WO2003064526A1 - Composition de resine diffusant la lumiere - Google Patents

Composition de resine diffusant la lumiere Download PDF

Info

Publication number
WO2003064526A1
WO2003064526A1 PCT/JP2003/000799 JP0300799W WO03064526A1 WO 2003064526 A1 WO2003064526 A1 WO 2003064526A1 JP 0300799 W JP0300799 W JP 0300799W WO 03064526 A1 WO03064526 A1 WO 03064526A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
resin composition
block copolymer
weight
diffusing
Prior art date
Application number
PCT/JP2003/000799
Other languages
English (en)
Japanese (ja)
Inventor
Teiji Kohara
Original Assignee
Zeon Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corporation filed Critical Zeon Corporation
Publication of WO2003064526A1 publication Critical patent/WO2003064526A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a light-diffusing resin composition having excellent light-transmitting, light-diffusing properties and moldability, and a light-diffusing molded article made of the light-diffusing resin composition.
  • the light diffusion molded body is a molded body that diffuses incident light and emits the light.
  • This light-diffusing molded article is used when it is desired to uniformly irradiate the whole, but it is difficult to irradiate the whole due to the positional relationship with the light source.
  • the plate-shaped molded body is installed between the light source and the back of the display, so that light from the pack-light source in the immediate vicinity of the liquid crystal is uniformly emitted from the display surface, and Light and dark are not generated on the spray.
  • Such a light-diffusing molded article has a high ratio of outgoing light to incident light, that is, the total light transmittance, which is the sum of parallel light transmittance and diffuse light transmittance, in order to effectively use the light of the light source.
  • the total light transmittance which is the sum of parallel light transmittance and diffuse light transmittance, in order to effectively use the light of the light source.
  • a molded article in which particles are dispersed in a transparent resin matrix is known (for example, Japanese Patent Application Laid-Open No. Hei 5-218408 / Japanese Patent Application Laid-Open No. Hei 6-178781). Gazettes).
  • this molded article when the number of particles to be dispersed is increased, the light diffusion property is improved, but the light transmittance is reduced. Conversely, when the number of particles is reduced, the light transmittance improves, but the light diffusivity decreases. Light transmission and light diffusion have an inverse correlation. Therefore, depending on the application, either light transmittance or light diffusivity may be insufficient, and there has been a demand for a light diffusing molded body having both high light transmittance and high light diffusion ⁇ fe.
  • the light diffusing plate made of this composition has practically sufficient characteristics, the light stability and dimensional accuracy may be slightly insufficient depending on the selection of molding conditions. is there.
  • a transparent resin a resin in which an aromatic ring portion of polystyrene is added to hydrogen, or a light diffusing resin using a resin containing an alicyclic structure-containing ethylenically unsaturated monomer unit Compositions have been proposed (for example, Japanese Patent Application Laid-Open No. 2001-131419, Japanese Patent Application Laid-Open No. 2001-210613).
  • An object of the present invention is to provide a water-soluble resin composition and a light-diffusing molded article formed by using the resin composition.
  • a block copolymer having a specific structure obtained by hydrogenating a block copolymer of an aromatic vinyl compound having a specific block composition and a conjugated gen to an aromatic ring is obtained.
  • the gate is formed by injection molding a light diffusing plate using a light diffusing resin composition having a specific modulus of elasticity equal to or higher than a specific value, in which a transparent organic filler 7 and an inorganic filler are dispersed.
  • the inventors have found that even when the thickness is reduced, no crack is generated even when the mold is released, and the mechanical strength is improved so that no crack or the like is generated even during the cutting process, and the present invention has been completed.
  • a light-diffusing resin composition comprising an alicyclic structure-containing block copolymer and a filler
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • R 2 — R 12 represent R 2 , R 3 , R 4 , R 5 , R s , R 7 , R 7 8 , R 9 , R xo , R 11 and R 12 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group the expressed. even R 2 one R 12 is each the same or different.
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • two polymer blocks [A] are bonded to both ends of one polymer block [B] ([A]-[B]).
  • — [A]) is a type of triplock copolymer.
  • the block copolymer having an alicyclic structure has a weight-average molecular weight (Mw) of 20,000 to 400,000, and the weight-average molecular weight (Mw) is a gel permeate using tetrahydrofuran as a solvent. Chillon. Chromatography (GP)
  • the block copolymer having an alicyclic structure has a weight average molecular weight (Mw) and a number average molecular weight ( ⁇ ) ratio (Mw / Mn) of 3 or less, and the weight average molecular weight (Mw / Mn).
  • Mw) and number average molecular weight (Mn) are the values in terms of polystyrene measured by gel 'permeation' chromatography (GPC) using tetrahydrofuran as a solvent.
  • the alicyclic structure-containing block copolymer is obtained by living anion polymerization.
  • the filler has an average particle size of 1 ⁇ m or more and 30 ⁇ m or less.
  • the filler is an organic filler composed of a polymer or a crosslinked product of the polymer.
  • the organic filler has a total light transmittance of 70% or more, and the total light transmittance is a value when a plate-like molded body having a thickness of 1 mm is formed.
  • the refractive index of the alicyclic structure-containing block copolymer is ⁇ 1 and the refractive index of the organic filler is ⁇ 2
  • the organic filler is a fine particle made of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof.
  • the filler is at least one inorganic filler selected from the group consisting of talc, silicon oxide, alumina and silica alumina.
  • a light diffusing molded article obtained by molding any of the light diffusing resin compositions described above.
  • the light diffusing molded article according to the present invention is a light diffusing plate.
  • the light diffusing resin composition according to the present invention has an alicyclic structure-containing block copolymer and a filler.
  • the alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A] containing 90% by weight or more of a repeating unit [1] represented by the following formula (1), and a polymer block [A] represented by the following formula (2). And a polymer block [B] containing a total of 30% by weight or more of the repeating unit [2] and Z represented by the formula (3) or the repeating unit [3] represented by the following formula (3).
  • the repeating unit [1] contained in the polymer block [A] is represented by the following formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 2 — R 12 represents R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , each of which is independently a hydrogen atom Represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group.
  • R 2 —R 12 may be the same or different.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 to R 12 are all hydrogen atoms.
  • the repeating unit [2] contained in the polymer block [B] is represented by the following formula (2).
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 120 carbon atoms, a halogen group or an aryl group.
  • a preferred structure of the repeating unit [2] represented by the formula (2) is that in which R 13 and R 14 are a hydrogen atom or a methyl group.
  • the repeating unit [3] contained in the polymer block [B] is represented by the following formula (3).
  • R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • R 15 is a hydrogen atom and R 16 is an ethyl group or an isopropyl group.
  • Polymer block [A] repeat units in [1], the weight fraction of total alicyclic structure-containing Proc co polymer (weight%) is taken as w 1AT, the ⁇ is better good It is preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 70% by weight. w When 1AT is in the above range, the heat resistance of the molded body is improved.
  • the remainder other than the repeating unit [1] in the polymer block [A] may be the one obtained by hydrogenating a carbon-carbon unsaturated bond of a repeating unit derived from a chain conjugated gen or a chain bull compound. preferable.
  • the weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire polymer block [B] is w 2BB
  • the repeating unit [3] in the polymer block [B] is the weight fraction of total polymer block [B] (weight 0/0)
  • the total amount (W2BB + W3BB) with W2BB C W3BB is 3
  • the weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire alicyclic structure-containing block copolymer is defined as w 2BT, and the repeating unit in the polymer block [B] is [ 2 ].
  • the weight fraction (weight 0 / ⁇ ) of the alicyclic structure-containing block copolymer in [3] is W3BT
  • the total amount (w 2B T + W 3B ⁇ ) of W 2BT and W 3BT is It is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. If the total amount (W2BT + W3BT) is too small, the flexibility of the resin molded article may be low and brittle, and if too large, the heat resistance may be reduced.
  • the polymer block [B] may contain the above-mentioned repeating unit [1].
  • 1 BT is preferably 30 weight. / 0 or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less.
  • the higher the w1BT the higher the transparency of the resin molded body. However, if the w1BT exceeds the above range, the resin may become brittle and have poor mechanical strength.
  • the polymer block [A] and the polymer block [B] may further contain a repeating unit [X] represented by the following formula (4).
  • R 17 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 18 represents a nitrile group, an alkoxycarbyl group, a hydrocarbyl group, a hydroxycarbyl group, or a halogen group.
  • R 19 is a hydrogen atom. R 18 and R 19 may form an acid anhydride group or an imido group.
  • the weight fraction of the repeating unit [X] in the total block copolymer containing an alicyclic structure is preferred.
  • the w XT preferably 2 0 wt% or less, preferably Ri yo 1 0 wt. / 0 or less.
  • the alicyclic structure-containing block copolymer used in the present invention has a weight fraction of WA of all the repeating units constituting the polymer block [A], and a weight fraction of all the repeating units constituting the polymer block [B].
  • the ratio (WA: WB) is preferably 10:90 to 95: 5.
  • the ratio (WA: WB) is more preferably 50:50 to 90:10, and particularly preferably. 60: 40 to 85: 15.
  • T, WXT, WA, and WB are values calculated as follows.
  • the amount of each monomer in the reaction solution is quantified by gas chromatography analysis.
  • W 1 AT, W XAA, ( 2BT + W 3BT),, W 2BB + W 3BB), W 1BT, WXT N WA, WB is calculated.
  • W 2BT and W SBT are calculated from the ratio of vinyl groups to vinylene groups by iH-NMR analysis of the block copolymer before hydrogenation.
  • the alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A]
  • [A]-[B]) type triblock copolymer a block copolymer in which a total of four or more polymer blocks [A] and polymer blocks [B] are alternately connected may be used.
  • ([A]-[B]-[A]) type triplock copolymers are preferred from the viewpoints of flexibility, mechanical strength, and productivity.
  • Each polymer block may have the same or different molecular length. However, in order to increase the elastic modulus of the molded article of the light-diffusing resin composition of the present invention, at least two A blocks (A 1 block, It is preferable that the ratio of the molecular length be different between the A2 blocks).
  • the ratio A 1 / A 2 of the molecular length of the block is preferably 1.5 to 8, more preferably 1.7 to 7, and particularly preferably 2 to 6.
  • the molecular length of each polymer block is a value calculated by measuring the molecular weight before and after polymerizing each polymer block by gel permeation 'chromatography analysis and calculating the molecular weight increase.
  • the molecular weight of the block copolymer containing an alicyclic structure used in the present invention is determined by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by (GPC) is preferably 20,000 to 400,000, more preferably 30,000 to 300,000, and particularly preferably 40,000 to 200,000. 000 range. If the Mw of the block copolymer containing an alicyclic structure is excessively small, the mechanical strength and heat resistance of the molded article may decrease.On the other hand, if the copolymer is excessively large, the productivity in the resin production stage and the resin addition may be reduced. There is a possibility that the moldability and the like may be reduced.
  • the molecular weight distribution of the block copolymer having an alicyclic structure can be appropriately selected depending on the purpose of use.
  • the ratio Mw between the polystyrene-converted Mw and the number average molecular weight ( ⁇ ) measured by genole permeation 'chromatography is described.
  • / Mn is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. preferable.
  • Mw / Mn is in the above range, the molded article is excellent in mechanical strength, heat resistance, and the like.
  • the block copolymer having an alicyclic structure used in the present invention can be produced, for example, as follows.
  • the unsaturated bond is hydrogenated step (3) And characterized in that:
  • Step (1) is a step of polymerizing the monomer mixture (a) to obtain a polymer block [A].
  • step (2) the monomer mixture (b) is polymerized to form a polymer block.
  • the monomer mixture (b) may contain at least one of an aromatic butyl compound, a bulcycloalkene, and a butylcycloalkene at a total amount of 70% by weight or less.
  • the production method of the present invention will be described more specifically by taking, as an example, a method for obtaining the most preferred triplock copolymer of the present invention. Since there are two steps of polymerizing the monomer mixture (a), the monomer mixture (a) used in each step is referred to as a monomer mixture ( ai ) and a monomer mixture (a 2 ).
  • the monomer mixture ( ai ) is polymerized to obtain a polymer block [A].
  • the monomer mixture (b) is polymerized in an organic solvent solution of the polymer.
  • a diblock copolymer composed of the polymer block [Ai] and the polymer block [B] is obtained.
  • a monomer mixture (a 2 ) is polymerized at the terminal on the polymer block [B] side, and a polymer block is attached to both terminals of the polymer block [B].
  • [A] is obtained one by one to obtain a triploc copolymer.
  • the block copolymer obtained as described above has an unsaturated bond (including one in an aromatic ring)
  • the unsaturated portion is saturated by a hydrogenation reaction, so that the present invention is the most preferable.
  • An alicyclic structure-containing block copolymer is obtained.
  • aromatic vinyl compound examples include styrene, ct-methinolestyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methynolestyrene, 2,4-diisopropynolestyrene, and 2,4-dimethino Examples thereof include styrene, 4-t-butynolestyrene, 5-t-butynole-2-methynolestyrene, 4-monochlorostyrene, dichlorostyrene, 4-monophenololerostyrene, and 4-phenylstyrene.
  • Examples of the bulcycloaken include 4-bulcyclohexene, 4-isopropininolecyclohexene, 1-methinole 4-vinylinolecyclohexene, 2-methinole 4-bienoresic mouth hexene, and 1-methinole 4-isopropeninolecin hexene.
  • 2-methinolay 4-isopropininolecyclohexene, 3-vinylinolecyclopentene, 4-bi-cyclopentene, 5-vinylinolecyclo [2.2.1] hept-2-ene, and the like.
  • bulcycloalkane examples include biercyclobutane, bursik pentane, vininolesik hexane, 2-vininolevisic mouth [2.2.1] heptane, isopropininolecyclohexane, 3-methinolebininolecyclohexane, Examples thereof include 4-methylvinylcyclohexane, 3-methylisopropenylcyclohexane, and 4-methylisopropenylvinylsiloxane.
  • These compounds may have a substituent such as a halogen group, an alkoxy group and a hydroxy group. These compounds may be used alone or in combination of two or more.
  • the use of the aromatic vinyl conjugate increases the polymerization yield. Furthermore, among these, styrene, high-methyl styrene, 2-methynolestyrene, 3- More preferably, one or more aromatic butyl compounds of methylstyrene and 4-methylstyrene are used.
  • linear biel compound examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1_heptene, 1-otaten, 1-nonene, 1_decene, 1-dodecene, 1- Examples include chain-like olefins such as eicosene, 4-methylino-11-pentene, and 4,6-dimethyl-11-heptene. Among them, ethylene and propylene are preferred.
  • chain conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among them, 1,3-butadiene and isoprene are preferred.
  • the monomer mixture (a) and the monomer mixture (b) may contain a butyl compound other than the above.
  • vinyl compounds include, for example, nitrile monomers such as acrylonitrile, methacrylonitrile, 1-cyano-1-chloroethylene; 2-methoxycarbyl-1-propene, 2-ethoxycarboloop-loop pen, 2-Propoxy lipoloop loop pen, 2-butoxycarboloop loop pen, 1-methoxycarbonylethylene, 1-ethoxycarboninoleethylene, 1-propoxycanolepounethylene, 1-butoxycanoleponinoleethylene (Meth) acrylate monomers such as 1-carboxyethylene, 1-carboxy-1-methylethylene, unsaturated fatty acid-based monomers such as maleic anhydride; 1-hydrocanoleponinoleethylene, 2-hydrocanolepo 2-propene, 1-methylcarbonylethylene, 2-methylca Boyuru one propene, N- Fueniruma Ray Mi de
  • any of radical polymerization, ion polymerization, cationic polymerization, coordination anion polymerization, coordination cation polymerization and the like may be used.
  • a method in which radical polymerization, anion polymerization, force polymerization, or the like is performed by living polymerization is preferable, and living polymerization is more preferably used.
  • living anion polymerization the hydrogenation reaction in the polymerization operation and the subsequent steps is facilitated, and the transparency of the obtained alicyclic structure-containing block copolymer is improved.
  • the polymerization temperature is usually 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C, particularly preferably 20 ° C to 80 ° C in the presence of a polymerization initiator.
  • a polymerization initiator for example, monoorganic lithium such as n-butylinolelithium, sec-butyllithium, t_butyllithium, hexyllithium, phenyllithium; dilithiomethane, 1,4-dilithiobutane, Polyfunctional organic lithium compounds such as 1,4-diethyl-2-ethylsilyl hexane can be used.
  • the type of polymerization reaction may be any of solution polymerization, slurry polymerization and the like, but the use of solution polymerization makes it easy to remove the heat of reaction. In this case, an inert solvent in which the polymer obtained in each step is dissolved is used.
  • inert solvent examples include aliphatic hydrocarbons such as n_butane, n-pentane, isopentane, n-hexane, ⁇ -heptane, and isootatan; cyclopentane, cyclohexane, methylcyclopentane, hexane Mechirushiku port, decalin, bicyclo [4 3 0..] nonane, preparative Rishikuro [4 3 0 I 2 '5...] alicyclic hydrocarbons such as decane, benzene, aromatic such torr E down Hydrocarbons and the like.
  • aliphatic hydrocarbons such as n_butane, n-pentane, isopentane, n-hexane, ⁇ -heptane, and isootatan
  • cyclopentane, cyclohexane, methylcyclopentane, hexane Mechirushiku port decalin
  • alicyclic hydrocarbons are preferable because it can be used as it is as an inert solvent also in the hydrogenation reaction described below and the solubility of the block copolymer is good.
  • Each of these solvents may be used alone, or two or more of them may be used in combination.
  • the amount of these solvents to be used is usually 200 to 2000 parts by weight based on 100 parts by weight of the total monomers used.
  • a randomizer or the like can be used to prevent a chain of one component from becoming long.
  • a Lewis base compound or the like it is preferable to use a Lewis base compound or the like as a randomizer.
  • Lewis base compounds include, for example, dimethinooleatenole, getinoleatenole, diisopropinoleatel, dibutinoleatel, tetrahydrofuran, dipheninoleatenole, ethyleneglycoreleetenole, ethyleneglycoreleatenole, ethyleneglycorelemethino Ethenolay conjugates, such as refenoleatenole; tertiary amine compounds such as tetramethinoleethylenediamine, trimethy ⁇ amine, triethylamine, pyridine, etc .; tertiary amine compounds, tertiary amine compounds; Alkali metal alkoxide compounds such as luoxide; phosphine compounds such as triphenylphosphine; and the like.
  • the molecular weight of the block copolymer obtained by the polymerization reaction according to the above method is preferably 20,000 to 400,000, more preferably 30,000, as Mw in terms of polystyrene measured by GPC using THF as a solvent. To 300,000, particularly preferably in the range of 40,000 to 200,000. Further, the molecular weight distribution MwZ ⁇ is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
  • the block copolymer obtained by the above polymerization method when an unsaturated bond (including an aromatic ring portion) is present therein, is obtained by hydrogenating the unsaturated bond.
  • the alicyclic structure-containing block copolymer of the present invention can be obtained.
  • the method of hydrogenating the unsaturated bond, the reaction form, and the like are not particularly limited, and may be performed according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and causes less polymer chain scission reaction is preferable. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, any of a heterogeneous catalyst and a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.
  • the heterogeneous catalyst can be used as it is, as a metal or a metal compound, or supported on a suitable carrier.
  • the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like.
  • the amount of the supported catalyst is usually in the range of 0.1 to 60% by weight, preferably 1 to 50% by weight, based on the total amount of the catalyst and the carrier.
  • Examples of the supported catalyst include a specific surface area of 100 to 500 m 2 Zg and an average pore diameter of 100. Those having ⁇ 100 A, preferably 200-500 OA are preferred.
  • the value of the specific surface area is a value calculated by measuring the amount of adsorbed nitrogen and using the BET equation, and the value of the average pore diameter is a value measured by a mercury intrusion method.
  • the homogeneous catalyst examples include a catalyst obtained by combining a nickel, cobalt, titanium or iron compound with an organometallic compound (eg, an organoaluminum compound, an organolithium compound); transition metals such as rhodium, palladium, platinum, ruthenium, and rhenium; A complex catalyst or the like can be used.
  • an organometallic compound eg, an organoaluminum compound, an organolithium compound
  • transition metals such as rhodium, palladium, platinum, ruthenium, and rhenium
  • a complex catalyst or the like can be used.
  • the nickel, cobalt, titanium or iron compound for example, acetyl acetonato compounds of various metals, carboxylate salts, cyclopentagenenyl compounds and the like are used.
  • organic aluminum compound examples include alkyl phenols such as triethylaluminum and triisobutylaluminum; aluminum halides such as getylaluminum chloride and ethylaluminum dichloride; and hydrogenation such as disobutylaluminum hydride. Alkyl aluminum and the like.
  • organometallic complex catalyst examples include dihydrido-tetrakis (triphenyl norephosphine) norethenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentagenenyl) And transition metal complexes such as Huckel.
  • Each of these hydrogenation catalysts may be used alone, or two or more of them may be used in combination.
  • the amount of the hydrogenation catalyst to be used is usually from 0.01 to: L00 parts by weight, preferably from 0.05 to 50 parts by weight, more preferably from 0 to 100 parts by weight of the polymer. : 30 to 30 parts by weight.
  • the hydrogenation reaction temperature is usually from 10 ° C to 250 ° C, preferably from 50 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C. Conversion increases and molecular cleavage decreases.
  • the hydrogen pressure is usually 0.1 MPa to 30 MPa, preferably 1 MPa to 20 MPa, more preferably 2 MPa to 1 OMPa, the hydrogenation rate increases and the molecular chain breaks. And the operability is excellent.
  • the hydrogenation rate of the block copolymer containing an alicyclic structure can be measured by iH-NMR using carbon-carbon unsaturated bonds in the main chain and side chains, and carbon-carbon unsaturated carbon in the aromatic ring and cycloalkene ring. All of the bonds are preferably 90% or more, more preferably 97% More preferably, it is set to 99% or more.
  • the hydrogenation rate is high, the obtained biblock copolymer having an aliphatic structure has improved low birefringence and thermal stability.
  • the hydrogenation reaction solution or polymerization reaction solution of the block copolymer contains a hydrogenation catalyst and / or a polymerization catalyst, it is removed by a method such as filtration or centrifugation, and then the reaction solution is removed from the reaction solution. An alicyclic structure-containing block copolymer is recovered.
  • the method for recovering the alicyclic structure-containing block copolymer from the reaction solution is not particularly limited.
  • a steam coagulation method in which the solvent is removed from the alicyclic structure-containing block polymer solution by steam stripping
  • a direct desolvent method in which the solvent is removed by heating under reduced pressure
  • a solution in which the alicyclic structure-containing block is used.
  • the polymer can be collected by a known method such as a solvent coagulation method in which the polymer is poured into a poor solvent and solidified.
  • the form of the recovered alicyclic structure-containing block copolymer is usually pelletized so as to be advantageous for the subsequent melt molding, but is not limited thereto.
  • a molten alicyclic structure-containing block copolymer may be extruded from a die into a strand, cooled, and then forced into a pellet by a pelletizer to form a pellet.
  • the obtained coagulate can be dried and then melt-extruded with an extruder to form pellets in the same manner as described above.
  • the filler used in the present invention may be an organic filler or an inorganic filler.
  • the organic filler examples include a polymer capable of forming transparent fine particles in an alicyclic structure-containing block copolymer or a crosslinked product thereof.
  • the total light transmittance is preferably 70% or more, more preferably 80% or more. Preferably, those with 90% or more are particularly preferred. If the total light transmittance is too low, the light transmittance of the obtained light diffusing molded article is reduced due to light loss inside the polymer.
  • the total light transmittance here is generally 400 to
  • the refractive index of the organic filler is nlZn2 or n2Zn1 when the refractive index of the alicyclic structure-containing block copolymer is nl and the refractive index of the organic filler is n2.
  • the lower limit is preferably 1.01, more preferably 1.015, particularly preferably 1.025, and the upper limit is preferably 1.2, more preferably 1.1.
  • n2 is preferably from 1.4 to 1.8, more preferably from 1.45 to 1.72. If this refractive index ratio is too low, the light diffusibility of the obtained molded article will be low. If the refractive index ratio is too high, the light transmittance of the obtained molded article decreases.
  • the refractive index is a value at a wavelength according to the purpose of use.
  • the refractive index varies depending on the type of the polymer used, but the value can be adjusted by, for example, the amount of a monomer containing a ferul group. As the amount of the monomer containing a phenyl group increases, the refractive index of the polymer tends to increase.
  • organic fillers examples include (1) butyl monomers such as styrenes and acrylonitriles; methyl (meth) acrylate, ethyl (meth) acrylate,
  • (Meth) acrylate monomers such as butyl (meth) acrylate; homopolymers or copolymers such as (2) the above monomers and diethylene glycol di (meth) acrylate which can be copolymerized with them; , 1,3—butylene glycol di
  • Copolymers with polyfunctional monomers such as (meth) atalilate, dibielbenzene,
  • the organic filler needs to maintain the shape as fine particles in the molded body. If the shape cannot be maintained during molding, a uniform light-diffusing molded body cannot be obtained as described later. Therefore, it is preferably a crosslinked product.
  • Those which can be crosslinked at the time of polymerization such as a copolymer obtained by adding a polyfunctional monomer and copolymerizing, are preferably crosslinked to obtain particles.
  • Fine particles which are crosslinked by a method such as irradiation with ultraviolet light after being formed into particles after polymerization or after being polymerized into particles can also be used.
  • cross-linked polymethyl methacrylate cross-linked polystyrene, cross-linked sodium polyacrylate, cross-linked silicone, cross-linked acryl-styrene copolymer, cross-linked polydimethylsiloxane, and the like.
  • fine particles composed of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof are preferred.
  • the method of converting the above polymer used in the present invention into fine particles is not particularly limited, but the particles can be formed by suspension polymerization or the like.
  • suspension polymerization or the like For example, styrene and dibulbene If suspension-polymerization of a monomer containing a polyfunctional monomer, such as copolymerization of zen, is performed, crosslinked polymer fine particles can be obtained.After polymerization, washing, drying, and classification using a wind micron separator, etc. Thus, crosslinked fine particles having a desired particle size distribution can be obtained.
  • the inorganic filler examples include inorganic fine particles capable of forming transparent fine particles in an alicyclic structure-containing block copolymer. Specific examples include silica, silica alumina, alumina, aluminum hydroxide, magnesium hydroxide, tanolek, glass flakes, glass beads, sodium silicate, and the like. Among these inorganic fillers, silica and talc are preferable because of their excellent transparency. These inorganic fillers can be used alone or in combination of two or more, or can be used in combination with a transparent organic filler.
  • the inorganic filler in the case of blending the inorganic filler by melt-kneading the block copolymer having an alicyclic structure with a twin-screw kneader or the like, avoid deterioration of the color tone of the resin composition due to abrasion of the cylinder screw. For this reason, among the above-mentioned inorganic fillers, it is preferable to use one having a low hardness, such as talc.
  • the particle size of the organic filler and / or the inorganic filler is not particularly limited, but the lower limit of the average particle size is preferably 1 m, more preferably 3 / ⁇ , and particularly preferably 5 ⁇ m.
  • the upper limit is preferably 30 m, more preferably 20 ⁇ m, particularly preferably 15 m. If it is too small, the light diffusivity of the composition of the present invention increases, but the light transmittance decreases.If it is too large, the light transmissivity increases but the light diffusivity decreases, and the surface smoothness of the molded article further decreases. It may be reduced or unevenness may occur.
  • the organic filler and the Z or inorganic filler include a large number of spherical fillers.
  • spherical refers to fine particles having a minor axis and a major axis of preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 0.9 or more, and have no corner.
  • the minor diameter refers to the smallest diameter of one fine particle.
  • the longest diameter is the largest diameter of the same fine particles.
  • the ratio of the spherical fine particles in the fine particles to be used is preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%.
  • the minor axis, major axis, average particle diameter, and the presence or absence of a corner may be measured based on a micrograph image. If there are many non-spherical ones, dispersion tends to be non-uniform at the time of molding, or it becomes difficult to obtain a molded article having uniform orientation and light diffusion.
  • the organic filler and / or the inorganic filler need not be a single kind.For example, a plurality of kinds of organic fillers may be used for the purpose of adjusting the light transmittance and light diffusivity and for the purpose of adjusting to the use environment. Agent and Z or an inorganic filler may be used in combination.
  • the amount of the organic filler and / or the inorganic filler in the resin composition varies depending on the desired optical path length of the light diffusion molded article.
  • the amount in the case of a light diffusion plate having a thickness of 100, the amount is usually from 10 to 30% by weight, and in the case of a light diffusion plate having a thickness of 1 mm, it is usually from 1 to 15% by weight.
  • the content is usually 0.1 to 2% by weight, and for a light diffusing plate having a thickness of 10 mm, usually 0.1 to 0.1% by weight. 2% by weight.
  • the light diffusing resin composition according to the present invention may contain various compounding agents in addition to the alicyclic structure-containing block copolymer and the filler.
  • compounding agents there are no particular limitations on the compounding agents, but stabilizers such as antioxidants, heat stabilizers, light stabilizers, weather stabilizers, ultraviolet absorbers, near infrared absorbers, etc .; esters of aliphatic alcohols, polyhydric alcohols Lubricants such as partial esters and partial ethers; plasticizers; coloring agents such as dyes and pigments; antistatic agents and the like.
  • a blue colorant blueing agent
  • compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.
  • the antioxidant examples include a phenol-based antioxidant, a phosphorus-based antioxidant, and a zeolite-based antioxidant.
  • a phenol-based antioxidant particularly an alkyl-substituted phenol-based antioxidant is preferable.
  • antioxidants may be used alone or in combination of two or more.
  • the blending amount is appropriately selected within a range not to impair the object of the present invention, but is usually 0.001 to 5 parts by weight based on 100 parts by weight of the alicyclic structure-containing block copolymer. , Preferably 0.01-:! Parts by weight.
  • the light-diffusing resin composition according to the present invention has a flexural modulus at 25 ° C. of 10,000 to 27, measured at a temperature of 25 ° C., measured by molding into a plate having a thickness of 2 mm based on the ASTM-D790 method. 000 kgf / cm 2 , preferably 14,000 to 24,000 kgf / cm 2 , and more preferably 17,000 to 21,000 kgf / cm 2 .
  • the flexural modulus is in the above range, there is no cracking of the gate at the time of molding release, and the occurrence of cracks at the time of cutting can be prevented.
  • the light-diffusing resin composition according to the present invention uses a compounding agent blended as required in addition to the alicyclic structure-containing block copolymer and the filler described above, and uses a usual melt-kneading method, such as 1 It can be prepared (manufactured) by a method using a shaft kneader or a twin-screw kneader.
  • the melt-kneading temperature is usually from 200 to 280 ° C, preferably from 220 to 270 ° C, particularly preferably from 240 to 260 ° C, in order to suppress the thermal decomposition of the alicyclic structure-containing block copolymer and the filler. It is desirable to do.
  • the organic filler and the Z or inorganic filler are uniformly dispersed in the block copolymer having an alicyclic structure. If the organic filler and the Z or inorganic filler are not uniformly dispersed due to agglomeration or the like, unevenness in light diffusion and light transmittance occurs, which is undesirable.
  • the light-diffusing resin composition according to the present invention can be molded into various molded articles and used for various applications.
  • a method of molding a general thermoplastic resin can be used. Specifically, extrusion molding, injection molding, compression molding, compressed air molding, vacuum molding and the like are used.
  • the obtained compact is used as a light diffusing plate, etc., and when a product of different size is to be produced in a large variety and small quantity, the extruded plate-like compact is cut, punched, etc. Whatever shape you want, you can produce a lot of the same size In this case, a method by injection molding is advantageous.
  • the light diffusing resin composition is extruded with a T-die or the like, and then sandwiched and pressed by a roll having a mat pattern, so that the mat pattern is formed on the surface. Any method may be used, such as a method of transferring.
  • the molding conditions are appropriately selected depending on the molding method.
  • the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 200 to 280 ° C, more preferably 220 to 250 ° C.
  • the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 180 to 270 ° C, more preferably 200 to 240 ° C. If the resin temperature is excessively low, the fluidity will deteriorate, and the molded product may have sink marks, distortion, and rough surfaces. Conversely, if the resin temperature is excessively high, silver streaks and die lines are generated due to thermal decomposition of the resin. There is a risk of molding defects such as rubbing and yellowing of the molded product.
  • the light diffusing molded article according to the present invention has various shapes such as a spherical shape, a rod shape, a plate shape, a column shape, a cylindrical shape, a lens shape, a film or sheet shape, and has an arbitrary shape depending on the application. be able to.
  • Examples of the light diffusing molded body include a light diffusing plate used for a pack-light type liquid crystal display and the like.
  • the light diffusing plate is disposed between the light source and the irradiation target, so that the light from the pack light source is uniformly emitted, and the light and dark on the emission surface are uniform.
  • Other applications include anti-reflection films, light-diffusing films, lighting covers, reflective screens, transmissive screens, and bulletin board backlights.
  • Mn was measured by GPC at 30 ° C. using THF as a solvent, Mn in terms of standard polystyrene was determined, and the ratio of Mw to Mn (MwZMn) determined in the above (1) was calculated.
  • the hydrogenation rates of the main chain and the aromatic ring of the hydrogenated block copolymer were calculated by measuring the ⁇ H-NMR spectrum.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and the antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate] (ilganox 1010, Ciba Specialty Chemicals) 0.1
  • the antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate] (ilganox 1010, Ciba Specialty Chemicals) 0.1
  • Add 1 part dissolve, and remove solvent using a thin film dryer (Conto Kokuchi, Hitachi, Ltd.) at 260 ° C and 1 OTorr. went.
  • the desolventized block copolymer was extruded as a strand from a die in a molten state by an extruder, cooled with water, and then cut to obtain pellets.
  • the pellet obtained here is a.
  • the obtained hydrogenated block copolymer is a ternary block copolymer composed of a block (St) containing a repeating unit derived from styrene, a block (Ip) containing a repeating unit derived from isoprene, and St. It was a polymer.
  • the block copolymer had Mw of 130,000, MwZMn of 1.20, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%.
  • the pellet was compression molded at 220 ° C to produce a 0.1 mm thick sheet, and the refractive index measured by Abbe refractometer was 1.51.
  • the same reactor as in Production Example 1 was charged with 300 parts of dehydrated cyclohexane, 30 parts of styrene and 0.20 parts of dibutyl ether, and stirred at 60 ° C. while stirring at a temperature of 60 ° C. to a content of 15%. (Xan solution) 0.25 parts was added to initiate the polymerization reaction. After performing the polymerization reaction for 1 hour, 10 parts of styrene was added to the reaction solution, and the polymerization reaction was further performed for 1 hour. Thereafter, 20 parts of isoprene was further added, and the polymerization reaction was further performed for 1 hour. Thereafter, 40 parts of styrene was further added, and the polymerization reaction was continued for another hour. Then, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
  • the pellet obtained here is referred to as resin b.
  • the obtained hydrogenated block copolymer was a ternary block copolymer composed of St, Ip, and St.
  • the block copolymer had an Mw of 134,000, an Mw / M of 1.21, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%.
  • the refractive index measured in the same manner as in Production Example 1 was 1.51.
  • the pellet obtained here is referred to as resin c.
  • the obtained hydrogenated block copolymer was a random copolymer composed of St and Ip.
  • the Mw of the random copolymer was 138,000, MwZMn was 1.22, and the hydrogenation ratio of the main chain and the aromatic ring was 99.9%.
  • the refractive index measured in the same manner as in Production Example 1 was 1.51.
  • Resin a obtained in Production Example 1 100 parts by weight, and spherical crosslinked polystyrene beads (Techpolymer SB X-8, manufactured by Sekisui Plastics Co., Ltd., average particle size 8111, refractive index 1.59) 5 parts by weight
  • a twin-screw kneader TEM-35B, manufactured by Toshiba Machine Co., Ltd.
  • the light diffusing resin composition was extruded from a twin-screw kneader into a strand, cooled with water, and pelletized by a pelletizer.
  • injection molding is performed using an injection molding machine (IS 450, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 260 ° C and a mold temperature of 90 ° C. Length 295 mm, width 225 mm, thickness A 2 mm light diffusion plate was made.
  • the haze which is an index of the total light transmittance and light diffusivity of this light diffusion plate, was measured by a turbidity meter (NDH-300 mm, manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method of JIS K7105.
  • a turbidity meter NDH-300 mm, manufactured by Nippon Denshoku Industries Co., Ltd.
  • JIS K7105 JIS K7105
  • the mechanical strength of the light diffusing plate is determined by cutting out the light diffusing plate into test pieces 100 mm long and 15 mm wide, and using a strograph (manufactured by Toyo Seiki Seisakusho; V10-B) in accordance with ASTM D790 The bending strength at 25 ° C was measured. The bending test showed a yield point and was flexible.
  • the outer shape of the longitudinal end of the light diffuser plate is cut by 2 mm width from the both ends by 100 mm from the both ends with a NC machine, leaving a 25 mm long positioning projection at the center of the end, cracking, cracking, etc. It was confirmed that there was no occurrence of poor appearance. Table 1 shows the results of the evaluation, in which there was no noticeable defect and the appearance was good.
  • spherically crosslinked silicone resin beads (Tospearl 145, manufactured by Toshiba Silicone Co., average particle size 4.5 Mm, refractive index 1.43): 5 parts by weight Except for use, a light diffusing resin composition was obtained in the same manner as in Example 1, and this light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. It was evaluated similarly. The results are shown in Table 1.
  • Example 4 Light diffusing property was obtained in the same manner as in Example 1 except that talc (Microace, manufactured by Nippon Talc Co., average particle size: 4111): 5 parts by weight was used instead of the spherical crosslinked polystyrene beads of Example 1. A resin composition was obtained, and this light-diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light-diffusing plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Example 4
  • a light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin b obtained in Production Example 2 was used instead of the resin a of Example 1.
  • the hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • resin b obtained in Production Example 2 100 parts by weight, spherical spherical crosslinked polystyrene beads used in Example 2 in place of spherical crosslinked polystyrene beads
  • Resin beads A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin c obtained in Production Example 3 was used instead of the resin a of Example 1.
  • the hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 parts by weight, and in place of the spherical crosslinked polystyrene beads, the same spherical crosslinked silicone as used in Example 2 was used.
  • Resin beads A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 3 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 weight parts, and in place of the spherical crosslinked polystyrene beads, the same talc used in Example 3 was used: 5 parts by weight.
  • a light diffusing resin composition was obtained in the same manner as in Example 1 except that the light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. Was evaluated. The results are shown in Table 1.
  • Compounding amount (parts by weight) Compounding amount (parts by weight) 'Thickness of the ancestral material ⁇ Heinos, like 3 ⁇ 4lA "o fam ⁇ " ft' gfsCr
  • Example 1 100 5-19,000 Good appearance 62 94 Good appearance
  • Example 4 100 5 14,000 Good appearance 61 93 Good appearance
  • Example 5 100 5 14,000 Good appearance 68 92 Good appearance
  • a St-Ip-St hydrogenated ternary block copolymer obtained in Production Example 1 and Production Example 2 and a filler had a flexural modulus of 10, 000 ⁇ 27, OOO kg fZcm 2 It was confirmed that the light diffusing molded product (Examples 1-6) comprising the light diffusing resin composition of the present invention was excellent in both light transmittance and light diffusivity. did it.
  • the light-diffusing molded articles of Examples 1 to 6 consist of the conventional hydrogenated styrene-based random copolymer obtained in Production Example 3 and a filler, and have a flexural modulus of 27, OOO kgf Xcm Mechanical flexibility is imparted as compared to the light-diffusing molded article made of the light-diffusing resin composition of 2 or more (Comparative Examples 1 to 3), and the gate portion cracks at the time of release from the injection molding, It was confirmed that chipping and cracking hardly occurred on the cut surface during cutting of the light diffusion plate.
  • the improved mechanical flexibility has a great industrial advantage because small and large variety of molded products can be easily prepared from extruded plates or plates of a certain size by cutting or the like. Industrial applicability
  • a light-diffusing resin suitable for light-diffusing molded articles such as a light-diffusing plate, which has both excellent light-transmitting properties and light-diffusing properties, and has mechanical strength that is hard to be broken during molding and actual use.
  • a composition is provided.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Liquid Crystal (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Composition diffusant la lumière et comprenant un copolymère bloc contenant une structure alicyclique, ainsi qu'une charge, ce copolymère bloc consistant en un polymère bloc (A) contenant une unité récurrente spécifique (1) en quantité égale ou supérieure à 90 % en poids et en un autre polymère bloc (B) contenant une unité récurrente spécifique (2) et/ou une autre unité récurrente spécifique (3) en quantité totale égale ou supérieure à 30 % en poids. Cette composition présente un module de flexion déterminé par son moulage en plaque de 2 mm d'épaisseur et sa mesure à 25 °C selon ASTM-D790, située entre 10000 et 27000 kgf/cm2. Cette composition est appropriée pour des articles moulés diffusant la lumière (par exemple, plaque de diffusion) possédant une perméabilité élevée à la lumière, des propriétés excellentes de diffusion de lumière et une résistance exceptionnelle à la rupture au moulage ou à l'utilisation.
PCT/JP2003/000799 2002-01-29 2003-01-28 Composition de resine diffusant la lumiere WO2003064526A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002020760A JP2003221486A (ja) 2002-01-29 2002-01-29 光拡散性樹脂組成物
JP2002-20760 2002-01-29

Publications (1)

Publication Number Publication Date
WO2003064526A1 true WO2003064526A1 (fr) 2003-08-07

Family

ID=27654368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/000799 WO2003064526A1 (fr) 2002-01-29 2003-01-28 Composition de resine diffusant la lumiere

Country Status (2)

Country Link
JP (1) JP2003221486A (fr)
WO (1) WO2003064526A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112006003336T5 (de) 2005-12-08 2008-10-16 3M Innovative Properties Co., Saint Paul Diffuse mehrschichtige optische Anordnung
US7710511B2 (en) 2004-10-15 2010-05-04 3M Innovative Properties Company Liquid crystal displays with laminated diffuser plates

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006040864A (ja) * 2004-01-14 2006-02-09 Sumitomo Bakelite Co Ltd 直下型バックライト用拡散板およびバックライトシステム
JP4604767B2 (ja) * 2005-03-03 2011-01-05 日本ゼオン株式会社 直下型バックライト装置
JP4808435B2 (ja) * 2005-05-18 2011-11-02 株式会社クラレ 水系電解質電池用水素吸収材
JP2007018939A (ja) * 2005-07-08 2007-01-25 Nippon Zeon Co Ltd 直下型バックライト装置
DE102005050072A1 (de) * 2005-10-19 2007-04-26 Bayer Materialscience Ag Lichtstreuende Folien sowie deren Verwendung in Flachbildschirmen
RU2009116941A (ru) * 2006-10-05 2010-11-10 Дау Глобал Текнолоджиз Инк. (Us) Композиция, способная к объемному рассеянию света

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10116442A (ja) * 1988-01-21 1998-05-06 Mitsubishi Chem Corp 光ディスク基板
JP2001201613A (ja) * 1999-11-10 2001-07-27 Mitsui Chemicals Inc 光拡散板

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10116442A (ja) * 1988-01-21 1998-05-06 Mitsubishi Chem Corp 光ディスク基板
JP2001201613A (ja) * 1999-11-10 2001-07-27 Mitsui Chemicals Inc 光拡散板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7710511B2 (en) 2004-10-15 2010-05-04 3M Innovative Properties Company Liquid crystal displays with laminated diffuser plates
DE112006003336T5 (de) 2005-12-08 2008-10-16 3M Innovative Properties Co., Saint Paul Diffuse mehrschichtige optische Anordnung

Also Published As

Publication number Publication date
JP2003221486A (ja) 2003-08-05

Similar Documents

Publication Publication Date Title
US7980734B2 (en) Bulk light diffuser composition
JP4277525B2 (ja) 樹脂組成物
JPH01132603A (ja) 光学材料
WO2016152871A1 (fr) Film optique
EP1245637B1 (fr) Composition resineuse a diffusion de la lumiere
WO2003064526A1 (fr) Composition de resine diffusant la lumiere
JPWO2003018656A1 (ja) ブロック共重合体、その製造方法、および成形体
JP6756361B2 (ja) 複層フィルム及び製造方法
JP2008013604A (ja) テトラシクロドデセン含有開環重合体水素化物、光学樹脂材料および光学成形体
JP2001048924A (ja) 脂環式炭化水素系共重合体
JPWO2007119512A1 (ja) 光学素子及び光学用樹脂レンズ
JP2002105151A (ja) フィルム及びシート
JP6557108B2 (ja) 透明導電性フィルム及びタッチパネル
JP2003276047A (ja) ビニル脂環式炭化水素重合体組成物の成形方法及び成形体
JPWO2019065401A1 (ja) 光学積層フィルム及びタッチパネル
JP2006189523A (ja) 導光板
JP5097541B2 (ja) 透明耐熱性樹脂およびその製造方法、並びに透明耐熱性樹脂を含有する光学材料
JP2006232879A (ja) 表示窓保護用シート
JP7226333B2 (ja) 偏光板保護フィルム、偏光板及び表示装置
JP2002071964A (ja) 導光板
JP2004149610A (ja) 光拡散性樹脂組成物及び光拡散性成形体
JP4214686B2 (ja) 樹脂積層体及びその製造方法
JP2002053631A (ja) 新規なブロック共重合体及び光学式情報記録媒体
JP2007269961A (ja) 透明耐熱性樹脂、その水素添加物、およびそれらの製造方法、並びに透明耐熱性樹脂を含有する光学材料
JP2008208361A (ja) 重合体組成物及びそれを用いて得られる成形体

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase