1)，Japan Oil Co's system) 200g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 80g (solid content 11.2g) that volume average particle size is 0.45 μm that obtains will be manufactured in example 1 as seed particles dispersion in above-mentioned seed particles，Carry out similarly to Example 1 in addition obtaining polymer particle I.
{ comparative example 4: the comparative example of polymer particle }
nullUsing the styrene 240g as monofunctional styrenic's monomer、Methyl methacrylate 320g as simple function (methyl) acrylic monomer、Divinylbenzene 300g as the polymerizable vinyl class monomer of cross-linkable monomer、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (trade name " Block レ Application マ (registered trade mark) 50PEP-300 " as the hydroxyl monomer shown in described formula (1)，Japan Oil Co's system) 50g、As polymerization initiator 2,2 '-azobis isobutyronitrile 8g obtains monomer mixture after being mutually dissolved，The seed particles dispersion 14.3g (solid content 2.0g) that volume average particle size is 1.01 μm that obtains will be manufactured in example 2 as seed particles dispersion in above-mentioned seed particles，Carry out similarly to Example 1 in addition obtaining polymer particle J.
{ manufacture of the antiglare film adjustment with dispersion liquid resin combination and antiglare film }
nullUsing the mixture (trade name " ア ロ ニ ッ Network ス (registered trade mark) M-305 " as the pentaerythritol triacrylate of uv curing resin and tetramethylol methane tetraacrylate，Toagosei Co., Ltd's system) 80 weight portions，Mixture (volume ratio of IPA and Ketocyclopentane is 5:5) 120 weight portions as the isopropanol (IPA) of organic solvent and Ketocyclopentane、By above-described embodiment 1～6、Polymer particle 5 weight portion that comparative example 1～4 manufactures、Photoepolymerizationinitiater initiater (2-methyl isophthalic acid-(4-methylphenyl-sulfanyl)-2-morpholinopropane-1-ketone，Trade name " イ Le ガ キ ュ ア (registered trade mark) 907 "，BASF (registered trade mark)) ジ ャ パ Application Co., Ltd. system) 5 weight portions mixing，It is configured to the antiglare film dispersion liquid resin combination as dispersion liquid resin combination.
Prepare polyethylene terephthalate (PET) film of overlay, i.e. thickness 0.2mm as base material film.With the rod coating machine that wet coating thickness is 60 μm, above-mentioned antiglare film dispersion liquid is coated in the one side of above-mentioned polyethylene terephthalate film, form film.Then, above-mentioned film is heated 1 minute at 80 DEG C, makes above-mentioned dried coating film.Afterwards, with high-pressure mercury-vapor lamp at accumulative light quantity 300mJ/cm2The lower above-mentioned film of ultraviolet radiation, makes above-mentioned curing of coating obtain Antidazzle hard rete.Thus, making contains the anti-glare dura mater manufacturing the polymer particle obtained in above-described embodiment 1～6, comparative example 1～4 respectively as antiglare film (products formed) respectively.
{ evaluation methodology of the anti-glare of antiglare film }
The evaluation methodology of the anti-glare of the antiglare film that following description is made by said method.Each uncoated face of the antiglare film of making is attached on ABS resin (acrylonitrile-butadiene-phenylethylene copolymer resins) plate, from the brightness 10000cd/cm of the place apart from this antiglare film 2m2Fluorescent lamp coated face, the anti-glare of visual assessment antiglare film.The metewand of anti-glare is as follows: when cannot be seen clearly that the reflected image profile of fluorescent lamp, and anti-glare is evaluated as "○" (well), and when being seen clearly that the reflected image profile of fluorescent lamp, anti-glare is evaluated as "×" (bad).
nullFor embodiment 1～6 and comparative example 1～4，The embodiment of polymer particle shown in table 1 or comparative example、The volume average particle size (μm) of the seed particles that polymer particle is used in being formed，Monomer " the methyl methacrylate (MMA) that polymer particle is used in manufacturing、N-BMA (n-BMA)、Styrene (St)、Ethylene glycol dimethacrylate (EGDMA)、Divinylbenzene (DVB)、Poly-(ethylene glycol and 1,2-propylene glycol) monomethacrylates (Block レ Application マ (registered trade mark) 50PEP-300)、Lactone-modified hydroxyethyl meth acrylate (the input amount (g) of プ ラ Network セ Le ((registered trade mark) FM2D)，Monomer containing ratio (weight %)，The measurement result of the volume average particle size (μm) of polymer particle and the particle diameter coefficient of variation (CV value (%))，The hydroxy value measuring value (mgKOH/g) of polymer particle，The evaluation result of alcoholic solvent distributed test，And on base material film, it is coated with the anti-glare evaluation result (coating is evaluated) of the film (antiglare film) of formation.Further, by polymer particle from the Component units of each monomer form with acrylic monomer/styrene monomer/cross-linkable monomer/hydroxyl monomer, represent monomer containing ratio with weight %.
[table 1]
The observed result of a part of polymer particle relevant to alcoholic solvent distributed test evaluation result in his-and-hers watches 1 illustrates.Fig. 1 and Fig. 2 indicates that the image of the polymer particle of embodiment 1 dispersity in alcoholic solvent distributed test.Fig. 3 and Fig. 4 indicates that the image of the polymer particle of comparative example 2 dispersity in alcoholic solvent distributed test.Fig. 1 represents polymer particle A dispersity in isopropanol, and Fig. 2 represents polymer particle A dispersity in methanol.It addition, Fig. 3 represents polymer particle H dispersity in isopropanol, Fig. 4 represents polymer particle H dispersity in methanol.Comparison diagram 1～Fig. 4 it can be seen that in Fig. 1 and Fig. 2, the substantially uniform dispersion of polymer particle A, and in Fig. 3 and Fig. 4, polymer particle has localized agglomeration, it does not have obtain uniform dispersity.As shown in Figure 3 and Figure 4, polymer particle H has localized agglomeration at isopropanol solvent or methanol solvate, and the evaluation result of alcoholic solvent distributed test as shown in table 1 is bad "×".
Result shown in table 1 can confirm that, the volume average particle size of polymer particle is less than 5 μm, and when hydroxyl value is more than 5.0mgKOH/g and below 15mgKOH/g, evaluation result and the anti-glare evaluation result of alcoholic solvent distributed test can obtain good result.
It addition, when any one in polymer particle diameter and hydroxyl value is beyond above-mentioned scope, may result in the result that anti-glare is bad.Particularly hydroxyl value polymer particle H the thinking poorly of in alcohol distributed test less than 5.0mgKOH/g, and also cannot be coated with.Think dispersed in disperse medium when hydroxyl value is more than 5.0mgKOH/g, but hydroxyl value more than 15mgKOH/g time or particle diameter more than 5 μm time, the evaluation result of anti-glare is relatively low.Its reason is, when hydroxyl value is too high, it is believed that formed in the process of film on film base material after coating, and coherency is relatively low and not sufficiently forms the protuberance on anti-glare generation impact.It addition, when the volume average particle size of polymer particle is more than 5 μm, it is believed that the protuberance owing to being formed on film base material becomes precipitous, excessive scattering exterior light.
And then, in the comparative example 2 less than 3 weight % of the Component units from hydroxyl monomer, dispersibility is not enough, application difficulties.In the Component units comparative example 3 more than 15%, coating, dried dispersibility are superfluous, it is impossible to obtaining desired coherency, result cannot obtain the anti-glare of target.
The present invention is under the premise without departing from its spirit or principal character, it is possible to implement with other various forms.Therefore above-described embodiment is only all example on all of point, it is impossible to make an explanation with limiting.The scope of the invention is such as shown in claims, not by any constraint of description text.And belong to the deformation in the equivalency range of claims and change, broadly fall in the scope of the present invention.
[industrial applicability]
The polymer particle of the present invention, for instance coat on base material as by the scattered dispersion liquid of binding agent, thus as optics parts such as the optical film such as optical diffusion film, antiglare film, light diffusing sheets, additionally also may utilize in various uses at other field.
Claims (8)
1. a polymer particle, it is characterized in that, including: carry out the Component units of the hydroxyl monomer shown in free following formula (1) and/or following formula (2), from the Component units of simple function (methyl) acrylic monomer, monofunctional styrenic's monomer and the Component units from cross-linkable monomer
The volume average particle size of described polymer particle is less than 5 μm, and hydroxyl value is more than 5.0mgKOH/g and below 15mgKOH/g,
Formula (1)
In formula (1), R represents H or CH3, m represents the numeral of 0～50, and n represents the numeral of 0～50, is 0 during m and n difference,
Formula (2)
In formula (2), R separately represents the numeral that H or CH3, p represent 1～50.
2. the polymer particle according to claim 1, it is characterised in that
The Component units from described hydroxyl monomer containing 3～15 weight %.
3. the polymer particle according to claim 1 or 2, it is characterised in that
The Component units from described cross-linkable monomer containing 3～35 weight %.
4. the polymer particle according to claim 1 or 2, it is characterised in that
At least include described simple function (methyl) acrylic monomer dissolubility to water at simple function (methyl) acrylic monomer that 25 DEG C is below 0.45 weight %.
5. the polymer particle according to claim 1 or 2, it is characterised in that
Described polymer particle is used for optics.
6. a manufacture method for polymer particle, makes vinyl monomer polymerization manufacture polymer particle, it is characterised in that
Described vinyl monomer includes the hydroxyl monomer shown in following formula (1) and/or following formula (2), simple function (methyl) acrylic monomer, monofunctional styrenic's monomer and cross-linkable monomer,
Relative to the total amount of described vinyl monomer, containing the described hydroxyl monomer of 3～15 weight %,
The polymerization of described vinyl monomer is that seed particles absorbs described vinyl monomer and the seeding polymerization that carries out in an aqueous medium,
Formula (1)
In formula (1), R represents H or CH3, m represents the numeral of 0～50, and n represents the numeral of 0～50, is 0 during m and n difference,
Formula (2)
In formula (2), R separately represents H or CH3, p represents the numeral of 1～50.
7. a dispersion liquid, it is characterised in that
Containing the polymer particle according to any one of Claims 1 to 5 and binding agent, described polymer particle is scattered in described binding agent as dispersate.
8. an optical film, it is characterised in that
Dispersion liquid described in claim 7 is coated base material film is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410836102.7A CN105778008B (en) | 2014-12-26 | 2014-12-26 | The manufacturing method and application thereof of polymer particle, polymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410836102.7A CN105778008B (en) | 2014-12-26 | 2014-12-26 | The manufacturing method and application thereof of polymer particle, polymer particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105778008A true CN105778008A (en) | 2016-07-20 |
| CN105778008B CN105778008B (en) | 2018-08-28 |
Family
ID=56389580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410836102.7A Active CN105778008B (en) | 2014-12-26 | 2014-12-26 | The manufacturing method and application thereof of polymer particle, polymer particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105778008B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110637232A (en) * | 2017-05-24 | 2019-12-31 | 积水化学工业株式会社 | Latex particle for measurement reagent, sensitized latex particle, and measurement reagent for immunoturbidimetry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428382A (en) * | 2001-12-28 | 2003-07-09 | 花王株式会社 | Water printing ink |
| CN101575188A (en) * | 2009-05-31 | 2009-11-11 | 上海三瑞化学有限公司 | Gypsum particle dispersing agent and preparation method thereof |
| CN103408705A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Water-borne epoxy resin and super-amphiphobic coat as well as preparation method and application of water-borne epoxy resin and super-amphiphobic coat |
| CN103772625A (en) * | 2014-01-17 | 2014-05-07 | 广州市东雄化工有限公司 | Freezing-resistant acrylate suspended thickening emulsion and preparation method thereof |
-
2014
- 2014-12-26 CN CN201410836102.7A patent/CN105778008B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428382A (en) * | 2001-12-28 | 2003-07-09 | 花王株式会社 | Water printing ink |
| CN101575188A (en) * | 2009-05-31 | 2009-11-11 | 上海三瑞化学有限公司 | Gypsum particle dispersing agent and preparation method thereof |
| CN103408705A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Water-borne epoxy resin and super-amphiphobic coat as well as preparation method and application of water-borne epoxy resin and super-amphiphobic coat |
| CN103772625A (en) * | 2014-01-17 | 2014-05-07 | 广州市东雄化工有限公司 | Freezing-resistant acrylate suspended thickening emulsion and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110637232A (en) * | 2017-05-24 | 2019-12-31 | 积水化学工业株式会社 | Latex particle for measurement reagent, sensitized latex particle, and measurement reagent for immunoturbidimetry |
| CN110637232B (en) * | 2017-05-24 | 2023-08-18 | 积水医疗株式会社 | Latex particles for measurement reagent, sensitized latex particles, and measurement reagent for immunoturbidimetry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105778008B (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101452207B1 (en) | Resin particles and process for producing same, antiglare film, light-diffusing resin composition, and external preparation | |
| CN110229267B (en) | Polymer particles and use thereof | |
| KR101947402B1 (en) | POLYMER PARTICLE, METHOD FOR PRODUCING POLYMER PARTICLE | |
| JP6231030B2 (en) | POLYMER PARTICLE, METHOD FOR PRODUCING POLYMER PARTICLE, AND USE THEREOF | |
| JP5592735B2 (en) | Method for producing hydrophilic polymer particles and hydrophilic polymer particles | |
| CN105778008A (en) | Polymer particles, and preparation method and application of polymer particles | |
| JP2019052306A (en) | Polymer particle and application thereof | |
| CN102443234B (en) | Crosslinked resin particle and optical diffusion film | |
| TWI619748B (en) | Polymer particles and manufacturing method and use thereof | |
| JP2006084927A (en) | Light diffusing agent and its manufacturing method | |
| CN107236070B (en) | Polymer particles, process for producing the same, and use thereof | |
| KR102159531B1 (en) | Polymer particles, production method for polymer particles, and its application | |
| JP5433536B2 (en) | Method for producing polymer particles | |
| KR20160079391A (en) | Polymer particles, production method for polymer particles, and its application | |
| WO2023153109A1 (en) | Polymer particles, polymer particle composition, and optical film | |
| CN103119088A (en) | Coloring resin particles, and production method and uses therefor | |
| JP5377373B2 (en) | Modified urethane resin particles, method for producing the same, and light diffusion film | |
| KR20100080431A (en) | Spherical polymer beads and preparation method thereof | |
| KR20110105130A (en) | Crosslinked resin particles and method for producing the same | |
| JP2023118042A (en) | Polymer particles, polymer particle composition, and optical film | |
| CN118679197A (en) | Polymer particles, polymer particle compositions, and optical films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |