CN102918066A - Resin particle having convex portions on surface, method for producing same, and coating composition, coating material, and preparation for external use, each using same - Google Patents
Resin particle having convex portions on surface, method for producing same, and coating composition, coating material, and preparation for external use, each using same Download PDFInfo
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- CN102918066A CN102918066A CN2010800671275A CN201080067127A CN102918066A CN 102918066 A CN102918066 A CN 102918066A CN 2010800671275 A CN2010800671275 A CN 2010800671275A CN 201080067127 A CN201080067127 A CN 201080067127A CN 102918066 A CN102918066 A CN 102918066A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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Abstract
Disclosed is a resin particle having convex portions on the surface thereof, which is of a substantially spherical shape, has a particle diameter of 10 to 500 [mu]m, and has a plurality of convex portions capable of diffusely reflecting light when the entire surface thereof is irradiated with light, wherein the number of the plurality of convex portions present on the outer circumference of the resin particle measured from the projection of a photograph taken per resin particle is 8 or more and the average height of the plurality of convex portions present on the outer circumference is 2 to 10% of the particle diameter.
Description
Technical field
The present invention relates to resin particle and manufacture method thereof, the coating composition that has used it, coating thing and external preparation that the surface has protuberance.More specifically, the present invention relates to have excellent specific property aspect light diffusing, extinction effect, the sense of touch and be suitable as matting agent, makeup, light diffusion film, light diffusing sheet, anti-dazzle film, LED illuminating cover etc. additive, the surface has resin particle and the manufacture method thereof of protuberance, the coating composition that uses this resin particle, coating thing and external preparation.
Background technology
Different from common spherical particle, the particle with special shape has special character at aspects such as light diffusing, senses of touch.Therefore, in the fields such as the matting agent of coating, makeup, expectation provides to have and results from the particle of specific physique of special shape.In addition, in recent years, the particle with special shape in the image display device field also through being usually used in the purposes of light diffusing sheet, light diffusion film, anti-dazzle film and so on.
As the particle with special shape, known have make that the mixture that comprises the unsaturated monomer that can carry out radical polymerization and polymkeric substance carries out in the presence of radical polymerization initiator that suspension polymerization obtains, particle (with reference to patent documentation 1) that Porous and surface are concaveconvex shape.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-7704 communique
Summary of the invention
The problem that invention will solve
Yet the ratio of the protuberance of disclosed particle in the patent documentation 1 (height of protuberance, quantity) does not claim fully to be the shape of subglobular.Therefore as can be known, this particle does not have the optical characteristics such as light diffusing of the degree that can deserve to be called significantly different from spherical particle.
For the scheme of dealing with problems
The present inventor finds: particle surface is very excellent with the optical characteristics such as light diffusing of the resin particle of the protuberance with specified altitude of regulation number, thereby has finished the present invention.
So, according to the present invention, can provide a kind of surface to have the resin particle of protuberance, it is approximate spherical resin particle, the particle diameter of described resin particle is 10 ~ 500 μ m, when having the rayed of being subject to, whole surface can carry out irreflexive a plurality of protuberance, wherein, be more than 8 from the fall into a trap quantity of a plurality of protuberances of measuring, be present in the resin particle periphery of the sciagraph of making based on the photo of 1 resin particle being taken 1, the mean value of height that is present in a plurality of protuberances of periphery is 2 ~ 10% of particle diameter.
In addition, according to the present invention, can provide above-mentioned surface to have the manufacture method of the resin particle of protuberance, it comprises the non-crosslinked vinylformic acid (ester) of the ethene base system monomer that makes 100 weight parts and 1 ~ 30 weight part thereby based polymer carries out the operation that suspension polymerization obtains resin particle in the presence of tensio-active agent, and aforementioned surfactants is the straight chain shape, the optional non-reacted phosphate cpd that contains ester group of carbonatoms 4 ~ 40.
The effect of invention
Surface of the present invention has the resin particle of protuberance and since particle surface have more than 8, highly for particle diameter 2 ~ 10% namely highly account for the protuberance of particle diameter larger proportion, thereby possess and the remarkable different optical characteristics such as light diffusing of spherical particle.Possess the resin particle of this light diffusing can be compatibly as matting agent, the makeup of coating, in addition can be compatibly as the additive in the light diffusing sheet of image display device, light diffusion film, anti-dazzle film, the LED illuminating cover etc.
In addition, when the resin particle that the surface has a protuberance contains from the component of polymer of non-crosslinked vinylformic acid (ester) based polymer of the ethene base system monomer of 100 weight parts and 1 ~ 30 weight part, can realize all excellent resin particles of light diffusing, the transparency.
In addition, above-mentioned ethene base system monomer is vinylformic acid (ester) when being monomer or styrenic monomers, can access light diffusing, resin particle that the transparency is more excellent.
In addition, when non-crosslinked vinylformic acid (ester) based polymer is the multipolymer of Propenoic acid, 2-methyl, isobutyl ester polymkeric substance or Propenoic acid, 2-methyl, isobutyl ester and methyl methacrylate, can access light diffusing, transparent more excellent resin particle.
In addition, because the coating composition that has used surface of the present invention to have the resin particle of protuberance has excellent light diffusing, therefore the coating thing based on this coating composition can compatibly be used as matting agent.
In addition, compare with the external preparation that has used the spherical resin particle, the external preparation that has used surface of the present invention to have the resin particle of protuberance can contain a large amount of makeup, external application pharmaceuticals, therefore can expect its improve makeup, external application pharmaceuticals in skin amounts of saturation and soak into the time length.
In addition, have the manufacture method of the resin particle of protuberance by surface of the present invention, can make have the light diffusing significantly different from spherical particle etc., the surface has the resin particle of protuberance.The surface that obtains by this manufacture method have the resin particle of protuberance can be compatibly as matting agent, the makeup of coating, in addition can be compatibly as the additive in the light diffusing sheet of image display device, light diffusion film, anti-dazzle film, the LED illuminating cover etc.
Description of drawings
Fig. 1 is the SEM picture of the resin particle of embodiments of the invention 1.
Fig. 2 is the SEM picture of the resin particle of embodiments of the invention 2.
Fig. 3 is the SEM picture of the resin particle of embodiments of the invention 3.
Fig. 4 is the SEM picture of the resin particle of embodiments of the invention 4.
Fig. 5 is the SEM picture of the resin particle of comparative example 1 of the present invention.
Fig. 6 is the SEM picture of the resin particle of comparative example 2 of the present invention.
Fig. 7 is the SEM picture of the resin particle of comparative example 3 of the present invention.
Fig. 8 is the SEM picture of the resin particle of comparative example 4 of the present invention.
Fig. 9 is the SEM picture of the resin particle of comparative example 5 of the present invention.
Figure 10 is explanation to the quantity of the protuberance on resin particle of the present invention surface and the schematic diagram (schematic diagram is based on the sciagraph of resin particle and the figure that describes) that highly carries out method for measuring.
Embodiment
The resin particle (below, also referred to as resin particle) that surface of the present invention has protuberance is approximate spherical resin particle, and the particle diameter of described resin particle is 10 ~ 500 μ m, can carry out irreflexive a plurality of protuberance when having the rayed of being subject on whole surface.Be more than 8 from the fall into a trap quantity of a plurality of protuberances of measuring, be present in the resin particle periphery of the sciagraph of making based on the photo of 1 resin particle being taken 1, the mean value of height that is present in a plurality of protuberances of periphery is 2 ~ 10% of particle diameter.This is because when not having the protuberance of above-mentioned height and number, can't expect that it has the optical characteristics significantly different from the irregular spherical resin particle of known surperficial tool.In addition, about the quantity of a plurality of protuberances of being present in the resin particle periphery and the concrete measuring method of height, describe in an embodiment.
With Particle Phase ratio in the past, for example with surperficial concave-convex surface but global shape is spherical Particle Phase ratio, the resin particle that surface of the present invention has protuberance has excellent light diffusing.About such light diffusing, can estimate by mist degree and total light transmittance that mensuration makes resin particle of the present invention be dispersed in the optical thin film that obtains in the resin glue.Detailed content describes in an embodiment.
Can form the resin particle that above-mentioned surface has protuberance as long as consist of the kind of the component of polymer of resin particle, then not limit especially.For example, resin particle can contain the component of polymer from ethene base system monomer and non-crosslinked vinylformic acid (ester) based polymer.
As ethene base system monomer, such as listing: (methyl) acrylate derivatives such as methyl acrylate, methyl methacrylate, ethyl propenoate, β-dimethyl-aminoethylmethacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, methacrylic acid-2-ethylhexyl, stearyl acrylate ester, methacrylic acid stearyl ester etc.; Vinylbenzene, alpha-methyl styrene, Vinyl toluene, chloro-styrene etc.They can use separately, perhaps also may be used two or more.
As ethene base system monomer, the preferred monomer that uses except being used for the monomer of non-crosslinked vinylformic acid (ester) based polymer.
Ethene base system monomer also can use bridging property ethene base system monomer.As bridging property ethene base system monomer, can use the bridging property ethene base system monomer with the two keys of 2 above polymerizabilitys.For example, can use separately or mix multiple use: Vinylstyrene, divinyl naphthalene and their divinyl aromatic compounds such as derivative; The divinyl type carboxylicesterss such as ethylene glycol dimethacrylate, Diethylene Glycol dimethacrylate, triethylene glycol diacrylate, Viscoat 295; N, the divinyl compounds such as N-divinyl aniline, divinyl ether, vinyl thioether; And has compound of 3 above vinyl etc.
With respect to the monomer mixture of 100 weight parts, the consumption of bridging property ethene base system monomer is preferably 3 ~ 20 weight parts.5 ~ 10 weight parts more preferably.The consumption of bridging property ethene base system monomer is during less than 3 weight part, exists to be dissolved in the solvent and to cause playing situation as the effect of coating thing.On the other hand, when surpassing 20 weight part, exist the surface of resin particle not form the situation of protuberance.
As non-crosslinked vinylformic acid (ester) based polymer, be preferably the multipolymer of Propenoic acid, 2-methyl, isobutyl ester polymkeric substance or Propenoic acid, 2-methyl, isobutyl ester and methyl methacrylate.
With respect to the ethene base system monomer of 100 weight parts, the consumption of non-crosslinked vinylformic acid (ester) based polymer is preferably 1 ~ 30 weight part.5 ~ 20 weight parts more preferably.During less than 1 weight part, there is the situation that is not separated, does not form protuberance.On the other hand, when surpassing 30 weight part, there is non-crosslinked vinylformic acid (ester) based polymer undissolved situation in monomer.
Obtain method resin particle, that make the Polymerizable composition polymerization as being used for, can use known polymerization process, such as suspension polymerization, emulsion polymerization, dispersion copolymerization method etc.Below an example making the method for resin particle based on suspension polymerization is described, but the present invention is not limited in this manufacture method.
In different containers, prescription preparation monomer is used miscellany and water mutually according to the rules respectively.Dissolving non-crosslinked vinylformic acid (ester) based polymer adds non-reacted arbitrarily tensio-active agent in ethene base system monomer, uses mixing tank, homogenizer to mix/disperse., add arbitrarily bridging property ethene base system monomer and polymerization starter, use mutually miscellany as monomer thereafter.
In addition, separately by the ratio with regulation is added dispersion stabilizer in aqueous medium, aqueous medium obtains water with tensio-active agent and mix and blend.In addition, as aqueous medium, can enumerate the mixture of water outlet or water and water-soluble solvent (for example, the lower alcohols such as methyl alcohol, ethanol, Virahol).Consider preferably water from the viewpoint of liquid waste disposal.In addition, use mutually miscellany with respect to the monomer of 100 weight parts, water preferably is made as 100 ~ 1000 weight parts.Mixed stirring device as adopt this moment can use common mixing tank, homogenizer.Mix and blend is so that integral body reaches even.
Inject monomer at the aqueous phase that forms according to the above-mentioned steps adjustment and use mutually miscellany, use homogenizer etc. carries out mix and blend, thereby obtains suspension (water/monomer phase/aqueous phase emulsion).At this moment, by using homogenizer as whipping appts, can decide by changing the agitation conditions such as churning time, rotating speed the particle size of monomer phase.
To be imported by suspension obtained above the warming apparatuss such as autoclave, and heat while stirring and carry out the polymerization of monomer phase.Polymer filtration with so operating and obtaining carries out drying behind the washing filtering thing, can obtain resin particle.In addition, also can before washing, remove dispersion stabilizer.
Polymerization starter preferably uses oil-soluble polymerization initiator.As oil-soluble polymerization initiator, for example can list: benzoyl peroxide, lauroyl peroxide, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, 3, the organo-peroxides such as 5,5-trimethyl acetyl superoxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, ditertiary butyl peroxide; Diisopropyl azodicarboxylate, azo two cyclohexanenitriles, the two azo based compounds such as (2,4-methyl pentane nitriles) of azo.
As dispersion stabilizer, so long as normally used dispersion stabilizer in the suspension polymerization of polymkeric substance does not then limit, especially such as using: water-soluble polymers such as methylcellulose gum, Natvosol, polyvinyl alcohol; The slightly water-soluble inorganic salt such as calcium phosphate, magnesium hydroxide, magnesium pyrophosphate, barium sulfate, calcium carbonate, silicon-dioxide.Monomer with respect to 100 weight parts is used miscellany mutually, dispersion stabilizer preferably in aqueous medium the ratio with 0.1 ~ 20.0 weight part carry out compounding.
As tensio-active agent, use the straight chain shape of carbonatoms 4 ~ 40 and non-reacted phosphate cpd.The optional ester group that contains of this phosphate cpd.The such carbonatoms of the preferred lauryl phosphoric acid of tensio-active agent is the tensio-active agent more than 6.With respect to the ethene base system monomer of 100 weight parts, the consumption of tensio-active agent is preferably 0.01 ~ 10 weight part.
During suspension polymerization, in order to suppress to produce target resin particle new particulate in addition, also can use water miscible stopper.As water-soluble stopper, can list nitrites, sulfites, hydroquinone type, Vitamin C acids etc.With respect to the aqueous medium of 100 weight parts, the consumption of stopper is preferably 0.01 ~ 0.1 weight part.
Polymerization temperature preferably is made as 30 ~ 100 ℃.More preferably 40 ~ 80 ℃.And, keep the time of this polymerization temperature to be preferably 0.1 ~ 20 hour.By with this polymer beads methods such as suction filtration, centrifuge dehydration, centrifugation, pressurizing and dehydrating from aqueous medium, through washing the operation of moisture filter cake, drying, can obtain the target resin particle.
Resin particle of the present invention is by being distributed in the resin glue and moulding etc. on transparent substrate resin, can be as light diffusing resin-formed bodies such as the light diffusion film of backlight type display panels, light guiding plates.As transparent substrate resin, can compatibly use polymethylmethacrylate, polystyrene, copolymer of methyl methacrylatestyrene, polycarbonate, polyvinyl chloride, norbornene-based polymer, alicyclic vinyl ring type hydrocarbon polymer etc.
In addition, in the scope of not damaging effect of the present invention, according to forming process, the use-pattern of light diffusing resin-formed body, also can use the various compounding agent of usually adopting.For example, when the purposes of the perviousness that not needing to be used for light, diffustivity etc., also can add pigment etc.
When using resin particle of the present invention to form the light diffusion film, can consider with the diactinic relation of light from light diffusing, be preferably 10 ~ 500 % by weight with respect to the content of the resin particle of resin glue.In the situation of the content of resin particle less than 10 % by weight, sometimes do not have sufficient light diffusing energy.On the other hand, when surpassing 500 % by weight, sometimes can't further promote light diffusing and can reduce on the contrary the light transmission performance, be difficult to evenly to be applied on the film, resin particle becomes and is easy to come off from film.
In addition, when using resin particle of the present invention to form light guiding plate, be preferably 0.05 ~ 0.5 % by weight with respect to the content of the resin particle of resin glue.In the situation of the content of resin particle less than 0.05 % by weight, exist photopermeability to become too high and do not possess the situation of the required light diffusing of light guiding plate.On the other hand, when surpassing 0.5 % by weight, exist light diffusing to become too high and situation that the leaded light distance shortens.
Light diffusing sheet, light guiding plate are except obtaining by the coating process based on coating machine etc.; also can be by using the common resin kneading device such as single screw extrusion machine, twin screw extruder that substrate resin and resin particle is mixing; and be situated between and be shaped to this resin combination after mixing tabular by T mould, roller group; perhaps use injection moulding machine, pressure forming machine etc. to carry out moulding, thereby obtain.
Use the haze value of the light diffusion film that resin particle of the present invention obtains to be preferably more than 85%, more preferably more than 90%, more preferably more than 95%.Wherein, haze value can be by using NDH-2000 that Japanese electric look industrial makes according to the measuring method of JIS K 7136 or by using NDH-1001DP that Japanese electric look industrial makes to measure according to the measuring method of JIS K 7105 etc.In addition, total light transmittance is preferably more than 70%, more preferably more than 75%.
In addition, the coating (coating composition) that uses resin particle of the present invention to obtain can compatibly be used as light diffusing coating, Flat paint.For the effect that obtains expecting, light diffusing coating, Flat paint preferably use the resin particle of median size 10 ~ 50 μ m.About the consumption of resin particle, with respect to the total of resin glue and resin particle, be preferably 5 ~ 70 % by weight during for light diffusing coating, and be preferably 10 ~ 30 % by weight when being Flat paint.
In addition, can contain in the coating and be useful on the solvent (for example, the organic solvents such as water, toluene, butylacetate, methylethylketone, Virahol) of giving desired viscosity.Usually, with respect to the resin particle of 100 weight parts, contain the solvent of 100 ~ 1000 weight parts.And then, by coating composition being coated on the base material and carrying out drying, can obtain being coated with thing.Base material is not limited especially.The thickness of coating thing can suitably be set according to the character of expectation.When wishing to obtain the coating thing of thick film, also can repeatedly be coated with.
In addition, resin particle of the present invention also can be as the raw material of external preparation.The content of resin particle can suitably be set according to the kind of external preparation in the external preparation, is preferably 0.1 ~ 50 % by weight, more preferably 0.2 ~ 30 % by weight.
During less than 0.1 % by weight, sometimes can't confirm the clear and definite effect of bringing by containing resin particle with respect to the content of the resin particle of external preparation total amount.In addition, the content of resin particle is during greater than 50 % by weight, sometimes can't confirm and the unusual effect that increases content and match, and is therefore not preferred aspect production cost.
As external preparation, such as listing makeup, external application pharmaceuticals etc.
As makeup, so long as obtain the makeup of above-mentioned effect by containing above-mentioned resin particle, then do not limit especially, be makeup such as listing liquid such as scraping Hu Pao, skin cream, astringent, breast frost, emulsion, body wash, antioperspirant; The washings such as soap, frosted face cleaning milk apply some make up; The healths such as facial mask class, shaving cream, cosmetic white powder class, foundation cream, lipstick, lipstick, rouge, eyebrow makeup, manicure makeup, hair washing apply some make up, hair dye, setting agent, aromaticity makeup, toothpaste, baths, anti-sunburn goods, sunscreen, toilet powder shui, baby talcum powder apply some make up.
As the external application pharmaceuticals, then be not particularly limited so long as be applicable to the external application pharmaceuticals of skin, for example, can list pharmaceutical breast frost, ointment, pharmaceutical emulsion, pharmaceutical lotion etc.
In addition, in the scope of not damaging effect of the present invention, these external preparations can be according to the normally used additive of purpose compounding.As such additive, such as can enumerate water outlet, lower alcohol, grease and wax class, hydrocarbon, higher fatty acid, higher alcohols, sterol, fatty acid ester, metallic soap, wetting Agent for Printing Inks, tensio-active agent, macromolecular compound, colouring material, spices, anticorrosion/sterilant, antioxidant, UV light absorber, silicon is other resin particle such as particle, granules of polystyrene, special compounding additive etc.
Embodiment
Below, specifically describe the present invention with embodiment, but the present invention is not subject to the restriction of these embodiment.
The measuring method, the evaluation method of light diffusion film of number, height and length of protuberance of observational technique, the resin particle on measuring method, the resin particle surface of measuring method, the molecular-weight average of median size at first, is described.
(measuring method of median size)
(KAO. Corp. SA makes: 0.3% aqueous solution 10ml RHEODOL TW-L120) to drop into resin particle 0.1g and nonionic surface active agent in test tube.Use contact mixer (YAMATO SCIENTIFIC CO., LTD makes: TOUCHMIXER MT-31) and ultrasonic cleaner (ULTRASONICCLEANER VS-150) it is pre-dispersed.Make at the ISOTONII(Beckman Coulter Corporation that is full of that is equipped on main frame: in beaker mensuration electrolytic solution), the limit is slowly stirred the limit and is dripped this pre-dispersed liquid with dropper, makes the reading of the densitometer of host picture reach 10% front and back.Then, at Ku Erte grain graininess and calculating instrument III(Coulter Multisizer III) (Beckman Coulter Corporation makes: determinator) aperture (aperture) is set in the main frame, meets in electric current (Current), gain factor (Gain), polarity (Polarity) under the prescribed condition of aperture size and measure.In the mensuration with the degree of not introducing bubble to slowly stirring in the beaker, when having measured 100,000 resin particles, finish to measure.Calculate the weighted volumetrically mean diameter (arithmetic average diameter of volume % pattern: volume medium) be used as the median size of resin particle.The micropore diameter size of the aperture that uses is 280 μ m.
(measuring method of molecular-weight average)
The measuring method of molecular-weight average (Mw) adopts gel permeation chromatography (GPC) to carry out.Wherein, molecular-weight average refers to polystyrene (PS) conversion weight-average molecular weight.Particularly, measure in such a way.
The 50mg sample is dissolved in 10 milliliters of tetrahydrofuran (THF)s (THF), after the chromatodisk filtration with non-water system 0.45 μ m, use chromatographic instrument to measure.Chromatographic condition is as follows.
Liquid chromatograph: TOSOH CORPORATION makes, trade(brand)name " GelPermeation Chromatography HLC-8020 "
Post: TOSOH CORPORATION makes, trade(brand)name " TSKgelGMH-XL-L " Φ 7.8mm * 30cm * 2
Column temperature: 40 ℃
Carrier gas: tetrahydrofuran (THF) (THF)
Carrier gas flux: 1 ml/min
Injection/pump temperature: 35 ℃
Detect: RI
Injection rate: 100 microlitres
The typical curve polystyrene standard: clear and electrician company makes, trade(brand)name " shodex " weight-average molecular weight: 1030000 and TOSOH CORPORATION make weight-average molecular weight: 5480000,3840000,355000,102000,37900,9100,2630,870
(observational technique of the protuberance of particle surface)
(NEC company makes: JSM-6360LV) under 500 ~ 5000 times of multiplying powers resin particle is arbitrarily observed, observing the resin particle surface has no concave-convex to use scanning electronic microscope.
(measuring method of the quantity of the protuberance of particle surface, the height of protuberance and length)
At first, make sciagraph based on the SEM picture of 1 resin particle being taken 1.
Then, assert the protuberance of resin particle periphery by sciagraph.Particularly, low-lying position between the adjacent protuberance (position that is identified) is regarded as the basic point of protuberance.Then, be connected with straight line between contiguous basic point and the basic point.When the operation that intercardinal connects with straight line is finished, form the image shown in the sketch of Figure 10.
The part (curved portion that is present in the straight line top that connects intercardinal) of the band numeral of Figure 10 is regarded as protuberance.Number by the above-mentioned protuberance of assert (among Figure 10 for (1) ~ (9) 9) is made as " number of protuberance "." length of protuberance " is made as (each straight line) mean value of the length of the straight line that connects intercardinal.Peaked (each protuberance) mean value of the length of the vertical line till being made as from each protuberance (on the curve) to the straight line that connects intercardinal with " height of protuberance ".10 resin particles are arbitrarily carried out this mensuration, with separately mean value as the quantity of protuberance, the height of protuberance and the length of protuberance.
(evaluation method of light diffusion film)
The light diffusion film adopts total light transmittance and mist degree to estimate.Measure total light transmittance according to JIS K 7361.In addition, measure mist degree according to JIS K 7136.Wherein, the NHD-2000 that measure to use Japanese electric look industrial to make.
Make non-crosslinked vinylformic acid (ester) based polymer 1 ~ 3 that uses in embodiment and the comparative example.
(manufacturing of non-crosslinked vinylformic acid (ester) based polymer 1)
In the autoclave of internal capacity 5L, add 1000g water, 40g as the calcium phosphate of suspension stabilizer, the 0.1g Sodium Lauryl Sulphate BP/USP as tensio-active agent, form water.Be used as monomer phase as azo two valeronitriles, the 1.0g of polymerization starter as the n-dodecyl mercaptan of molecular weight regulator with 500g Propenoic acid, 2-methyl, isobutyl ester, 1.0g, add previous aqueous phase to and form mixed solution.(special machine chemical industry company makes: TK HOMO MIXER) mixed solution is stirred at high speed, form fine droplet in mixed solution by using homogenizer.The mixed solution that comprises fine droplet carried out 5 hours heated and stirred under 50 ℃, in mixed solution, form particle.Add hydrochloric acid and decompose suspension stabilizer in above-mentioned mixed solution, water washs afterwards.After the washing, obtain particle by carrying out centrifuge dehydration.The gained solid particulate is carried out vacuum-drying in 10 hours under 60 ℃.Obtain the particle of median size 50 μ m, molecular-weight average 300,000.With it as non-crosslinked vinylformic acid (ester) based polymer 1.
(manufacturing of non-crosslinked vinylformic acid (ester) based polymer 2)
In the autoclave of internal capacity 5L, add 1000g water, 40g as the calcium phosphate of suspension stabilizer, the 0.1g Sodium Lauryl Sulphate BP/USP as tensio-active agent, form water.Be used as monomer phase as azo two valeronitriles, the 0.5g of polymerization starter as the n-dodecyl mercaptan of molecular weight regulator with 500g Propenoic acid, 2-methyl, isobutyl ester, 1.0g, add previous aqueous phase to and form mixed solution.(special machine chemical industry company makes: TK HOMO MIXER) mixed solution is stirred at high speed, form fine droplet in mixed solution by using homogenizer.The mixed solution that comprises fine droplet carried out 5 hours heated and stirred under 50 ℃, in mixed solution, form particle.Add hydrochloric acid and decompose suspension stabilizer in above-mentioned mixed solution, water washs afterwards.After the washing, obtain particle by carrying out centrifuge dehydration.The gained solid particulate is carried out vacuum-drying in 10 hours under 60 ℃.Obtain the particle of median size 50 μ m, molecular-weight average 600,000.With it as non-crosslinked vinylformic acid (ester) based polymer 2.
(manufacturing of non-crosslinked vinylformic acid (ester) based polymer 3)
In the autoclave of internal capacity 5L, add 1000g water, 40g as the calcium phosphate of suspension stabilizer, the 0.1g Sodium Lauryl Sulphate BP/USP as tensio-active agent, form water.Be used as monomer phase as azo two valeronitriles, the 0.5g of polymerization starter as the n-dodecyl mercaptan of molecular weight regulator with 425g Propenoic acid, 2-methyl, isobutyl ester, 75g methyl methacrylate, 1.0g, add previous aqueous phase to and form mixed solution.(special machine chemical industry company makes: TK HOMO MIXER) mixed solution is stirred at high speed, form fine droplet in mixed solution by using homogenizer.The mixed solution that comprises fine droplet carried out 5 hours heated and stirred under 50 ℃, in mixed solution, form particle.Add hydrochloric acid and decompose suspension stabilizer in above-mentioned mixed solution, water washs afterwards.After the washing, obtain particle by carrying out centrifuge dehydration.The gained solid particulate is carried out vacuum-drying in 10 hours under 60 ℃.Obtain the particle of median size 50 μ m, molecular-weight average 600,000.With it as non-crosslinked vinylformic acid (ester) based polymer 3.
(embodiment 1)
(a-1) manufacturing of resin particle
In the autoclave of internal capacity 5L, add 1000g water, 40g as the calcium phosphate of suspension stabilizer, form water.Dissolving 25g non-crosslinked vinylformic acid (ester) based polymer 2 in the 450g methyl methacrylate, add therein 50g ethylene glycol dimethacrylate (MITSUBISHI RAYON CO., light ester EG), 1.0g is as azo two valeronitriles, the 0.4g lauryl phosphoric acid of polymerization starter LTD makes:, and stir with homogenizer, with it as the monomer phase.Aqueous phase formerly adds the monomer phase and forms mixed solution.(special machine chemical industry society makes: TK HOMO MIXER) mixed solution is stirred at high speed, form fine droplet in mixed solution by using homogenizer.The mixed solution that comprises fine droplet is carried out 5 hours heated and stirred under 50 ℃, in mixed solution, form particle.Add hydrochloric acid and decompose suspension stabilizer in above-mentioned mixed solution, water washs afterwards.After the washing, obtain particle by carrying out centrifuge dehydration.The gained solid particulate is carried out vacuum-drying in 10 hours under 60 ℃.
(b-1) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 1, be the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the quantity of protuberance is 9, highly is that 1.5 μ m, length are 6.4 μ m.
(embodiment 2)
(a-2) manufacturing of resin particle
Lauryl phosphoric acid is made as 0.25g, and in addition, operation obtains resin particle similarly to Example 1.
(b-2) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 2, be the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the quantity of protuberance is 10, highly is that 1.8 μ m, length are 6.2 μ m.
(embodiment 3)
(a-3) manufacturing of resin particle
Lauryl phosphoric acid is made as 0.5g, and in addition, operation obtains resin particle similarly to Example 1.
(b-3) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 3, be the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the number of protuberance is 12, highly is that 1.4 μ m, length are 5.3 μ m.
(embodiment 4)
(a-4) manufacturing of resin particle
Use non-crosslinked vinylformic acid (ester) based polymer 1 to replace non-crosslinked vinylformic acid (ester) based polymer 2, in addition, operation obtains resin particle similarly to Example 1.
(b-4) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 4, be the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the quantity of protuberance is 9, highly is that 1.9 μ m, length are 6.9 μ m.
(embodiment 5)
(a-5) manufacturing of resin particle
Use vinylbenzene to replace methyl methacrylate, use Vinylstyrene to replace ethylene glycol dimethacrylate, in addition, operation obtains resin particle similarly to Example 1.
(b-5) state of resin particle
The median size of gained resin particle is 70 μ m.When observing resin particle with scanning electronic microscope (SEM), it is the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the quantity of protuberance is 9, highly is that 1.5 μ m, length are 6.4 μ m.
(embodiment 6)
(a-6) manufacturing of resin particle
Use vinylbenzene to replace methyl methacrylate, use non-crosslinked vinylformic acid (ester) based polymer 3 to replace non-crosslinked vinylformic acid (ester) based polymer 2, use Vinylstyrene to replace ethylene glycol dimethacrylate, in addition, operation obtains resin particle similarly to Example 1.
(b-6) state of resin particle
The median size of gained resin particle is 70 μ m.When observing resin particle with scanning electronic microscope (SEM), it is the particle that the surface has a plurality of large warty protuberances (forming and the spherical shape that differs greatly).When carrying out the mensuration based on quantity, height and the length of the protuberance of sciagraph, the quantity of protuberance is 9, highly is that 1.6 μ m, length are 6.2 μ m.
(comparative example 1)
(a-7) manufacturing of resin particle
(Japanese chemical drug company makes: KAYAMER PM-21) replace lauryl phosphoric acid, in addition, operation obtains resin particle similarly to Example 1 to use oxyethane modified phosphate acrylate.
(b-7) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 5, although some place, surface is low-lying, but be the particle of the shape of level and smooth subglobular.Quantity, height and the length of protuberance are measured in trial based on sciagraph, but do not have to think the place of protuberance.
(comparative example 2)
(a-8) manufacturing of resin particle
Also add the 0.12g Sodium Lauryl Sulphate BP/USP and do not add lauryl phosphoric acid mutually as monomer as water, in addition, operation obtains resin particle similarly to Example 1.
(b-8) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 6, the surface forms the tiny protuberance of a plurality of blisters.Because protuberance is less one by one, so particle is the shape of subglobular.Although attempt measuring based on sciagraph the quantity of protuberance, protuberance too much can't accurately be counted.In addition, the height of protuberance does not surpass 2% of particle diameter.
(comparative example 3)
(a-9) manufacturing of resin particle
Also add the 0.12g Sodium Lauryl Sulphate BP/USP and do not add non-crosslinked vinylformic acid (ester) based polymer and lauryl phosphoric acid mutually as monomer as water, in addition, operation obtains resin particle similarly to Example 1.
(b-9) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 7, although the visible a plurality of little shallow holes in surface, but still can be referred to as spherical particle.In addition, be attached with a small amount of emulsification.Quantity, height and the length of protuberance are measured in trial based on sciagraph, but do not have to think the place of protuberance.
(comparative example 4)
(a-10) manufacturing of resin particle
The amount of methyl methacrylate is made as 350g, uses non-crosslinked vinylformic acid (ester) based polymer 1 to replace non-crosslinked vinylformic acid (ester) based polymer 2, the amount of ethylene glycol dimethacrylate is made as 150g, in addition, operation obtains resin particle similarly to Example 1.
(b-10) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 8, although some local visible pitting of surface, but still can be referred to as spherical particle.In addition, be attached with a small amount of tiny emulsification.Quantity, height and the length of protuberance are measured in trial based on sciagraph, but do not have to think the place of protuberance.
(comparative example 5)
(a-11) manufacturing of resin particle
Use Propenoic acid, 2-methyl, isobutyl ester to replace methyl methacrylate, in addition, operation obtains resin particle similarly to Example 1.
(b-11) state of resin particle
The median size of gained resin particle is 40 μ m.When observing resin particle with scanning electronic microscope (SEM), as shown in Figure 9, although the visible a plurality of little shallow holes in the surface as the golf ball, but still can be referred to as spherical particle.In addition, be attached with a small amount of emulsification.Quantity, height and the length of protuberance are measured in trial based on sciagraph, but do not have to think the place of protuberance.
About the result of embodiment 1 ~ 6 and comparative example 1 ~ 5, conclude and be shown in table 1.
[table 1]
MMA: methyl methacrylate
St: vinylbenzene
IBMA: Propenoic acid, 2-methyl, isobutyl ester
Polymkeric substance 1: non-crosslinked vinylformic acid (ester) based polymer 1
Polymkeric substance 2: non-crosslinked vinylformic acid (ester) based polymer 2
Polymkeric substance 3: non-crosslinked vinylformic acid (ester) based polymer 3
Can think that the reason of comparative example 1 ~ 3 is not use the phosphate cpd straight chain shape and non-reacted of carbonatoms 4 ~ 40.
Can think that the reason of comparative example 4 is that vinylformic acid (ester) is that the ratio of monomer is less.
Can think that the reason of comparative example 5 is to use Propenoic acid, 2-methyl, isobutyl ester to replace methyl methacrylate.
Use the resin particle that obtains in embodiment 1, embodiment 2, comparative example 1 and the comparative example 3 to make optical thin film.
(embodiment 7)
Be binding agent (MITSUBISHI RAYONCO. with 140 parts by weight of acrylic acid (ester); LTD makes: DIANAL LR-102) mix with 280 weight part embodiment, 1 resulting resin particle, and interpolation with toluene and methylethylketone with mixed solution 260 weight parts of 1:1 as solvent.Use centrifugal blender that it is carried out stirring in 3 minutes, placed 3 hours.Afterwards, (Asahi Kasei ChemicalsCorporation makes: DURANATE TKA-100), reuse centrifugal blender and carry out stirring in 3 minutes to add 30 weight part solidifying agent.The solution coat that the coating machine that uses 200 μ m obtains stirring is on the PET film.With the drying machine that remains on 70 ℃ the film after being coated with is carried out 1 hour drying, obtain optical thin film.
In order to carry out the optical characteristics evaluation of this optical thin film, use haze meter (Japanese electric look company make) to measure mist degree and total light transmittance.
Mist degree is 95.8%, total light transmittance is 78.3%.
(embodiment 8)
Use embodiment 2 resulting resin particles to replace embodiment 1 resulting resin particle, in addition, operation obtains optical thin film similarly to Example 7.Measure mist degree and the total light transmittance of gained optical thin film.
Mist degree is 96.3%, total light transmittance is 78.1%.
(comparative example 6)
Usage comparison example 1 resulting resin particle replaces embodiment 1 resulting resin particle, and in addition, operation obtains optical thin film similarly to Example 7.Measure mist degree and the total light transmittance of gained optical thin film.
Mist degree is 92.3%, total light transmittance is 80.1%.
(comparative example 7)
Usage comparison example 3 resulting resin particles replace embodiment 1 resulting resin particle, and in addition, operation obtains optical thin film similarly to Example 7.Measure mist degree and the total light transmittance of gained optical thin film.
Mist degree is 91.1%, total light transmittance is 81.1%.
About the result of embodiment 7 ~ 8 and comparative example 6 ~ 7, conclude and be shown in table 2.
[table 2]
By the result of embodiment 7, embodiment 8, comparative example 6 and comparative example 7 as can be known, used the surface to be formed with the light diffusing of optical thin film of resin particle of protuberance of regulation number and height more excellent.
(making of external preparation)
Use embodiments of the invention 1 resulting resin particle to make as described below external preparation (powdery foundation cream).It is illustrated as embodiment 9.
(embodiment 9)
The manufacturing of powdery foundation cream
(composition and compounding amount)
Red iron oxide 3.0 weight parts
Zh 1 2.5 weight parts
Black iron oxide 0.5 weight part
Titanium oxide 10.0 weight parts
Mica 20.0 weight parts
Talcum 44.0 weight parts
Whiteruss 5.0 weight parts
Wickenol 142 2.5 weight parts
Vaseline 2.5 weight parts
Sanitas is an amount of
Spices is an amount of
(manufacture method)
With Henschel mixer resin particle, red iron oxide, Zh 1, black iron oxide, titanium oxide, mica, talcum are mixed, add therein the product that whiteruss, Wickenol 142, Vaseline and sanitas mixed dissolution are formed, and mix equably.After further adding spices and mixing, crushing screening.Will by the sieve material compressed moulding in metalware, thereby obtain the powdery foundation cream.
Claims (10)
1. a surface has the resin particle of protuberance, it is approximate spherical resin particle, the particle diameter of described resin particle is 10 ~ 500 μ m, when having the rayed of being subject to, whole surface can carry out irreflexive a plurality of protuberance, wherein, be more than 8 from the fall into a trap quantity of a plurality of protuberances of measuring, be present in the resin particle periphery of the sciagraph of making based on the photo of 1 resin particle being taken 1, the mean value of height that is present in a plurality of protuberances of periphery is 2 ~ 10% of particle diameter.
2. surface according to claim 1 has the resin particle of protuberance, wherein, the resin particle that described surface has protuberance contains component of polymer, and described component of polymer is from the ethene base system monomer of 100 weight parts and non-crosslinked vinylformic acid (ester) based polymer of 1 ~ 30 weight part.
3. surface according to claim 2 has the resin particle of protuberance, and wherein, described ethene base system monomer is that vinylformic acid (ester) is monomer or styrenic monomers.
4. surface according to claim 2 has the resin particle of protuberance, and wherein, described non-crosslinked vinylformic acid (ester) based polymer is the multipolymer of Propenoic acid, 2-methyl, isobutyl ester polymkeric substance or Propenoic acid, 2-methyl, isobutyl ester and methyl methacrylate.
5. coating composition, it contains resin particle, resin glue and solvent that surface claimed in claim 1 has protuberance.
6. one kind is coated with thing, and it contains resin particle and resin glue that surface claimed in claim 1 has protuberance.
7. coating thing according to claim 6, wherein, described coating thing has haze value and the 75% above total light transmittance more than 95%.
8. external preparation, it contains the resin particle that surface claimed in claim 1 has protuberance.
9. external preparation according to claim 8, wherein, described external preparation is makeup or external application pharmaceuticals.
10. a surface has the manufacture method of the resin particle of protuberance, it is the manufacture method that surface claimed in claim 1 has the resin particle of protuberance, it comprises the non-crosslinked vinylformic acid (ester) of the ethene base system monomer that makes 100 weight parts and 1 ~ 30 weight part thereby based polymer carries out the operation that suspension polymerization obtains resin particle in the presence of tensio-active agent, and described tensio-active agent is the straight chain shape, the optional non-reacted phosphate cpd that contains ester group of carbonatoms 4 ~ 40.
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| JP2010075805A JP5613431B2 (en) | 2010-03-29 | 2010-03-29 | Resin particles having convex portions on the surface, method for producing the same, coating composition using the same, coated product, and external preparation |
| PCT/JP2010/066727 WO2011121821A1 (en) | 2010-03-29 | 2010-09-27 | Resin particle having convex portions on surface, method for producing same, and coating composition, coating material, and preparation for external use, each using same |
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| CN104250328A (en) * | 2013-06-28 | 2014-12-31 | 积水化成品工业株式会社 | Acrylic acid series resin particle and externally used agent using acrylic acid series resin particle |
| CN110229267A (en) * | 2014-09-30 | 2019-09-13 | 积水化成品工业株式会社 | Polymer beads and application thereof |
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| JP5844889B2 (en) * | 2012-04-27 | 2016-01-20 | 積水化成品工業株式会社 | POLYMER PARTICLE, PROCESS FOR PRODUCING THE SAME, AND USE THEREOF |
| KR101943851B1 (en) * | 2013-06-26 | 2019-01-30 | 세키스이가세이힝코교가부시키가이샤 | Acrylic based resin particle and external preparation using the same |
| JP6131383B2 (en) * | 2014-03-18 | 2017-05-17 | 株式会社日本触媒 | Resin particles, conductive fine particles, and anisotropic conductive materials using the same |
| KR101817032B1 (en) | 2014-05-12 | 2018-01-09 | 다이니치 세이카 고교 가부시키가이샤 | Resin beads, method for manufacturing resin beads and product containing resin beads |
| WO2016006540A1 (en) * | 2014-07-09 | 2016-01-14 | 大日精化工業株式会社 | Resin beads, method for manufacturing resin beads and product including resin beads |
| JP6478528B2 (en) * | 2014-09-01 | 2019-03-06 | キヤノン株式会社 | Resin fine particle dispersion, ink for ink jet recording, ink jet recording method, ink cartridge, and ink jet recording apparatus |
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| KR20130018255A (en) | 2013-02-20 |
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| JP5613431B2 (en) | 2014-10-22 |
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