WO2013161843A1 - 光拡散性樹脂組成物およびその成形品 - Google Patents

光拡散性樹脂組成物およびその成形品 Download PDF

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Publication number
WO2013161843A1
WO2013161843A1 PCT/JP2013/061976 JP2013061976W WO2013161843A1 WO 2013161843 A1 WO2013161843 A1 WO 2013161843A1 JP 2013061976 W JP2013061976 W JP 2013061976W WO 2013161843 A1 WO2013161843 A1 WO 2013161843A1
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Prior art keywords
fine particles
light
light diffusing
resin composition
resin fine
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PCT/JP2013/061976
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English (en)
French (fr)
Japanese (ja)
Inventor
直彦 斎藤
徳弘 平野
松崎　英男
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東亞合成株式会社
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Priority to JP2014512629A priority Critical patent/JP5958533B2/ja
Priority to CN201380015155.6A priority patent/CN104204867B/zh
Priority to KR1020147029268A priority patent/KR20150003205A/ko
Publication of WO2013161843A1 publication Critical patent/WO2013161843A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V3/00—Globes; Bowls; Cover glasses
    • F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
    • F21V3/06—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material
    • F21V3/062—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material the material being plastics
    • F21V3/0625—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material the material being plastics the material diffusing light, e.g. translucent plastics

Definitions

  • the present invention relates to a light diffusing resin composition and a molded product thereof. More specifically, the present invention relates to a light diffusing resin composition that exhibits good light diffusibility and diffusion efficiency, and is excellent in heat resistance, impact resistance, and flame retardancy, and a molded product thereof.
  • a diffusion plate in which a light diffusing agent is dispersed in a matrix made of a transparent resin such as polymethyl methacrylate, polystyrene, and polycarbonate in order to uniformly diffuse light from a light source. It is used.
  • a transparent resin such as polymethyl methacrylate, polystyrene, and polycarbonate
  • inorganic particles such as crystalline silica, amorphous silica, calcium carbonate, barium sulfate, aluminum hydroxide, and titanium oxide, or inorganic fibers such as glass fibers have been used as the light diffusing agent.
  • Patent Document 1 discloses a light diffusing plate using polymer particles having an average particle size of 3 to 20 ⁇ m and a narrow particle size distribution with a CV value of 20% or less as a light diffusing agent.
  • Patent Document 2 discloses that the average particle diameter is 0.6 to 1.5 ⁇ m, the standard deviation of the particle diameter is 0.01 ⁇ m to 0.5 ⁇ m, and the styrene monomer / methacrylic acid copolymer and A light diffusing plate containing a diffusing agent having an absolute value of the refractive index difference of 0.05 or more is disclosed.
  • Patent Document 3 discloses a composition in which acrylic resin-based fine particles having an average particle size of 1 to 4 ⁇ m as a light diffusing agent and having a specific particle size distribution are dispersed in a polycarbonate resin.
  • Patent Document 4 discloses a composition containing crosslinked polymer fine particles having a refractive index different from that of polycarbonate resin and having an average particle diameter in the range of 0.5 to 100 ⁇ m.
  • Patent Document 5 discloses a composition in which polymer fine particles having a refractive index in the range of 1.495 to 1.504 are dispersed in a polycarbonate resin.
  • Patent Document 6 discloses a composition containing crosslinked resin fine particles comprising a specific (meth) acrylate ester resin having a volume average particle size of 0.7 to 2.5 ⁇ m and a narrow particle size distribution. Has been.
  • a cover for a lighting fixture there is a demand for a molding material that exhibits good light diffusibility in a wide range of total light transmittance.
  • a molding material containing a light diffusing agent that can achieve a target light diffusibility (dispersion degree) with a small amount of addition.
  • the light diffusibility of a resin composition in which a light diffusing agent particle is blended with a transparent resin and a molded product made from the resin composition are the refractive index difference between the resin and the light diffusing agent particle, the particle size of the light diffusing agent particle, and the light diffusing agent particle.
  • the refractive index difference between the resin and the light diffusing agent particle is larger, and the particle size of the light diffusing agent particle is larger, the light from one light diffusing agent particle is known.
  • the diffusion coefficient increases. However, if the particle size of the light diffusing agent particles is large, the mass of the light diffusing agent particles becomes large.
  • the mass ratio of the light diffusing agent particles in the resin is constant, the large particles contained in the resin The number of light diffusing agent particles having a smaller diameter is reduced, and the overall light diffusibility based on the product of the light diffusion coefficient of each light diffusing agent particle and the number of light diffusing agent particles contained in the resin is not necessarily high. Don't be.
  • the particle size of the light diffusing agent particles contained in the transparent resin is too small, the light diffusion coefficient decreases exponentially, so that sufficient light diffusibility cannot be obtained.
  • the degree of dispersion tends to decrease, but a material exhibiting a high degree of dispersion in a wide range of total light transmittance is preferable, and the light diffusing agent has a total light transmittance of, for example, There is a demand for performance that shows a high degree of dispersion even in a high region of 85% and that can be used in a wide range of total light transmittance.
  • the difference between the refractive index of the transparent resin and the refractive index of the light diffusing agent particles becomes too large, the amount of reflected light from the molded body increases. Then, the total light transmittance is reduced, and for example, sufficient brightness cannot be obtained in a light diffusing plate of a display, a transmissive screen, a cover of a lighting fixture, an electric signboard, and the like. Furthermore, since the light diffusing plate may be molded under a high temperature condition exceeding 300 ° C., the light diffusing agent has excellent heat resistance such that decomposition or the like hardly occurs even under a high temperature condition. Is also required.
  • Patent Document 1 Japanese Patent Document 1
  • Patent Document 2 shows good light diffusibility with a relatively small amount of light diffusing agent, but the light diffusibility in a region where the total light transmittance is 70% or more is not sufficient. For this reason, it cannot be used for applications that require high light transmission, such as covers for lighting fixtures.
  • the light diffusing agents described in Patent Documents 3 to 5 need to be added in an amount in order to obtain good light diffusibility in a region where the total light transmittance is less than 80%. There was a problem from the aspect.
  • Patent Document 6 although it is possible to express good light diffusibility in a wide range of total light transmittance with a small amount of light diffusing agent, there is room for improvement in terms of heat resistance.
  • An object of the present invention is to provide a light diffusing resin composition that exhibits high dispersion in a wide range of total light transmittance, has excellent light diffusibility, and has excellent heat resistance, impact resistance, and flame retardancy, and a molded product thereof. It is to be.
  • the present inventors have used light-diffusing properties, heat resistance, impact resistance by using crosslinked resin fine particles having a specific particle size, particle size distribution, refractive index and the like as a light diffusing agent. It has been found that a light diffusing resin composition having excellent properties and the like can be obtained.
  • the present invention is as follows. 1. An absolute value of a difference between the refractive index of the transparent resin (X) and the refractive index of the crosslinked resin fine particles (Y) (hereinafter referred to as “ ⁇ n”) including the transparent resin (X) and the crosslinked resin fine particles (Y). 0.095 to 0.115, the volume average particle diameter of the crosslinked resin fine particles (Y) is 1.5 to 3.3 ⁇ m, and the coefficient of variation of the particle diameter of the crosslinked resin fine particles (Y) is 20%.
  • the cross-linked resin fine particles (Y) are characterized in that the temperature at which the mass is halved is 320 ° C. or higher when pyrolyzed in a nitrogen gas atmosphere at a temperature rising rate of 10 ° C./min.
  • a light diffusing resin composition 2. 2. The light diffusing resin composition as described in 1 above, wherein the crosslinked resin fine particles (Y) contain a structural unit derived from a (meth) acrylic acid ester. 3. A sheet of 1.5 mm thickness produced using the light diffusing resin composition, which has a total light transmittance of 85% for white light, is irradiated with light in a vertical direction using a goniometer. 3. The light diffusing resin composition according to 1 or 2 above, wherein an angle at which the emitted light having a luminance of 50% with respect to the emitted light at 0 degree is 20 degrees or more when the incident light is incident. 4).
  • the light diffusing resin composition of the present invention exhibits a high degree of dispersion in a wide range of total light transmittance and is excellent in light diffusibility. Moreover, the light diffusable resin composition of this invention is excellent also in heat resistance, impact resistance, and a flame retardance.
  • the light diffusing resin composition of the present invention comprises crosslinked resin fine particles (Y) having a specific particle size, particle size distribution, refractive index, composition and the like as a light diffusing agent, and a transparent resin (X).
  • the present invention relates to a light diffusing resin composition that exhibits good light diffusivity and diffusion efficiency and is excellent in heat resistance and the like, and a molded body using the same.
  • the crosslinked resin fine particles (Y) have an action as a light diffusing agent.
  • the transparent resin (X) according to the present invention is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate (PMMA), styrene resins such as polystyrene and styrene / methacrylic acid copolymers, Polycarbonate resin etc. are mentioned. Of these, styrene resins are preferred when importance is placed on cost, but polycarbonate resins are preferred when impact resistance and flame retardancy are required.
  • acrylic resins such as polymethyl methacrylate (PMMA)
  • styrene resins such as polystyrene and styrene / methacrylic acid copolymers
  • Polycarbonate resin etc. are mentioned.
  • styrene resins are preferred when importance is placed on cost, but polycarbonate resins are preferred when impact resistance and flame retardancy are required.
  • the content ratio of the structural unit derived from the styrenic monomer from the viewpoint of the melt fluidity, moldability, heat resistance, moisture absorption resistance, refractive index, etc. of the composition is styrene resin. It is preferable to use a resin that is 80% by mass or more with respect to a total amount of 100% by mass of all the structural units to be configured. More preferred is 90% by mass or more, and particularly preferred is 95 to 100% by mass.
  • styrene monomer forming the styrene resin examples include styrene, ⁇ -methyl styrene, p-methyl styrene, o-methyl styrene, m-methyl styrene, vinyl toluene, p-ethyl styrene, p-tert.
  • the styrenic resin may contain only one type of structural unit derived from these styrenic monomers, or may contain two or more types. Of these, styrene is preferable from the viewpoint of availability of styrene-based resin, cost, polymerizability, and the like.
  • the styrenic resin may be either a homopolymer or a copolymer. In the latter case, a copolymer obtained by copolymerizing a monomer containing a styrene monomer and methacrylic acid can be used.
  • the content of the styrene monomer unit constituting the copolymer is preferably 80 to 95 mol%, more preferably 85 to 95 mol% from the viewpoint of heat resistance.
  • the copolymer may contain a structural unit derived from another monomer copolymerizable with these, in addition to the styrene monomer and methacrylic acid.
  • Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as benzyl and 2-hydroxyethyl (meth) acrylate; acrylic acid, maleic anhydride, (meth) acrylonitrile and the like.
  • Other monomers can be used alone or in combination of two or more.
  • the molecular weight of the styrene resin is not particularly limited.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is 50,000 to 1 in terms of the moldability of the composition, particularly melt moldability, and the strength of the resulting molded product. It is preferably 1,000,000, more preferably 100,000 to 500,000.
  • the molecular weight distribution (Mw / Mn) of the styrenic resin is preferably 1.5 to 3.5 from the viewpoint of the strength of the obtained molded article.
  • polycarbonate resin examples include aromatic polycarbonate resin, aliphatic polycarbonate resin, and aromatic-aliphatic copolymer polycarbonate resin.
  • An aromatic polycarbonate resin is often used for the light diffusing resin composition. Specifically, it is an aromatic polycarbonate resin obtained by a reaction between a divalent phenol compound and phosgene or diphenyl carbonate.
  • divalent phenol examples include 2,2- (4-hydroxyphenyl) propane (bisphenol A), 2,2- (4-hydroxyphenyl) butane, and 2,2- (4-hydroxyphenyl).
  • examples include pentane, 4,4′-biphenol, hydroquinone, resorcinol and the like.
  • 2,2- (4-hydroxyphenyl) propane (bisphenol A) is preferred because of its good impact resistance and the like.
  • the polycarbonate resin may be a polycarbonate resin obtained by any method of interfacial polymerization and melt transesterification.
  • the viscosity average molecular weight of the polycarbonate resin is not particularly limited, but is preferably 1 ⁇ 10 4 to 1 ⁇ 10 5 , more preferably 1.3 ⁇ 10 4 to from the viewpoint of mechanical properties and fluidity during injection molding. 3 ⁇ 10 4 .
  • Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, flame retardancy, etc., and is relatively inexpensive for its performance, so it is widely used in optical applications such as lighting equipment and displays. . Accordingly, the transparent resin (X) according to the present invention is particularly preferable.
  • the cross-linked resin fine particles (Y) are not limited as long as they are fine particles made of a resin having a cross-linked structure. Since the selectivity of the monomer to be used is high and the refractive index can be easily adjusted, the fine particles are composed of a (meth) acrylate crosslinked resin containing a structural unit derived from (meth) acrylate. preferable.
  • the crosslinked structure contained in the fine particles can be based on cleavage by polymerization of a polyfunctional polymerizable unsaturated compound containing a plurality of carbon-carbon double bonds, or can be based on a siloxane bond.
  • the content ratio of the structural unit derived from the (meth) acrylic acid ester constituting the (meth) acrylic acid ester-based crosslinked resin is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass. % Or more, particularly preferably 95 to 100% by mass.
  • the refractive index of the crosslinked resin fine particles (Y) is easily adjusted to the range of 1.460 to 1.510. This is preferable because it can be performed.
  • the method for producing the crosslinked resin fine particles (Y) used in the present invention is not particularly limited, but the following methods can be exemplified.
  • the crosslinked resin fine particles obtained by the above methods (i) and (ii) may be used alone or in combination.
  • the method for producing (meth) acrylic ester-based crosslinked resin fine particles is generally suspension polymerization, but in the case of suspension polymerization, it is necessary to produce crosslinked resin fine particles having a narrow particle size distribution and uniform size. Is generally difficult.
  • crosslinked resin fine particles having a narrow particle size distribution and a uniform size can be produced smoothly by polymerization in an alcohol solvent, particularly a mixed solvent of alcohol and water. Further, the particle size and particle size distribution can be controlled by adjusting the ratio of alcohol and water. From this point, in the present invention, the above methods (i) and (ii) are preferably used.
  • the seed particle is preferably a (meth) acrylic acid ester resin and is produced by subjecting the vinyl monomer (m1) to dispersion polymerization in a water / alcohol polar solvent. can do.
  • a carboxyl group-containing macromonomer is used as a dispersion stabilizer, dispersion polymerization proceeds more smoothly.
  • the carboxyl group-containing macromonomer is not particularly limited as long as it has a radical polymerizable unsaturated bond at the molecular end or side chain. Examples of the radical polymerizable unsaturated bond include a terminal vinylidene group, a terminal (meth) acryloyl group, a side chain (meth) acryloyl group, and a terminal styryl group.
  • Examples of the vinyl monomer (m1) forming the seed particles include (meth) acrylic acid esters and aromatic vinyl compounds. Specific monomers include methyl (meth) acrylate, (meta ) Ethyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid 2 -Alkyl esters of (meth) acrylic acid such as ethylhexyl, lauryl (meth) acrylate and stearyl (meth) acrylate; alicyclics of (meth) acrylic acid such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate Group-containing ester; (meth) such as glycidyl (meth) acrylate and tetrahydrofurfuryl
  • Examples include hydroxyalkyl esters of (meth) acrylic acid; alkoxyalkyl esters of (meth) acrylic acid such as 2-methoxyethyl (meth) acrylate. These compounds may be used alone or in combination of two or more.
  • the vinyl monomer (m1) preferably contains a (meth) acrylic acid ester, and methyl methacrylate and isobutyl methacrylate are particularly preferable.
  • the amount of the (meth) acrylic acid ester used for the formation of the seed particles is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, based on the total mass of the vinyl monomer (m1). It is.
  • the seed particles are preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70 to 100% by mass based on 100% by mass of the total amount of structural units constituting the seed particles. It is preferable from the point of the heat-resistant blocking property of a particle
  • the macromonomer When producing the seed particles, the macromonomer is used in an amount of preferably 0.5 to 50 parts by mass, more preferably 1.0 to 20 parts by mass with respect to 100 parts by mass of the vinyl monomer (m1). Part.
  • the weight average molecular weight (Mw) of the seed particles is preferably 1,000 to 2,000,000 in terms of polystyrene measured by gel permeation chromatography (GPC), preferably 5,000 to 1,000. 1,000 is more preferable.
  • the vinyl monomer (m2) to be polymerized after being absorbed in the seed particles obtained by dispersion polymerization contains a polyfunctional vinyl monomer in order to form the crosslinked resin fine particles (Y).
  • a polyfunctional (meth) acrylate compound excellent in polymerizability is preferably used. Specific examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and the like.
  • Di (meth) acrylate of dihydric alcohol trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Examples include tri (meth) acrylates of trihydric or higher polyhydric alcohols such as tetra (meth) acrylate and poly (meth) acrylates such as tetra (meth) acrylate. Only 1 type may be used for a polyfunctional (meth) acrylate compound, and 2 or more types can be used for it.
  • ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate can be easily absorbed into seed particles made of (meth) acrylic ester resin, and can increase the crosslinking density. It is preferably used in terms of being possible and excellent in polymerization stability.
  • the vinyl monomer (m2) to be absorbed and polymerized in the seed particles contains a monofunctional vinyl monomer together with the polyfunctional vinyl monomer described above. This is preferable because the polymerization stability is advantageous.
  • This monofunctional vinyl monomer is a monomer that is the same as or similar to the monomer such as (meth) acrylic acid ester constituting the seed particle, for example, methyl methacrylate and isobutyl methacrylate. Is preferred.
  • the refractive resin is more refracted.
  • a monofunctional vinyl monomer that forms a polymer having a low rate and for example, isobutyl methacrylate, tert-butyl methacrylate and the like are preferably used.
  • the ratio of the preferred amount of seed particles and vinyl monomer (m2) used in the production of the crosslinked resin fine particles (Y) is not particularly limited, but the crosslinking structure is imparted to the particles and the monomer is absorbed into the seed particles. From the point of view, it is shown below.
  • the vinyl monomer (m2) is preferably 0.5 to 10 parts by mass and more preferably 0.7 to 5 parts by mass with respect to 1 part by mass of the seed particles.
  • the amount of the polyfunctional vinyl monomer used is preferably 3 to 95% by mass, particularly preferably 5 to 75% by mass, based on the total mass of the vinyl monomer (m2).
  • the resin fine particles having a hydrolyzable silyl group are subjected to dispersion polymerization using a vinyl monomer having a hydrolyzable silyl group and (meth) acrylic acid ester or the like. It is preferable that it is the fine particle obtained by performing.
  • the hydrolyzable silyl group means a functional group that can be crosslinked by forming a siloxane bond by hydrolysis condensation reaction, and includes methoxysilane, ethoxysilane, and the like.
  • Any vinyl compound having at least one hydrolyzable silyl group can be used as the vinyl monomer having a hydrolyzable silyl group.
  • vinyl silane such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, etc .
  • the vinyl monomer having a hydrolyzable silyl group a hydrolyzable silyl group-containing acrylate ester and a hydrolyzable silyl group-containing methacrylate ester are preferable. These monomers are preferable because they are excellent in copolymerizability with (meth) acrylic acid esters and the like, and fine particles excellent in heat resistance and weather resistance are obtained.
  • trimethoxysilylpropyl methacrylate also known as trimethoxysilylpropyl methacrylate
  • the amount of vinyl monomer having a hydrolyzable silyl group is generally based on the total mass of monomers (including macromonomers) used for the production of resin fine particles having hydrolyzable silyl groups. Thus, it is preferably 2 to 50% by mass, particularly 5 to 30% by mass.
  • Examples of monomers other than vinyl monomers having hydrolyzable silyl groups used in the production of resin fine particles having hydrolyzable silyl groups include (meth) acrylic acid esters. The monomer is as described above.
  • a macromonomer type dispersion stabilizer having a (meth) acryloyl group it is preferable to use a macromonomer type dispersion stabilizer having a (meth) acryloyl group.
  • a macromonomer type dispersion stabilizer having a (meth) acryloyl group a (meth) acrylic acid ester system having a target particle size and a hydrolyzable silyl group having a narrow particle size distribution with a small amount of use. Resin fine particles can be obtained smoothly.
  • the macromonomer type dispersion stabilizer more preferably has a carboxyl group.
  • the (meth) acryloyl group may be bonded to any position of the end of the polymer chain and the side chain.
  • a macromonomer type dispersion stabilizer with a (meth) acryloyl group bonded to the side chain stably produces (meth) acrylic ester resin fine particles having the desired hydrolyzable silyl group with a smaller amount of use. It is preferable from the point which can be performed.
  • a carboxyl group-containing prepolymer is synthesized by emulsion polymerization, and then the carboxyl group of this prepolymer, A method of reacting with an epoxy group in an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate to give a (meth) acryloyl group can be mentioned. At this time, a part of the carboxyl group of the prepolymer may remain. With this method, a high-performance macromonomer can be easily produced. In the case of using an epoxy group-containing (meth) acrylate, it is preferable to add 0.6 to 2.0 per polymer chain, whereby fine particles having a narrower particle size distribution and a uniform particle size can be produced. .
  • the polystyrene equivalent weight average molecular weight (Mw) of the macromonomer measured by gel permeation chromatography (GPC) is preferably 500 to 50,000, more preferably 1,000 to 10,000.
  • the macromonomer type dispersion stabilizer having a (meth) acryloyl group and a carboxyl group used for the production of resin fine particles having a hydrolyzable silyl group is preferably neutralized. This makes it possible to stably produce resin fine particles having hydrolyzable silyl groups due to the electrostatic repulsion effect of the neutralized carboxy anion.
  • the amount of alkali used for neutralization is preferably not more than twice the equivalent of the carboxyl group. If it exceeds 2 equivalents, the alkalinity of the reaction solution becomes strong, and a hydrolyzable silyl group may react during polymerization to cause aggregation.
  • Examples of the alkali for neutralization include ammonia and triethylamine. Among these, ammonia that can be easily removed is preferably used.
  • a known polymerization initiator used in dispersion polymerization can be used.
  • Specific examples include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butylperoxy-2-ethylhexanoate , Organic peroxides such as di-tert-butyl peroxide, di-tert-hexyl peroxide, di-tert-amyl peroxide, tert-butyl peroxypivalate; azobisisobutyronitrile, azobiscyclohexa Examples thereof include azo compounds such as carbonitrile and azobis (2,4-dimethylvaleronitrile); persulfate compounds such as potassium persulfate.
  • the hydrolyzable silyl groups in the (meth) acrylic acid ester resin fine particles having hydrolyzable silyl groups obtained above are subjected to a crosslinking reaction to produce crosslinked resin fine particles (Y).
  • the cross-linking reaction can be performed by adding a cross-linking catalyst to a dispersion containing (meth) acrylic ester resin fine particles having a hydrolyzable silyl group.
  • a hydrolyzable silyl group can be subjected to a condensation reaction to form a siloxane bond.
  • an alkaline material is preferable, and in particular, ammonia that can be easily removed after the crosslinking reaction or a low-boiling amine is preferably used.
  • the amount of the alkali material used is preferably 3 times equivalent or more and 6 times equivalent or more with respect to the silyl group in the resin fine particles having a hydrolyzable silyl group from the viewpoint of increasing the degree of silyl crosslinking. More preferred.
  • the method (ii) for carrying out the crosslinking reaction after obtaining the resin fine particles having hydrolyzable silyl groups by dispersion polymerization It is preferable because it can be produced simply and at low cost.
  • the light diffusable resin composition of this invention can contain an additive so that it may mention later.
  • the crosslinked resin fine particles (Y) may be particles containing an antioxidant, a light stabilizer and the like.
  • a light diffusing resin composition containing these additives is a preferable embodiment because it is particularly excellent in heat decomposition stability and weather resistance.
  • the antioxidant include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like. Of these, examples of phosphorus antioxidants include phosphite compounds.
  • phosphite compound examples include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tert-4- (3-tert- 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, trioctyl phosphite, tridecyl phosphite, trioctadecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, dioctyl mono Phenyl phosphite, diisopropyl monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, mono
  • phenolic antioxidant examples include n-octadecyl- ⁇ - (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, tetrakis [methylene-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl -5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert- Butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6) tert-butylphenol), 2,2'-methylenebis (4-ethyl
  • sulfur-based antioxidants examples include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. .
  • the said antioxidant can be used 1 type or in combination of 2 or more types.
  • Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, poly ⁇ [6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino] ⁇ , polymethylpropyl 3-oxy- [4- (2,2,6,6-tetra Methyl) piperi Sulfony
  • the volume average particle diameter (dv) of the crosslinked resin fine particles (Y) according to the present invention is 1.5 to 3.3 ⁇ m, preferably 1.8 to 2.8 ⁇ m, more preferably 2.1 to 2.5 ⁇ m. It is.
  • the volume average particle diameter (dv) is less than 1.5 ⁇ m, the ratio of diffuse light per particle decreases, so the ratio of regular transmitted light that does not diffuse increases, and the total light transmittance is high. This is not preferable because the diffusibility (dispersion degree) decreases.
  • the volume average particle diameter (dv) exceeds 3.3 ⁇ m, the number of particles at the same mass decreases, and the amount added to obtain the same total light transmittance increases, which is not preferable.
  • fine-particles (Y) are large, since diffused transmission light increases more straightness, it is not preferable.
  • the coefficient of variation (CV) is 20% or less, preferably 10% or less.
  • the degree of dispersion in the high transmittance region tends to decrease.
  • the coefficient of variation (CV) can be used as an index representing the spread of the particle size distribution. The smaller the coefficient of variation (CV), the narrower the particle size distribution. If it is 20% or less, it can be said that the distribution width is very narrow.
  • the coefficient of variation (CV) is 0, but about 2% is considered to be the lower limit as what is actually obtained.
  • volume average particle diameter (dv) and coefficient of variation (CV) of the crosslinked resin fine particles (Y) in the present specification are measured or measured using a laser diffraction scattering type particle size distribution meter and a scanning electron microscope, respectively. It is calculated and its detailed method is as described in the examples described later.
  • the temperature at which the mass becomes half that is, 50% by weight.
  • the temperature reduction (Td 50 ) is 320 ° C. or higher, preferably 350 ° C. or higher.
  • the upper limit temperature is 400 ° C. for general acrylic fine particles.
  • Td 50 can be measured, for example, using a thermogravimetric / differential thermal analyzer.
  • methacrylic polymers are known to have a higher decomposition rate when heated compared to other polymer materials, and the Td 50 of crosslinked resin fine particles consisting only of methacrylic monomers is low.
  • the copolymerization of acrylic monomer, styrene monomer, etc. by about several mass% reduces the decomposition rate at the time of heating, so that the value of Td 50 can be increased.
  • the light diffusing resin composition of the present invention includes the transparent resin (X) and the crosslinked resin fine particles (Y), and the refractive index of the transparent resin (X) and the refractive index of the crosslinked resin fine particles (Y)
  • the absolute value ( ⁇ n) of the difference is 0.095 to 0.115, preferably 0.100 to 0.110.
  • the amount of the light diffusing agent added is too small, it is not preferable because the regular transmitted light that does not hit the particles in the resin composition and is transmitted increases and the diffuse transmitted light decreases. In such a case, the degree of dispersion tends to decrease in a region where the total light transmittance is high. If ⁇ n exceeds 0.115, these problems may occur. On the other hand, when ⁇ n is less than 0.095, the ratio of the diffused light per particle is reduced, so that it is necessary to increase the amount of the light diffusing agent, which is not preferable.
  • the content ratio of the transparent resin (X) and the crosslinked resin fine particles (Y) in the light diffusing resin composition of the present invention is shown.
  • the content of the crosslinked resin fine particles (Y) is preferably 0.1 to 2.0 parts by mass, more preferably 0.3 to 1.5 parts by mass, and still more preferably 100 parts by mass of the transparent resin (X). Is 0.3 to 1.0 part by mass.
  • the content of the crosslinked resin fine particles (Y) exceeds 2.0 parts by mass, impact resistance and flame retardancy tend to be lowered.
  • it is less than 0.1 parts by mass the light diffusibility tends to be insufficient.
  • the light diffusing resin composition of the present invention may contain fine particles other than the crosslinked resin fine particles (Y) (hereinafter referred to as “other fine particles”) as necessary.
  • the light diffusibility can be finely adjusted by including other fine particles.
  • the other fine particles include cross-linked (meth) acrylate-based fine particles, cross-linked polystyrene-based fine particles, cross-linked polyorganosiloxane-based fine particles, and silica fine particles. These other fine particles may be used alone or in combination of two or more.
  • the light diffusing resin composition of the present invention can contain additives as long as the object of the present invention is not impaired.
  • additives include light stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, lubricants, flame retardants, colorants (dyes, pigments), fluorescent brighteners, selective wavelength absorbers, plasticizers, and the like. Can do.
  • the antioxidant and the light stabilizer the compounds described above that can be added to the crosslinked resin fine particles (Y) can be used.
  • the light diffusing resin composition of the present invention can be produced by melt-kneading a raw material containing transparent resin (X) and crosslinked resin fine particles (Y).
  • the production apparatus include a melt extruder, a kneader, a mill, and the like.
  • the temperature is equal to or higher than the melting temperature of the transparent resin (X) and lower than the thermal decomposition temperature of the transparent resin (X) and the crosslinked resin fine particles (Y). Melt and knead.
  • the whole amount of the transparent resin (X) and the whole amount of the crosslinked resin fine particles (Y) can be used. Further, a master batch having a high content ratio of the crosslinked resin fine particles (Y) is prepared in advance using a part of the transparent resin (X) and the total amount of the crosslinked resin fine particles (Y). The batch and the remaining transparent resin (X) may be kneaded.
  • the preferred light diffusibility of the light diffusing resin composition of the present invention is shown below.
  • the angle (hereinafter referred to as “dispersion degree (I)”) at which the emitted light has a luminance of 50% with respect to the emitted light at 0 degree is preferably 20 degrees or more, more preferably 23 degrees. That's it.
  • the light diffusing resin composition of the present invention is also suitable as a molding material for members such as displays and lighting fixtures.
  • the degree of dispersion is adjusted by balancing the difference in refractive index ( ⁇ n) between the transparent resin (X) and the crosslinked resin fine particles (Y), the particle diameter of the crosslinked resin fine particles (Y), the particle size distribution, and the amount added. Is done.
  • the angle (hereinafter referred to as “dispersion degree (II)”) at which the emitted light has a luminance of 50% with respect to the emitted light at 0 degree when the light is incident on the surface in the vertical direction using a goniometer is preferable. Is 22 degrees or more, more preferably 23 degrees or more. If the degree of dispersion (II) is 22 degrees or more, it is preferable because light diffusion is excellent.
  • a goniometer (variable photometer) was used to irradiate parallel light in the thickness direction perpendicular to one surface of a 1.5 mm thick sheet. It is obtained by measuring the light distribution of transmitted light on the other surface side.
  • B ⁇ I ⁇ / cos ⁇ (1)
  • the method for forming the sheet is not particularly limited, and can be obtained, for example, by subjecting the light diffusing resin composition to compression molding using a compression molding machine or the like. Moreover, since the value obtained by dispersion
  • a molded article can be produced by various molding methods conventionally employed for molding resin compositions such as polycarbonate resins.
  • the molding method for producing the molded body is appropriately selected according to the purpose of use and application, and is not particularly limited.
  • extrusion molding, injection molding, compression molding, extrusion blow molding, injection blow molding, flow Examples include melt molding such as rolling, calendar molding, and casting.
  • the molded body obtained by melt molding may be subjected to secondary molding processing such as bending, vacuum molding, blow molding, press molding, or the like, if necessary, to obtain a target molded body.
  • secondary molding processing such as bending, vacuum molding, blow molding, press molding, or the like, if necessary, to obtain a target molded body.
  • a processing method in which a lens shape and an embossed shape are formed on the surface of the molded body can be performed according to the purpose of use and application to adjust the optical characteristics.
  • the molded body comprising the light diffusing resin composition of the present invention can be effectively used for optical applications such as a light diffusing plate, a Fresnel lens, a lenticular lens, a lighting fixture, and an electric signboard in a liquid crystal display device.
  • the polymer is dissolved in tetrahydrofuran (THF) to prepare a 0.2% concentration solution, and 100 ⁇ L of the solution is injected into the column.
  • THF tetrahydrofuran
  • the eluent is THF
  • the column temperature is 40 ° C.
  • the eluent (THF) flow rate is 1. Measurement was performed at 0 mL / min.
  • volume average particle diameter (dv) Methanol was added to the slurry containing the crosslinked resin fine particles obtained in Production Examples 1 to 13 shown in Table 1 to adjust the concentration of the fine particles to 5%, and the mixture was sufficiently shaken and dispersed uniformly.
  • the dispersion was irradiated with ultrasonic waves for 10 minutes, and then particle size distribution measurement was performed using a laser diffraction scattering type particle size distribution analyzer “MT-3000” manufactured by Nikkiso Co., Ltd. Ion exchange water or acetone was used as a circulating dispersion medium at the time of measurement.
  • the crosslinked resin fine particles of the commercial products 1 to 3 were put into acetone so that the concentration of the dry powder was 5%, and were sufficiently shaken to be uniformly dispersed. This dispersion was irradiated with ultrasonic waves for 10 minutes, and then particle size distribution measurement was performed. The median diameter ( ⁇ m) was calculated from the volume-based particle size distribution obtained by the particle size distribution measurement, and was defined as the volume average particle size (dv).
  • the number average particle diameter (dn) for obtaining the coefficient of variation (CV) and the standard deviation ( ⁇ ) is the particle diameter (di) obtained by the SEM observation and the number of particles having the particle diameter (Ni). It was calculated from the following formula (4).
  • dn ( ⁇ Nidi / ⁇ Ni) (4)
  • homopolymers were synthesized by solution polymerization or photopolymerization, and measured with an Abbe refractometer “DR-M2” manufactured by Atago Co., Ltd., at a temperature of 25 ° C. and with a wavelength of 589 nm. .
  • Td 50 Thermal decomposition temperature
  • TG-DTA differential thermothermal gravimetric simultaneous measurement apparatus
  • Total light transmittance of molded body Using the light diffusable resin composition, a sheet having a thickness of 1.5 mm was prepared, and this was cut into an appropriate size to obtain a measurement sample. The total light transmittance (Tt) was measured using a Nippon Denshoku haze meter “Haze meter NDH2000” (model name).
  • Dispersion of molded product The same sheet as the total light transmittance was used as a measurement sample. As shown in FIG. 1, as a device including a light source 2, a variable angle photometer “GP-200” manufactured by Murakami Color Research Laboratory Co., Ltd. is used to irradiate a light beam perpendicularly to the surface of the sheet 1. The distribution of transmitted light (emitted light) was measured on the side to determine the degree of dispersion.
  • GP-200 manufactured by Murakami Color Research Laboratory Co., Ltd.
  • the angle ⁇ when the luminance of the light becomes 50 was calculated, and this ⁇ was defined as the degree of dispersion.
  • B ⁇ I ⁇ / cos ⁇ (6)
  • Synthesis Example 1 (Production of Macromonomer MM-1) 200 parts of ion-exchanged water was charged into a glass reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe, and a liquid feed pipe connecting part. Next, the water temperature in the reaction vessel was adjusted to 80 ° C. while stirring and introducing nitrogen gas.
  • MMA methyl methacrylate
  • IBMA isobutyl methacrylate
  • MAA methacrylic acid
  • OTG 2-ethylhexyl thioglycolate
  • the initiator aqueous solution dissolved in the part was added and stirred. Then, 5 minutes later, the supply of the monomer mixture was started from the glass container connected to the glass reaction container via the liquid feeding pipe connecting part using a metering pump. The monomer mixture was supplied at a constant rate over 240 minutes. After completing the supply of the monomer mixture, the temperature inside the reaction vessel was raised to 90 ° C. over 30 minutes. And it maintained at 90 degreeC for 4.5 hours, and obtained the dispersion liquid of the prepolymer. When a part of the dispersion was sampled and the prepolymer after removing the medium by drying was subjected to GPC measurement, Mn in terms of polystyrene was 2,700 and Mw was 4,600.
  • Synthesis Example 2 (Production of macromonomer MM-2) A 500 ml pressurized stirred tank reactor equipped with a hot oil heating device was filled with ethyl 3-ethoxypropionate. The reactor was then warmed to about 250 ° C. Meanwhile, 20 parts of MMA, 55 parts of cyclohexyl acrylate (hereinafter “CHA”), 25 parts of acrylic acid (hereinafter “AA”) and 0.1 part of di-tert-butyl peroxide (hereinafter “DTBP”) are mixed. Then, a monomer mixed solution was prepared and stored in a raw material tank.
  • CHA cyclohexyl acrylate
  • AA acrylic acid
  • DTBP di-tert-butyl peroxide
  • the monomer mixed solution is continuously supplied from the raw material tank to the reactor while keeping the pressure in the reactor constant by the pressure regulator above the vapor pressure of ethyl 3-ethoxypropionate. Polymerization was carried out at 0 ° C. At this time, the feed rate was set so that the average residence time of the monomer mixture in the reactor was 12 minutes. A reaction solution corresponding to the supply amount of the monomer mixture was continuously taken out from the outlet of the reactor. The temperature in the reactor was maintained at 230 ° C. ⁇ 2 ° C. while supplying the monomer mixture.
  • the reaction liquid taken out from the outlet of the reactor is introduced into a thin film evaporator to remove volatile components such as unreacted monomers in the reaction liquid, Monomer MM-2 was obtained.
  • the macromonomer MM-2 was collected for 60 minutes and then cooled to obtain a solid macromonomer MM-2.
  • Mn in terms of polystyrene was 3,100 and Mw was 10,600.
  • concentration of terminal ethylenically unsaturated bonds contained in the macromonomer MM-2 was measured by nuclear magnetic resonance spectrum (hereinafter referred to as 1 H-NMR).
  • the terminal ethylenically unsaturated bond introduction rate (hereinafter referred to as F value) of the macromonomer MM-2 calculated from the number average molecular weight and the concentration of the terminal ethylenically unsaturated bond was 98%.
  • 100 parts of pulverized solid macromonomer MM-2, 260 parts of water and 22.5 parts of 25% aqueous ammonia were charged into a glass flask with a condenser tube, and a warm bath was used. The internal temperature was 90 ° C. Then, stirring was performed to make the macromonomer MM-2 water-soluble. After confirming that the macromonomer MM-2 was dissolved, water was added so that the solid content was 25% to obtain an aqueous solution of the macromonomer MM-2.
  • crosslinked resin fine particles The crosslinked resin fine particles used in the production of the light diffusing resin composition are a synthetic product and a commercial product, and are shown below.
  • Production Example 1 (Production of crosslinked resin fine particles A1)
  • a glass reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas introduction pipe and a liquid feed pipe connection part 100.4 parts of ion exchange water, 475.6 parts of methanol, 0.12 part of 25% ammonia water
  • 5.86 parts of a dispersion containing the macromonomer MM-1 obtained in Synthesis Example 1 15.0 parts of MMA, 50.0 parts of IBMA, and 10.0 parts of 2-ethylhexyl acrylate (hereinafter “HA”) were charged. It is.
  • the internal temperature of the reaction vessel was adjusted to 55 ° C. while stirring and introducing nitrogen gas.
  • TMOS-PMA trimethoxysilylpropyl methacrylate
  • the internal temperature was maintained at 55 ° C., and after 6 hours, the polymerization was terminated to obtain a dispersion of polymer fine particles having hydrolyzable silyl groups.
  • 32.8 parts of 25% aqueous ammonia was added to the dispersion as a basic catalyst for crosslinking hydrolyzable silyl groups, the internal temperature was 62 ° C., and the mixture was held for 3 hours with stirring. As a result, fine particles having a crosslinked structure were formed.
  • 1.0 part of an antioxidant (trade name “Irganox 245” manufactured by BASF Corporation) was added.
  • Production Examples 2 to 6 and 9 to 13 (Production of crosslinked resin fine particles A2 to A6 and A9 and B1 to B4) The same procedure as in Production Example 1 was carried out except that the types and amounts of monomers used in the presence of the macromonomer, and the amounts of ion-exchanged water and methanol used were changed as shown in Table 1. Fine particles A2 to A6, A9 and B1 to B4 were obtained. Table 1 shows the physical properties of the obtained crosslinked resin fine particles.
  • Production Example 7 (Production of crosslinked resin fine particles A7)
  • the types and amounts of monomers used in the presence of the macromonomer, and the amounts of ion-exchanged water and methanol used are as shown in Table 1, and 9/10 of the monomers used are initially charged, and the rest was added in 10 minutes after adding the polymerization initiator, and the same operation as in Production Example 1 was performed to obtain crosslinked resin fine particles A7.
  • the physical properties of the obtained A7 are shown in Table 1.
  • crosslinked resin fine particles A8 were obtained by preparing seed particles SD-1 made of resin fine particles and then polymerizing a vinyl monomer containing a crosslinkable monomer in the presence of the seed particles SD-1. Fine particles.
  • the obtained dispersion of seed particles SD-1 was subjected to centrifugal separation, and the supernatant was removed.
  • the volume average particle diameter (dv) of the collected fine particles was measured with a laser diffraction / scattering particle size distribution analyzer. .65 ⁇ m.
  • an emulsifier aqueous solution in which 1.5 parts of sodium lauryl sulfate as an emulsifier (trade name “Emar 2F-30”) as an emulsifier is dissolved in 100 parts of ion-exchanged water is added to the obtained mixture, followed by emulsification.
  • the mixture was emulsified using a vessel to prepare an emulsion of vinyl monomer.
  • the vinyl monomer emulsion prepared above is added to the reaction vessel containing the seed particles SD-1, and 2,2′-azobis (2,4-dimethylvalero) as a polymerization initiator is further added.
  • Nitrile (trade name “V-65”, manufactured by Wako Pure Chemical Industries, Ltd.) 1 part was added, and the mixture was stirred at 20 ° C. for 12 hours to allow the seed monomer SD-1 to absorb the vinyl monomer and the polymerization initiator. . Thereafter, nitrogen gas was introduced into the gas phase portion in the reaction vessel through a nitrogen gas introduction pipe. And the vinyl monomer absorbed by the seed particle was polymerized by heating up internal temperature over 2 hours from 20 degreeC to 70 degreeC. After reaching 70 ° C., the mixture was further stirred for 2 hours while maintaining the temperature at 70 ° C.
  • B5 Cross-linked polymethyl methacrylate fine particles “GM-0105” (trade name) manufactured by Ganz Kasei Co., Ltd.
  • B6 Cross-linked polymethyl methacrylate fine particles “GM-0401S” (trade name) manufactured by Ganz Kasei Co., Ltd.
  • B7 Silicone resin fine particle “Tospearl 120” (trade name) manufactured by Momentive Performance Materials.
  • MMA Methyl methacrylate (refractive index 1.4900)
  • IBMA Isobutyl methacrylate (refractive index: 1.4770)
  • IBA Isobutyl acrylate (refractive index 1.4608)
  • HA 2-ethylhexyl acrylate (refractive index: 1.4625)
  • TMOS-PMA Trimethoxysilylpropyl methacrylate (refractive index 1.4800)
  • TMPTA Trimethylolpropane triacrylate (refractive index 1.5135)
  • St Styrene (refractive index 1.5900)
  • Example 1 Production of Light Diffusing Resin Composition and Its Molded Product
  • a composition containing a polycarbonate resin (trade name “Iupilon S-3000F”, refractive index 1.585) manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and a crosslinked resin fine particle A1 are carried out. It was. After mixing 0.3 g of the crosslinked resin fine particles A1, 59.64 g of the polycarbonate resin, and 0.06 g of an antioxidant (trade name “Irganox B225” manufactured by BASF Corp.), Laboplast mill (manufactured by Toyo Seiki Co., Ltd., LABO PLASTOMILL) was melt-kneaded for 9 minutes at 250 ° C.
  • a polycarbonate resin trade name “Iupilon S-3000F”, refractive index 1.585
  • an antioxidant trade name “Irganox B225” manufactured by BASF Corp.
  • Laboplast mill manufactured by Toyo Seiki Co., Ltd., LABO PLASTOMILL
  • the light diffusing resin composition was compression-molded at 4 MPa with a compression molding machine (“SFA-37” manufactured by Shinto Metal Industries Co., Ltd.) using a mold having a cavity having a predetermined shape and size.
  • a flat plate molded product 120 mm long ⁇ 120 mm wide ⁇ 1.5 mm thick was produced. Thereafter, the thickness of the flat plate was measured using a micrometer and confirmed to be in the range of 1.50 mm ⁇ 0.05 mm.
  • the light-diffusing resin composition was prepared in the same manner as described above except that the blending amounts of the crosslinked resin fine particles A1 and the polycarbonate resin were changed as shown in (1), (2) or (4) of Table 2. And a flat plate molded article was manufactured. About each molded article obtained by the above, total light transmittance and dispersion degree were measured. The results are shown in Table 2. The absolute value ⁇ n of the refractive index difference between the transparent resin and the crosslinked resin fine particles is also shown.
  • Example 2 Example 1 except that a GP polystyrene resin (manufactured by Dongbu Chemicals, trade name “SOLARENE GPPS G-116HV”, refractive index 1.590) was used instead of the polycarbonate resin, and the kneading temperature was 200 ° C.
  • the light diffusing resin composition and the flat plate molded product were obtained. Separately, two types of compositions in which the content ratios of the polystyrene resin and the crosslinked resin fine particles A1 were changed were produced. About each obtained molded article, the total light transmittance and dispersion degree were measured. The results are shown in Table 2.
  • Examples 3 to 10 A light diffusing resin composition and a flat molded article were obtained in the same manner as in Example 1 using the polycarbonate resin and the crosslinked resin fine particles A2 to A9 with the formulation shown in Table 2. About each obtained molded article, the total light transmittance and dispersion degree were measured. The results are shown in Table 2.
  • Comparative Examples 1-7 A light diffusing resin composition and a flat molded product were obtained in the same manner as in Example 1 using the polycarbonate resin and the crosslinked resin fine particles B1 to B7 with the formulation shown in Table 3. About each obtained molded article, the total light transmittance and dispersion degree were measured. The results are shown in Table 3.
  • the addition amount of the crosslinked resin fine particles (light diffusing agent) necessary for obtaining a degree of dispersion (light diffusibility) of about 20 degrees is as small as 0.5% or less.
  • a result showing good diffusion efficiency was obtained.
  • it can be confirmed that good diffusibility is exhibited in a wide total light transmittance region of approximately 60 to 90% within a range of the addition amount of the crosslinked resin fine particles up to 2.0%. It was. Focusing on the average volume particle diameter (dv), in Examples 1 to 9 using crosslinked resin fine particles having a dv of 1.8 ⁇ m or more, the degree of dispersion at a total light transmittance of about 85% is 20 degrees or more.
  • Comparative Example 1 in which the refractive index difference ⁇ n between the transparent resin and the crosslinked resin fine particles is small, Comparative Example 3 in which the volume average particle size (dv) of the crosslinked resin fine particles is large, Comparative Example 5 in which the particle size distribution is wide, and Large particle size
  • the dispersion degree is less than 20 degrees when the addition amount of the crosslinked resin fine particles (light diffusing agent) is 0.5%, and the diffusion efficiency is inferior. there were. Further, from the result of Comparative Example 1, it is estimated that the region exhibiting diffusibility with a degree of dispersion of 20 degrees or more is about 70 to 90% or so in the range of the addition amount of the crosslinked resin fine particles up to 2.0%.
  • Example 1 the total light transmittance region showing good diffusibility compared with Example 1 was narrow.
  • Comparative Example 2 in which the volume average particle diameter (dv) of the crosslinked resin fine particles is small and in Comparative Example 7 in which the silicone-based crosslinked resin fine particles are used, the dispersion in a high total light transmittance region having a total light transmittance of about 85%. It has been found that the total light transmittance region that can be applied is limited.
  • Comparative Example 4 in which the monomer components constituting the crosslinkable fine particles are all methacrylic acid ester monomers has a high thermal decomposition rate, and when the crosslinked resin fine particles are used for a light diffusion plate or the like, The result of concern about heat resistance was obtained.
  • the present invention it is possible to obtain a light diffusing resin composition having good light diffusibility and showing a high degree of dispersion in a wide range of total light transmittance. Moreover, the molded object excellent also in heat resistance etc. can be obtained. For this reason, the light diffusing resin composition of the present invention is used for applications such as light diffusing plates, transmissive screens, liquid crystal panels, and electric signboards for displays that require sufficient luminance and light diffusibility, and a wide range of total light transmission. It is useful for applications such as a cover of a lighting fixture that requires light diffusibility in the rate region.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154828A (ja) * 2017-03-17 2018-10-04 三菱ケミカル株式会社 （メタ）アクリル樹脂組成物、樹脂成形体、照明灯カバー及び照明看板
JP7194610B2 (ja) 2019-02-13 2022-12-22 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物成形体

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6728334B2 (ja) * 2016-03-22 2020-07-22 積水化成品工業株式会社 中空粒子及びその用途
CN107266807B (zh) * 2017-06-07 2019-04-30 潮州明园新材料有限公司 一种光扩散材料
CN108803126B (zh) * 2018-06-29 2021-01-15 京东方科技集团股份有限公司 显示面板及其制造方法、显示装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002258274A (ja) * 2001-03-02 2002-09-11 Toppan Printing Co Ltd 光散乱膜、液晶表示装置用電極基板、及び液晶表示装置
JP2004252384A (ja) * 2003-02-21 2004-09-09 Mitsui Chemicals Inc 反射シート
JP2006169542A (ja) * 2006-03-10 2006-06-29 Jsr Corp 光拡散用成形品
JP2009175375A (ja) * 2008-01-24 2009-08-06 Nippon Shokubai Co Ltd 防眩性積層体
JP2010066761A (ja) * 2008-08-13 2010-03-25 Sony Corp 光学フィルムおよびその製造方法、防眩性フィルム、光学層付偏光子、ならびに表示装置
JP2010079101A (ja) * 2008-09-26 2010-04-08 Fujifilm Corp 光学フィルム、偏光板、及び画像表示装置
JP2010209351A (ja) * 2010-05-26 2010-09-24 Toyo Ink Mfg Co Ltd 光散乱膜用組成物の製造方法、およびそれを用いた光散乱膜
JP2010237623A (ja) * 2009-03-31 2010-10-21 Fujifilm Corp 反射防止フィルム、偏光板、画像表示装置
JP2011209658A (ja) * 2010-03-30 2011-10-20 Fujifilm Corp Ｌｅｄ照明用光拡散フィルム

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7022764B2 (en) * 2002-12-18 2006-04-04 General Electric Company Static dissipating resin composition and methods for manufacture thereof
JP4578091B2 (ja) * 2003-12-16 2010-11-10 東洋インキ製造株式会社 反射型液晶表示装置を構成する光硬化型光散乱膜用組成物、およびそれを用いた光散乱膜
KR100813738B1 (ko) * 2005-08-31 2008-03-13 주식회사 새 한 내스크래치성과 광학특성이 우수한 광확산판 제조방법
JP5057793B2 (ja) * 2007-01-30 2012-10-24 積水化成品工業株式会社 光拡散性粒子含有成形体
WO2010024167A1 (ja) * 2008-08-26 2010-03-04 東亞合成株式会社 スチレン系樹脂組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002258274A (ja) * 2001-03-02 2002-09-11 Toppan Printing Co Ltd 光散乱膜、液晶表示装置用電極基板、及び液晶表示装置
JP2004252384A (ja) * 2003-02-21 2004-09-09 Mitsui Chemicals Inc 反射シート
JP2006169542A (ja) * 2006-03-10 2006-06-29 Jsr Corp 光拡散用成形品
JP2009175375A (ja) * 2008-01-24 2009-08-06 Nippon Shokubai Co Ltd 防眩性積層体
JP2010066761A (ja) * 2008-08-13 2010-03-25 Sony Corp 光学フィルムおよびその製造方法、防眩性フィルム、光学層付偏光子、ならびに表示装置
JP2010079101A (ja) * 2008-09-26 2010-04-08 Fujifilm Corp 光学フィルム、偏光板、及び画像表示装置
JP2010237623A (ja) * 2009-03-31 2010-10-21 Fujifilm Corp 反射防止フィルム、偏光板、画像表示装置
JP2011209658A (ja) * 2010-03-30 2011-10-20 Fujifilm Corp Ｌｅｄ照明用光拡散フィルム
JP2010209351A (ja) * 2010-05-26 2010-09-24 Toyo Ink Mfg Co Ltd 光散乱膜用組成物の製造方法、およびそれを用いた光散乱膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018154828A (ja) * 2017-03-17 2018-10-04 三菱ケミカル株式会社 （メタ）アクリル樹脂組成物、樹脂成形体、照明灯カバー及び照明看板
JP7194610B2 (ja) 2019-02-13 2022-12-22 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物成形体

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