Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
• • 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
  • C08F2/32—Polymerisation in water-in-oil emulsions
• • 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
  • C08F212/00—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
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements

Definitions

• the present invention relates to a polymer fine particle composition and use thereof.
• the present invention relates to a (meth) acrylic crosslinked fine particle copolymer composition having a refractive index of 1.60 or more and an average particle diameter of 2 to 5 ⁇ m.
• the composition contains additives such as a polymerization stabilizer and a surfactant.
• the polymer fine particles are arranged in a concavo-convex shape using a binder on the surface of the acrylic light diffusing sheet, or are contained in the sheet to cause diffusion of transmitted light due to a difference in refractive index.
• the polymer fine particles are arranged in a concavo-convex shape using a binder on the surface of the acrylic light diffusing sheet, or are contained in the sheet to cause diffusion of transmitted light due to a difference in refractive index.
• a light diffusion sheet is used in order to make the light source arranged on the back of the screen function as a surface light source.
• this light diffusion sheet for example, there is one in which a transparent (meth) acrylic resin sheet is used as a base material and fine particles having higher refraction are applied or combined.
• inorganic particles such as silica and titanium dioxide were initially used.
• non-uniform dispersion due to insufficient affinity with the resin, white turbidity or translucency of the product due to the material itself being opaque, brightness reduction, and scratches when contacting with other flexible materials As a result, polymer-based fine particle compositions having flexibility have become mainstream.
• (Meth) acrylic crosslinked fine particles are a representative example, and various fine particle compositions have been proposed up to a refractive index of around 1.59 (for example, Patent Document 1).
• a polymer fine particle composition having a refractive index of 1.60 to 1.62 and an average particle size of 2 to 5 ⁇ m is required in order to meet the recent demand for thinner display devices and higher brightness.
• no specific proposal has been made for (meth) acrylic crosslinked fine particles. Although fine particles having a refractive index exceeding 1.60 are known, these are not (meth) acrylic materials (for example, Patent Documents 2 to 3).
• the present invention is used in a liquid crystal display device aiming at thinning and high brightness, for example, (meth) acrylic resin (meaning acrylic resin, methacrylic resin, the same shall apply hereinafter), a high function of a light diffusion sheet base material
• (meth) acrylic resin meaning acrylic resin, methacrylic resin, the same shall apply hereinafter
• An object of the present invention is to provide a high-refractive-index crosslinked acrylic fine particle composition that is effective for the preparation.
• the first of the present invention is 98 to 70% by mass of an ethoxylated o-phenylphenol (meth) acrylate compound represented by the chemical formula (1), 2 to 30% by mass of a divinyl compound having a molecular weight smaller than that of the chemical formula (1) ( It is related with the polymer fine particle composition formed by carrying out a copolymer reaction.
• R is H or —CH 3.
• the second of the present invention relates to the first polymer fine particle composition of the present invention in which the average particle diameter of the polymer fine particles is in the range of 2 to 5 ⁇ m and the refractive index is in the range of 1.60 to 1.62.
• the third aspect of the present invention relates to the polymer fine particle composition according to the first or second aspect of the present invention, wherein the divinyl compound contains divinylbenzene.
• the fourth aspect of the present invention relates to a light scattering sheet comprising the polymer fine particle composition according to any one of the first or first to third aspects of the present invention.
• the fifth aspect of the present invention relates to the use of the polymer fine particle composition according to any one of the first to third aspects of the present invention as a light scattering agent.
• the sixth of the present invention relates to a method for producing a polymer fine particle composition, which comprises the following steps: Ethoxylated-o-phenylphenol acrylate 98-70% by mass, divinyl compound having a molecular weight smaller than ethoxylated-o-phenylphenol (meth) acrylate (molecular weight 268 or 282) 2-30% by mass (both 100% by mass) A step of emulsifying the oil phase and the aqueous phase comprising an O / W emulsion, and a subsequent suspension polymerization step of the O / W emulsion.
• the polymer fine particle composition has an average particle diameter of 2 to 5 ⁇ m and a refractive index of 1.60 to 1.62.
• Seventh aspect of the present invention relates to a method for producing a polymer fine particle composition according to the sixth aspect of the present invention, wherein the divinyl compound contains divinylbenzene.
• the polymer fine particle composition according to the present invention for example, by applying to a (meth) acrylic transparent resin material substrate, or by combining (by laminating a thin film, kneading into a substrate, etc.), A light diffusing highly functional optical material having excellent light diffusibility can be obtained.
• the polymer fine particle composition according to the present invention comprises 98 to 70% by mass of an ethoxylated o-phenylphenol (meth) acrylate compound represented by the chemical formula (1) and a molecular weight smaller than that of the compound represented by the chemical formula (1). 2 to 30% by mass of the divinyl compound (100% by mass in total) is cross-linked and co-polymerized.
• R is H or —CH 3.
• the compound represented by the chemical formula (1) can be synthesized by a known method for synthesizing (meth) acrylic acid ester, and R in formula (1) is H (hydrogen).
• the acrylate can be obtained from the market under the trade name “A-LEN-10” (manufactured by Shin-Nakamura Chemical Co., Ltd.).
• the compound represented by the chemical formula (1) is known to have a large refractive index.
• Specific usage methods include a monomer for a photocurable resin (Shin-Nakamura Chemical Co., Ltd. website) and an intraocular lens (for example, Patent Publication 2006). No. 249381), a specific method of using the high refractive index fine particle composition as a raw material has not yet been clarified.
• the compound of the chemical formula (1) is relatively poor in hydrophilicity and has a high viscosity in the acrylate compound.
• a large oil phase or oil droplets, the same applies hereinafter
• the oil phase is likely to associate.
• a surfactant is added in order to reduce the oil phase in the O / W emulsion to 5 ⁇ m or less.
• a surfactant exhibiting a remarkable and remarkable effect is found in the compound of the chemical formula (1).
• it is necessary to add a large amount of a surfactant In this case, however, the post-treatment is complicated, and the remaining surfactant may impair the function of the light scattering agent of the particles.
• the compound represented by the chemical formula (1) is not easily divided or refined even when a normal amount of a surfactant is used in combination with vigorous stirring. Moreover, even after fragmentation / miniaturization, the particles are easily associated and returned to large particles, and the oil phase does not become 5 ⁇ m or less.
• the compound of the chemical formula (1) (wherein R is hydrogen, the molecular weight is 268, and when R is CH3, 282) is 98 to 70% by mass, and the compound of the chemical formula (1) By copolymerizing 2-30% by mass of a small molecular weight divinyl compound (100% by mass in combination), polymer fine particles capable of solving the problems of the present application can be obtained. Of these, an average particle size of 1-5 ⁇ m is particularly preferred. And a fine polymer particle composition having a refractive index of 1.60 to 1.62 was found to be preferable.
• the compound of the chemical formula (1) is preferably 98 to 70% by mass, more preferably 90 to 75% by mass. If the amount is less than 70% by mass, fine particles having a refractive index of 1.60 or more cannot be obtained, and if it exceeds 98% by mass, it is difficult to make the average particle size of the polymer fine particles 5 ⁇ m or less.
• the divinyl compound having a molecular weight smaller than the compound of the chemical formula (1) is preferably 2 to 30% by mass, and more preferably 10 to 25% by mass. If it is less than 2% by mass, it will be difficult to make the average particle size of the polymer fine particles 5 ⁇ m or less, and if it exceeds 30% by mass, it will be difficult to obtain fine particles having a refractive index of 1.60 or more. .
• the following measuring method is mentioned, for example.
• the average particle diameter can be measured using a Beckman Coulter Multisizer 4 with an aperture hole diameter of 30 ⁇ m.
• the refractive index can be measured according to the JISK7132B method.
• the average particle diameter of the polymer fine particles obtained may be large, and the refractive index may be out of a predetermined range and the light diffusion effect may be inferior. is there.
• the present inventors have found that divinyl compounds having a molecular weight smaller than the chemical formula (1) according to the present invention can be used in preparation of an O / W type emulsion and subsequent suspension polymerization in addition to the original function as a crosslinking agent. It is considered to have the effects i) to iv). i) Excellent miscibility (affinity) with the chemical formula (1) and easily forms a uniform oil phase (oil droplets). ii) In adjusting the O / W type emulsion, the effect of reducing the apparent viscosity of the oil phase mainly composed of the chemical formula (1) under shearing conditions is excellent. iii) It is excellent in the rapidity of the crosslinking rate at the time of suspension polymerization reaction progress, and suppresses the increase in particles due to re-association between particles. iv) Excellent copolymerization with the chemical formula (1).
• a preferred specific example of the divinyl compound in the present inventor is divinylbenzene (DVB, molecular weight 130) (obtained from the market) which has a sufficiently small molecular weight and is an aromatic compound similar to the compound of the chemical formula (1).
• DVB divinylbenzene
• BDDMA molecular weight 226)
• HAMA hydroxy-3-acryloyloxypropyl methacrylate
• the polymer fine particles according to the present invention can be obtained by a known suspension polymerization reaction apparatus or reaction step.
• a preferred production method is 98 to 70% by mass of chemical formula (1), 2 to 30% by mass of a divinyl compound having a molecular weight smaller than that of ethoxylated o-phenylphenol acrylate (molecular weight 268) having a molecular weight smaller than chemical formula (1) (both combined)
• the oil phase and the aqueous phase comprising the O / W type emulsion, and the subsequent emulsion polymerization step of the O / W type emulsion.
• the polymerization initiator used for the suspension polymerization according to the present invention is not limited. Usually, an oil-soluble peroxide polymerization initiator or an azo polymerization initiator used for aqueous suspension polymerization can be used. Specifically, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, peroxide polymerization initiators such as t-butyl hydroperoxide and diisopropylbenzene hydroperoxide, azobisvaleronitrile, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2′-azobis (2,3-dimethyl
• 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, etc. are suitable polymerization initiators. This is preferable in that it has a decomposition rate.
• the polymerization initiator is preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture. When the polymerization initiator is less than 0.01 parts by mass, it is difficult to fulfill the function of initiating the polymerization, and when it is used in excess of 10 parts by mass, the addition amount is more than necessary, which is not preferable because it is not economical. .
• An oil / water mixture containing the compound of the chemical formula (1) and a divinyl compound having a lower molecular weight is dissolved in a polymerization initiator according to a conventional method and then stirred and mixed with an aqueous solution containing a polymerization stabilizer and a surfactant. Adjust to W-type emulsion.
• the O / W emulsion mixture is heated with stirring to conduct a polymerization reaction to obtain the desired polymer fine particle composition.
• a water-soluble polymer such as polyvinyl alcohol or an inorganic stabilizer such as calcium phosphate can be used.
• ester types such as glycerin fatty acid ester and sorbitan fatty acid ester, polyoxyethylene (or POE) alkyl ether, polyoxyethylene (or POE) Ether type such as alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, etc., type with ethylene oxide added to fatty acid or polyhydric alcohol fatty acid ester, ester ether having both ester bond and ether bond in the molecule A mold or the like is used.
• ester types such as glycerin fatty acid ester and sorbitan fatty acid ester, polyoxyethylene (or POE) alkyl ether, polyoxyethylene (or POE) Ether type such as alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, etc., type with ethylene oxide added to fatty acid or polyhydric alcohol fatty acid ester, ester ether having both ester bond and ether bond in the molecule A mold or the like is used.
• the polymer fine particle composition particles are used after being subjected to a solid-liquid separation step and a drying step by a normal operation from the polymerization reaction solution and then taken out as a powder by crushing. That is, after removing moisture by a method of drying a shelf after obtaining a wet cake by centrifugation, a method of spray drying, etc., and then applying impact with a hammer mill, a bead mill, etc. Obtainable.
• the shape of the fine particles is not particularly limited, but a spherical shape, a spheroid and the like are preferable.
• the polymer fine particle composition of the present invention can be prepared by a known method, for example, a light scattering sheet prepared by melting and kneading into a (meth) acrylic light diffusion sheet material, or a (meth) acrylic solution. It can be used in any of a method of forming by suspending, casting and removing the solvent, and a method of coating the surface of the sheet by suspending in a transparent epoxy prepolymer. At that time, various additives, fillers, and the like can be added. Further, the sheet surface can be subjected to an uneven pattern or embossing.
• the thickness of these light diffusing sheets is not particularly limited, but is preferably from 0.1 ⁇ m to 20 mm, more preferably from the viewpoint of application, productivity, handleability, and transportability.
• the thickness is 5 ⁇ m to 15 mm, more preferably 1 ⁇ m to 10 mm.
• the light diffusion sheet is made of a plastic material that is generally used, for example, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyvinyl alcohol (PVA), polyvinyl chloride (PVC).
• resins such as polycarbonate (PC).
• the polymer fine particle composition of the present invention can be used in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the resin for sheet.
• a sheet obtained by kneading 100 parts of polyethylene terephthalate and 5 parts of the polymer fine particle composition of the present invention can be stretched to obtain a sheet having a thickness of 60 to 150 ⁇ m.
• a stabilizer, an ultraviolet absorber, a lubricant, etc. can be added in the range which does not impair the transparency of these resins.
• the polymer fine particle composition of the present invention can be blended in paints, printing, inks, cosmetics and the like in addition to the light diffusion sheet.
• the polymer fine particle composition of the present invention can be used for paints.
• examples thereof include organic solvent paints, water-based paints, emulsion paints, colloidal paints, and powder paints.
• 1 to 100 parts by mass can be blended with respect to 100 parts by mass of the coating resin content.
• the blending amount is preferably 1 to 70 parts by mass, and more preferably 1 to 20 parts by mass.
• the polymer fine particle composition of the present invention can be used for printing ink.
• Examples thereof include letterpress ink, flat plate ink, intaglio ink, metal plate ink, radiation curable ink, UV ink, EB ink, flexographic ink, screen ink, offset ink, gravure ink, and water-based ink.
• 1 to 100 parts by mass can be blended with respect to 100 parts by mass of the resin solid content in the ink.
• the blending amount is preferably 1 to 70 parts by mass, and more preferably 1 to 20 parts by mass.
• the polymer fine particle composition of the present invention can be used for cosmetics.
• makeup cosmetics, hair cosmetics, pack cosmetics and the like can be mentioned.
• it can be used for gels, lipsticks, foundation blushers, mascaras, nail enamels, eyebrows, eye shadows, eyeliners, hair preparations and the like.
• the compounding amount include 1 to 90 parts by mass.
• the polymer fine particle composition of the present invention can be used by blending with a color toner for copying machines.
• a part is a mass part. (Production method of polymer fine particle composition)
• the obtained oil / water mixture was subjected to a dispersion treatment at 19000 rpm for 2 minutes by a disperser to obtain an O / W emulsion.
• This emulsion was poured into a polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet, and a polymerization reaction was carried out at 80 ° C. for 4 hours while introducing nitrogen.
• TMPTA trivinylpropane triacrylate
• DDDA 10-decanediol diacrylate
• BPE-100 [2,2-bis (4- (methacryloxyethoxy) phenyl] propane
• the polymer fine particle composition according to the present invention has, for example, a high refractive index and an affinity with an acrylic resin, and is arranged in an uneven shape using a binder on the surface of the acrylic light diffusing sheet, or in the sheet Since it is possible to cause diffusion of transmitted light due to a difference in refractive index, it is suitably used as a light diffusing agent for a diffusion sheet for backlight.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Optical Elements Other Than Lenses (AREA)
• Polymerisation Methods In General (AREA)

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• 2015
  • 2015-05-18 TW TW104115737A patent/TW201546153A/zh unknown
  • 2015-05-21 JP JP2016521173A patent/JPWO2015178501A1/ja active Pending
  • 2015-05-21 KR KR1020167032286A patent/KR20170013227A/ko unknown
  • 2015-05-21 CN CN201580026389.XA patent/CN106661168A/zh active Pending
  • 2015-05-21 WO PCT/JP2015/065326 patent/WO2015178501A1/ja active Application Filing

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