CN104334641A - Resin composition having light-guiding ability, and light guide plate and surface light source body comprising same - Google Patents

Resin composition having light-guiding ability, and light guide plate and surface light source body comprising same Download PDF

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Publication number
CN104334641A
CN104334641A CN201380029867.3A CN201380029867A CN104334641A CN 104334641 A CN104334641 A CN 104334641A CN 201380029867 A CN201380029867 A CN 201380029867A CN 104334641 A CN104334641 A CN 104334641A
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China
Prior art keywords
carbonatoms
polycarbonate
phenyl
polydiorganosiloxane
resin combination
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CN201380029867.3A
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Inventor
高桥直
森嘉昭
三宅利往
品川明日香
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Teijin Ltd
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Teijin Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • 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
    • C08L2201/00—Properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0065—Manufacturing aspects; Material aspects

Abstract

The present invention provides a resin composition offering both a high level of light-guiding ability and high flowability, as well as a light guide plate and surface light source body comprising the same. The present invention is a resin composition having light-guiding ability, containing (A) a polycarbonate resin (A-component) and (B) a polycarbonate/polydiorganosiloxane copolymer resin (B-component), wherein the resin composition has a viscosity-average molecular weight in the range of 1.2*104 to 1.3*104, and the B-component is a polycarbonate/polydiorganosiloxane copolymer resin where a polydiorganosiloxane domain having a mean size of 0.5 to 40 nm is present in a matrix of polycarbonate polymer.

Description

There is the resin combination of guide-lighting performance and the light guiding plate be made up of it and surface light source unit
Technical field
The present invention relates to the resin combination with guide-lighting performance and the light guiding plate be made up of it and surface light source unit.More specifically, relate to can suitably at the also excellent optical element such as optical lens, light guiding plate (light guide) of the transparency, light conductivity excellent and thermostability, tone or display panel, illuminating cover, substitute the resin combination with guide-lighting performance used in the purposes etc. of glass, and the light guiding plate be made up of it and surface light source unit.
Background technology
Light guiding plate has to make light diffusion incident from the side and the plate sending the function of uniform light on surface.By light guiding plate is used for panel, thus do not need overleaf light source to be installed, can make thin and there is no uneven efficient panel, therefore expecting widespread use in the purposes such as the liquid crystal indicator such as Personal Computer, mobile telephone, lighting fixtures always.As the material of light guiding plate, self-evident pursuit is from the few characteristic of the decay of the light of light source and light conductivity, up to now in transparent resin, always using the materials'use of polymethylmethacrylate (hereinafter sometimes referred to " PMMA ") as the best.But the shock-resistance, thermostability etc. of PMMA may not be abundant, there is the problem that environment for use is restricted in above-mentioned purposes.In addition, from the view point of long lifetime low power consumption, the photodiode (LED) always carrying out light source is changed, and also starts requirement thermotolerance to light guiding plate except requiring above-mentioned characteristic.Therefore, excellence the technology that the light conductivity of polycarbonate resin is improved is received much concern in thermotolerance, shock-resistance.
As the example of the light conductivity of improvement polycarbonate, reporting in viscosity-average molecular weight is the light guiding plate aromatic copolycarbonate resin composition (patent documentation 1) coordinating specific stablizer and releasing agent in the polycarbonate resin of 13000 ~ 15000.But although set forth the raising of light conductivity and brightness, improve for tone and illustrate only so-called improvement of burning caused xanthochromia, in opposite, aberration is not set forth.The composition of mixed aromatic polycarbonate resin and transparent higher acrylic resin is reported in patent documentation 2 ~ 4.But the method, owing to adding acrylic resin, diffusant, cannot avoid gonorrhoea.Report mixed aromatic polycarbonate resin in patent documentation 5 and there is the composition of organopolysiloxane of side chain siloxane structure.But the generation of gas when considering shaping, the cohesion of siloxanes, the method cannot obtain good light guiding plate.
On the other hand, as the resin combination containing polycarbonate and polycarbonate-polydiorganosiloxane copolymer resins, report thermoplastic resin composition's (patent documentation 6) in the polysiloxane structure territory having imbedded average domain size 20 ~ 45nm or 20 ~ 40nm in the matrix of carbonate polymer.But without any the record about light conductivity in patent documentation 6.
In addition, in recent years, because the thin-walled of the display unit headed by televisor, Personal Computer maximizes, light guiding plate and circumferential component thereof also require that the trend that thin-walled maximizes strengthens further.Such as, the thickness of the liquid crystal indicator used in mobile telephone, smart mobile phone, tablet-type personal computer etc. is about 3mm, the thickness being assembled in light guiding plate is wherein thin, there is the light guiding plate of the thickness of about 0.2mm, resin material is required that high workability is certain, also requires to have excellent guide-lighting performance concurrently.
Patent documentation 1: Japanese Unexamined Patent Publication 2007-204737 publication
Patent documentation 2: Japanese Patent No. 3330498 publication
Patent documentation 3: Japanese Patent No. 3516908 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-201667 publication
Patent documentation 5: Japanese Patent No. 4446668 publication
Patent documentation 6: Japanese Unexamined Patent Application Publication 2006-523243 publication
Summary of the invention
The object of the present invention is to provide the resin combination and the light guiding plate be made up of it and surface light source unit that have guide-lighting performance highly and high workability concurrently.
The present inventor etc. to achieve these goals, repeatedly further investigate, found that the resin combination of the specific viscosity-average molecular weight obtained by combination polycarbonate resin and the polycarbonate-polydiorganosiloxane copolymer resins with specific polydiorganosiloxane structural domain, light conductivity is excellent, and little, the excellent hue of aberration in face, and high workability and plastic property are excellent, thus complete the present invention.
That is, according to the present invention, provide:
1. one kind has the resin combination of guide-lighting performance, containing (A) polycarbonate resin (A composition) and (B) polycarbonate-polydiorganosiloxane copolymer resins (B component), the viscosity-average molecular weight of this resin combination is 1.2 × 10 4~ 1.3 × 10 4scope, B component is in the matrix of carbonate polymer, there is polycarbonate-polydiorganosiloxane copolymer resins that mean sizes is the polydiorganosiloxane structural domain of 0.5 ~ 40nm.
2. according to the resin combination with guide-lighting performance that preceding paragraph 1 is recorded, wherein, B component is polycarbonate-polydiorganosiloxane copolymer resins that polydiorganosiloxane block that the polycarbonate block that represented by following formula (2) and following formula (4) represent is formed.
[in above-mentioned formula (2), R 1and R 2represent independently of one another and be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 18, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 3 ~ 14, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, group in cyano group and carboxyl, when existing multiple separately, they can be the same or different, e and f is respectively the integer of 1 ~ 4, W is singly-bound or at least 1 group in being selected from group that following formula (3) represents.
(in above-mentioned formula (3), R 11, R 12, R 13, R 14, R 15, R 16, R 17and R 18represent the group be selected from the aralkyl of hydrogen atom, the alkyl of carbonatoms 1 ~ 18, the aryl of carbonatoms 3 ~ 14 and carbonatoms 7 ~ 20 independently of one another, R 19and R 20represent the group be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 10, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 6 ~ 10, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, cyano group and carboxyl independently of one another, when existing multiple, they can be the same or different, g is the integer of 1 ~ 10, and h is the integer of 4 ~ 7.)]
(in above-mentioned formula (4), R 3, R 4, R 5, R 6, R 7and R 8be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or the aryl without replacement independently of one another, R 9and R 10be hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 10, the alkoxyl group of carbonatoms 1 ~ 10 independently of one another, p is natural number, and q is 0 or natural number, and p+q is the natural number of less than 150.X is the aliphatic divalent group of carbonatoms 2 ~ 8.)
3., according to the resin combination with guide-lighting performance that preceding paragraph 1 or 2 is recorded, wherein, with the gross weight of resin combination for benchmark, the content of the polydiorganosiloxane block that the following formula (5) contained in above-mentioned formula (4) represents is 0.001 ~ 1.0 % by weight.
(in above-mentioned formula (5), R 21, R 22, R 23, R 24, R 25and R 26be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or without the aryl replaced, r is natural number independently of one another, s is 0 or natural number, and r+s is the natural number of less than 150.)
4. the resin combination with guide-lighting performance recorded any one of preceding paragraph 1 ~ 3, wherein, with the gross weight of resin combination for benchmark, the content of the polydiorganosiloxane block that the above-mentioned formula (5) contained in above-mentioned formula (4) represents is 0.01 ~ 0.5 % by weight.
5. the resin combination with guide-lighting performance recorded any one of preceding paragraph 1 ~ 4, it is characterized in that, B component is in the matrix of carbonate polymer, there is polycarbonate-polydiorganosiloxane copolymer resins that mean sizes is the polydiorganosiloxane structural domain of 0.5 ~ 18nm.
6. the resin combination with guide-lighting performance recorded any one of preceding paragraph 1 ~ 5, wherein, relative to (A) polycarbonate resin (A composition) 100 weight parts, containing (B) polycarbonate-polydiorganosiloxane copolymer resins (B component) 0.01 ~ 10 weight part.
7. the resin combination with guide-lighting performance recorded any one of preceding paragraph 1 ~ 6, wherein, relative to polycarbonate resin (A composition) 100 weight parts, containing phosphorus system stablizer (C composition) 0.01 ~ 1.0 weight part that (C) following formula (1) represents.
(in formula (1), A 1, A 2be aryl or alkyl independently of one another, can be the same or different.)
8. a light guiding plate is by shaping for the resin combination recorded any one of preceding paragraph 1 ~ 7.
9., according to the light guiding plate recorded in preceding paragraph 8, wherein, the length of the long side direction of light guiding plate is 50 ~ 130mm.
10., according to the light guiding plate that preceding paragraph 8 or 9 is recorded, wherein, the thickness accounting for the region of at least 80% of light guiding plate is the scope of 0.2 ~ 0.4mm.
11. light guiding plates recorded any one of preceding paragraph 8 ~ 10, wherein, give the shape of prism in the one side of light guiding plate, the convex or concave shape in contrary face imparting arc-shaped.
12. 1 kinds of surface light source units are that the one side of the light guiding plate recorded any one of preceding paragraph 8 ~ 11 arranges reflector.
As the poly carbonate resin composition of the specific viscosity-average molecular weight obtained in the present invention, in its formed body, polydiorganosiloxane structural domain forms specific coherent structure, the transparency, high workability, plastic property are excellent, and play excellent light conductivity, above-mentioned characteristic therefore can be utilized in the parts that in the past cannot use to launch purposes.As concrete example, optics, electric/electronic device field, automotive field can be widely used in.More specifically, illuminating cover, indicating meter diffuser plate and light guiding plate, the various optical disc such as purposes, CD substituting glass and the various housing such as associated components, battery container products formed, lens barrel, storage card, loud speaker carton, disk cartridge, planar luminous body, micromachine mechanism part, with gemel products formed or hinge products formed, printing opacity light-conducting type button class, touch panel parts etc. can be illustrated.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the measuring method of the light conductivity (in brightness, face aberration) represented in the present invention.
Embodiment
Below, the present invention is specifically described.
(A composition: polycarbonate resin)
As the polycarbonate resin that A composition of the present invention uses, normally make the composition that dihydroxy compound and carbonate precursor are reacted by interface polycondensation, melt transesterification process and obtained, the composition that polycarbonate prepolymer thing is polymerized by solid phase ester-interchange method in addition, or the composition obtained by the ring-opening polymerization method polymerization of cyclic carbonate compound.As dihydroxyl composition used herein, as long as the composition used usually used as the dihydroxyl composition of aromatic copolycarbonate, can be bisphenols also can be aliphatic diol class.
As bisphenols, such as, can enumerate 4,4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) ethane of 1,1-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, two (4-hydroxy phenyl) propane of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxy phenyl)-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two (4-hydroxyl-3, the 3 '-biphenyl) propane of 2,2-, two (4-hydroxyl-3-isopropyl phenyl) propane of 2,2-, two (3-tert-butyl-hydroxy phenyl) propane of 2,2-, two (4-hydroxy phenyl) butane of 2,2-, two (4-hydroxy phenyl) octane of 2,2-, two (the bromo-4-hydroxy phenyl of the 3-) propane of 2,2-, two (3, the 5-dimethyl-4-hydroxy phenyl) propane of 2,2-, two (3-cyclohexyl-4-hydroxy phenyl) propane of 2,2-, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthene of 1,1-, two (4-hydroxy phenyl) ditan, two (4-hydroxy phenyl) fluorenes of 9,9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, 1,1-bis(4-hydroxyphenyl) cyclohexane, two (4-hydroxy phenyl) pentamethylene of 1,1-, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl ether, 4,4 '-sulfonyldiphenol, 4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenyl thioether, 2,2 '-dimethyl-4,4 '-sulfonyldiphenol, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfide, 2,2 '-phenylbenzene-4,4 '-sulfonyldiphenol, 4,4 '-dihydroxyl-3,3 '-phenylbenzene diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-phenylbenzene diphenylsulfide, two { 2-(4-hydroxy phenyl) propyl group } benzene of 1,3-, Isosorbide-5-Nitrae-bis-{ 2-(4-hydroxy phenyl) propyl group } benzene, Isosorbide-5-Nitrae-bis(4-hydroxyphenyl) cyclohexane, 1,3-bis(4-hydroxyphenyl) cyclohexane, 4,8-two (4-hydroxy phenyl) three ring [5.2.1.0 2,6] decane, 4,4 '-(1,3-diamantane two base) biphenol, 1,3-two (4-hydroxy phenyl)-5,7-dimethyladamantanes etc.
As aliphatic diol class, such as, can enumerate 2,2-pair-(4-hydroxy-cyclohexyl)-propane, 1,14-tetradecane diols, eight ethylene glycol, 1,16-hexadecane diol, 4,4 '-bis-(2-hydroxyl-oxethyl) biphenyl, two { (2-hydroxyl-oxethyl) phenyl } methane, two { (2-hydroxyl-oxethyl) phenyl } ethane of 1,1-, two { (2-hydroxyl-oxethyl) the phenyl }-1-diphenylphosphino ethane of 1,1-, two { (2-hydroxyl-oxethyl) phenyl } propane of 2,2-, two { (2-the hydroxyl-oxethyl)-3-aminomethyl phenyl } propane of 2,2-, two { (2-hydroxyl-oxethyl) phenyl }-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two { 4-(2-hydroxyl-oxethyl)-3, the 3 '-biphenyl } propane of 2,2-, two { (2-the hydroxyl-oxethyl)-3-isopropyl phenyl } propane of 2,2-, two { the 3-tertiary butyl-4-(2-hydroxyl-oxethyl) phenyl } propane of 2,2-, two { (2-hydroxyl-oxethyl) phenyl } butane of 2,2-, two { (2-hydroxyl-oxethyl) the phenyl }-4-methylpentane of 2,2-, two { (2-hydroxyl-oxethyl) phenyl } octane of 2,2-, two { (2-hydroxyl-oxethyl) phenyl } decane of 1,1-, two { the bromo-4-of 3-(2-hydroxyl-oxethyl) phenyl } propane of 2,2-, two { 3,5-dimethyl-4-(2-hydroxyl-oxethyl) phenyl } propane of 2,2-, two { 3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl } propane of 2,2-, two { 3-cyclohexyl-4-(2-hydroxyl-oxethyl) phenyl } hexanaphthene of 1,1-, two { (2-hydroxyl-oxethyl) phenyl } ditan, two { (2-hydroxyl-oxethyl) phenyl } fluorenes of 9,9-, two { 4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl } fluorenes of 9,9-, two { (2-hydroxyl-oxethyl) phenyl } hexanaphthene of 1,1-, two { (2-hydroxyl-oxethyl) phenyl } pentamethylene of 1,1-, 4,4 '-bis-(2-hydroxyl-oxethyl) diphenyl ether, 4,4 '-bis-(2-hydroxyl-oxethyl)-3,3 '-dimethyl diphenyl ether, 1,3-pair [2-{ (2-hydroxyl-oxethyl) phenyl } propyl group] benzene, Isosorbide-5-Nitrae-bis-[2-{ (2-hydroxyl-oxethyl) phenyl } propyl group] benzene, Isosorbide-5-Nitrae-bis-{ (2-hydroxyl-oxethyl) phenyl } hexanaphthene, two { (2-hydroxyl-oxethyl) phenyl } hexanaphthene of 1,3-, two { (2-hydroxyl-oxethyl) phenyl } three ring [5.2.1.0 of 4,8- 2,6] decane, 1,3-two { (2-hydroxyl-oxethyl) phenyl }-5,7-dimethyladamantanes, 3, two (2-hydroxyl-1, the 1-dimethyl ethyl)-2,4 of 9-, 8,10-tetra-oxaspiro (5,5) undecane, 1,4:3, dewater-D-Sorbitol Powder (isosorbide), Isosorbide-5-Nitrae: 3,6-bis-of 6-bis-dewaters-D-mannital (different mannitol), 1,4:3,6-bis-dewaters-L-iditol (different iditol) etc.
Wherein, optimization aromatic bisphenols, especially preferably 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 1, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyl)-3 of 1-, 3, 5-trimethyl-cyclohexane, 4, 4 '-sulfonyldiphenol, 2, 2 '-dimethyl-4, 4 '-sulfonyldiphenol, 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-, 1, two { 2-(4-hydroxy phenyl) propyl group } benzene and 1 of 3-, two { 2-(4-hydroxy phenyl) propyl group } benzene of 4-, particularly preferably 2, two (4-hydroxy phenyl) propane of 2-, 1, 1-bis(4-hydroxyphenyl) cyclohexane, 4, 4 '-sulfonyldiphenol and 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-.Wherein most preferably excellent strength, there are 2,2-two (4-hydroxy phenyl) propane of good weather resistance.In addition, they can be used alone or combine more than two kinds uses.
As the polycarbonate resin that A composition of the present invention uses, branching agent and above-mentioned dihydroxy compound also can be used and formed a point branched polycarbonate resin.As multi-functional the aromatics more than trifunctional used in above-mentioned branched polycarbonate resin, Phloroglucinol can be enumerated, 2,3', 4,5', 6-penta hydroxy group biphenyl, or 4,6-dimethyl-2,4,6-tri-(4-hydroxy phenyl) heptene-2, 2,4,6-trimethylammonium-2,4,6-tri-(4-hydroxy phenyl) heptane, 1,3,5-tri-(4-hydroxy phenyl) benzene, 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenol of 2,6-, 4-{4-[1,1-two (4-hydroxy phenyl) ethyl] benzene } trisphenol such as-alpha, alpha-dimethylbenzyl phenol, four (4-hydroxy phenyl) methane, two (2,4-dihydroxy phenyl) ketone, Isosorbide-5-Nitrae-bis-(4,4-dihydroxyl trityl group) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acyl chlorides etc., wherein preferred 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, particularly preferably 1,1,1-tri-(4-hydroxy phenyl) ethane.
These polycarbonate resins are by itself known reactive mode of common manufacture aromatic polycarbonate resin, and the method such as making the carbonate precursor such as phosgene, carbonic diester material and aromatic series dihydroxyl composition react manufactures.For the mode that this manufacture method simple declaration is basic.
Such as using in the reaction of phosgene as carbonate precursor material, usually reacting under the existence of acid binding agent and solvent.As acid binding agent, such as, can use the amine compound such as the alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or pyridine.As solvent, the such as halohydrocarbon such as methylene dichloride, chlorobenzene can be used.In addition, in order to promote that reaction also can use the such as catalyzer such as tertiary amine or quaternary ammonium salt.At this moment, temperature of reaction is generally 0 ~ 40 DEG C, and the reaction times is several minutes ~ 5 hour.
Use carbonic diester as the transesterification reaction of carbonate precursor material, by the aromatic series dihydroxyl composition of regulation ratio and carbonic diester being heated while stirring under non-active gas atmosphere, the method that the alcohol of generation or phenols are distillated and carrying out.Temperature of reaction is different according to the alcohol of generation or the boiling point of phenols etc., is generally the scope of 120 ~ 300 DEG C.Reaction was under reduced pressure carried out from its initial stage, terminated along with the alcohol or phenols that make generation distillate reaction.In addition, in order to promote reaction, the catalyzer used in usual transesterification reaction can also be used.As the carbonic diester used in above-mentioned transesterification reaction, such as, can enumerate diphenyl carbonate, carbonic acid dinaphthyl ester, two (phenylbenzene) carbonic ether, methylcarbonate, diethyl carbonate, dibutyl carbonate etc.Wherein particularly preferably diphenyl carbonate.
In the present invention, in polyreaction, use end terminator.End terminator be used for molecular-weight adjusting, in addition, because the end of the polycarbonate resin obtained is closed, thus compared with situation about not being closed excellent heat stability.As above-mentioned end terminator, the simple function phenols that following formula (6) represents can be shown.
[in formula, A is hydrogen atom, the alkyl of carbonatoms 1 ~ 9, alkyl phenyl (carbonatoms of moieties is 1 ~ 9), phenyl or phenylalkyl (carbonatoms of moieties is 1 ~ 9), r is 1 ~ 5, is preferably the integer of 1 ~ 3].
As the concrete example of the simple function phenols that above-mentioned formula (6) represents, such as, can enumerate phenol, isopropyl-phenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenylphenol and isooctyl phenol etc.Be preferably p-tert-butylphenol, p-cumylphenol or 2-phenylphenol.The end terminator of these simple function phenols imports at least 5 % by mole relative to whole ends of the polycarbonate resin obtained, and preferably at least import at 10 % by mole of ends, in addition, end terminator may be used singly or as a mixture of two or more.
As the polycarbonate resin that A composition of the present invention uses, in the scope not damaging purport of the present invention, also can be by the polyestercarbonate of aromatic dicarboxylic acid such as terephthalic acid, m-phthalic acid, the copolymerization of naphthalic acid or derivatives thereof.
The viscosity-average molecular weight of the polycarbonate resin used as A composition of the present invention preferably 1.15 × 10 4~ 1.35 × 10 4scope, more preferably 1.20 × 10 4~ 1.30 × 10 4scope, further preferably 1.22 × 10 4~ 1.28 × 10 4scope.Using the viscosity-average molecular weight as resin combination for 1.2 × 10 4~ 1.3 × 10 4the mode of scope use, if this scope, then formability when thin molded article is shaping (formability) is particularly excellent, and in addition, physical strength is also good.Should illustrate, said viscosity-average molecular weight in the present invention, first use formula viscometer difficult to understand to obtain by the solution at 20 DEG C of dissolved polycarbonate resin 0.7g in methylene dichloride 100ml the specific viscosity be calculated as follows, the specific viscosity of trying to achieve is substituted into following formula and obtains viscosity-average molecular weight M.
Specific viscosity (η sP)=(t-t 0)/t 0
[t 0for the drippage number of seconds of methylene dichloride, t is the drippage number of seconds of sample solution]
η sP/ c=[η]+0.45 × [η] 2c (wherein, [η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7
As the polycarbonate resin that A composition of the present invention uses, total Cl (chlorine) amount in resin is preferably 0 ~ 200ppm, is more preferably 0 ~ 150ppm.If the total Cl amount in polycarbonate resin is below 200ppm, then tone and good thermal stability, thus preferably.
(B component: polycarbonate-polydiorganosiloxane copolymer resins)
Polycarbonate-polydiorganosiloxane the copolymer resins used as B component of the present invention is in the matrix of carbonate polymer, there is polycarbonate-polydiorganosiloxane copolymer resins that mean sizes is the polydiorganosiloxane structural domain of 0.5 ~ 40nm.The mean sizes of polydiorganosiloxane structural domain is preferably 0.5 ~ 30nm, is more preferably 0.5 ~ 18nm, is further preferably 2.0 ~ 18nm, most preferably is 5.0 ~ 18nm.When this mean sizes is less than 0.5nm, do not have effect to aberration in improvement face and raising light conductivity, during more than 40nm, sometimes produce muddiness, full light transmittance reduces, and cannot obtain light conductivity, thus not preferred.The mean sizes of this polydiorganosiloxane structural domain is implemented to measure by low-angle scattering of X-rays method (Small Angel X-ray Scattering:SAXS).
Should illustrate, low-angle scattering of X-rays method is the method for the Scattering and diffracting being determined at the undiscipline that little angular zone that scattering angle (2 θ) is less than the scope of 10 ° produces.In this low-angle scattering of X-rays method, if there is the region of the size of different about the 1 ~ 100nm of electron density in material, then according to the diffuse scattering of its electron density difference measurements X-ray.The particle diameter of measuring object is obtained based on this scattering angle and scattering strength.For the polycarbonate-polydiorganosiloxane copolymer resins becoming the coherent structure being dispersed with polydiorganosiloxane structural domain in the matrix of carbonate polymer, because the electron density of polycarbonate substrates and polydiorganosiloxane structural domain is poor, produce the diffuse scattering of X-ray.Measure the scattering strength I that scattering angle (2 θ) is less than each scattering angle (2 θ) of the scope of 10 °, mensuration small angle X ray scattering is composed, assuming that polydiorganosiloxane structural domain is globular domain, there is the fluctuation of size distribution, then by supposition particle diameter and supposition size distribution model, use commercially available parsing software to carry out matching, obtain the mean sizes of polydiorganosiloxane structural domain.Adopt low-angle scattering of X-rays method, can high precision, easy and reproducibility be determined at well to utilize in the observation of transmission type microscope cannot Accurate Determining, the mean sizes of polydiorganosiloxane structural domain in the matrix that is dispersed in carbonate polymer.
The polycarbonate block that B component is preferably represented by following formula (2) and polycarbonate-polydiorganosiloxane copolymer resins that the polydiorganosiloxane block that following formula (4) represents is formed.
[in above-mentioned formula [2], R 1and R 2represent independently of one another and be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 18, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 3 ~ 14, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, group in cyano group and carboxyl, when existing multiple respectively, they can be the same or different, e and f is respectively the integer of 1 ~ 4, W is singly-bound or at least 1 group in being selected from group that following formula [3] represents.
(in above-mentioned formula [3], R 11, R 12, R 13, R 14, R 15, R 16, R 17and R 18represent the group be selected from the aralkyl of hydrogen atom, the alkyl of carbonatoms 1 ~ 18, the aryl of carbonatoms 3 ~ 14 and carbonatoms 7 ~ 20 independently of one another, R 19and R 20represent the group be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 10, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 6 ~ 10, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, cyano group and carboxyl independently of one another, when existing multiple, they can be the same or different, g is the integer of 1 ~ 10, and h is the integer of 4 ~ 7.)]
(in above-mentioned formula [4], R 3, R 4, R 5, R 6, R 7and R 8be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or the aryl without replacement independently of one another, R 9and R 10be hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 10, the alkoxyl group of carbonatoms 1 ~ 10 independently of one another, p is natural number, and q is 0 or natural number, and p+q is the natural number of less than 150.X is the aliphatic divalent group of carbonatoms 2 ~ 8.
As the dihydric phenol (I) that the carbonic ether Component units above-mentioned formula (2) represented is derivative, such as, can 4 be enumerated, 4 '-dihydroxybiphenyl, two (4-hydroxy phenyl) methane, two (4-hydroxy phenyl) ethane of 1,1-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, two (4-hydroxy phenyl) propane of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxy phenyl)-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two (4-hydroxyl-3, the 3 '-biphenyl) propane of 2,2-, two (4-hydroxyl-3-isopropyl phenyl) propane of 2,2-, two (3-tert-butyl-hydroxy phenyl) propane of 2,2-, two (4-hydroxy phenyl) butane of 2,2-, two (4-hydroxy phenyl) octane of 2,2-, two (the bromo-4-hydroxy phenyl of the 3-) propane of 2,2-, two (3, the 5-dimethyl-4-hydroxy phenyl) propane of 2,2-, two (3-cyclohexyl-4-hydroxy phenyl) propane of 2,2-, two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthene of 1,1-, two (4-hydroxy phenyl) ditan, two (4-hydroxy phenyl) fluorenes of 9,9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, 1,1-bis(4-hydroxyphenyl) cyclohexane, two (4-hydroxy phenyl) pentamethylene of 1,1-, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl ether, 4,4 '-sulfonyldiphenol, 4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenyl thioether, 2,2 '-dimethyl-4,4 '-sulfonyldiphenol, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl sulfide, 2,2 '-phenylbenzene-4,4 '-sulfonyldiphenol, 4,4 '-dihydroxyl-3,3 '-phenylbenzene diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-phenylbenzene diphenylsulfide, two { 2-(4-hydroxy phenyl) propyl group } benzene of 1,3-, Isosorbide-5-Nitrae-bis-{ 2-(4-hydroxy phenyl) propyl group } benzene, Isosorbide-5-Nitrae-bis(4-hydroxyphenyl) cyclohexane, 1,3-bis(4-hydroxyphenyl) cyclohexane, 4,8-two (4-hydroxy phenyl) three ring [5.2.1.0 2,6] decane, 4,4 '-(1,3-diamantane two base) biphenol and two (4-hydroxy phenyl)-5, the 7-dimethyladamantanes of 1,3-etc.
Wherein, preferably 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 1, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyl)-3 of 1-, 3, 5-trimethyl-cyclohexane, 4, 4 '-sulfonyldiphenol, 2, 2 '-dimethyl-4, 4 '-sulfonyldiphenol, 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-, 1, two { 2-(4-hydroxy phenyl) propyl group } benzene of 3-, and 1, two { 2-(4-hydroxy phenyl) propyl group } benzene of 4-, particularly preferably 2, two (4-hydroxy phenyl) propane of 2-, 1, 1-bis(4-hydroxyphenyl) cyclohexane, 4, 4 '-sulfonyldiphenol, and 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9-.Wherein most preferably excellent strength, there are 2,2-two (4-hydroxy phenyl) propane of good weather resistance.In addition, they can be used alone or combine more than two kinds uses.
In the carbonic ether Component units that above-mentioned formula (4) represents, R 3, R 4, R 5, R 6, R 7and R 8be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or the aryl without replacement independently of one another, be preferably hydrogen atom, the alkyl of carbonatoms 1 ~ 6 or the replacement of carbonatoms 6 ~ 12 or without the aryl replaced, particularly preferably the alkyl of hydrogen atom, carbonatoms 1 ~ 6 or phenyl.R 9and R 10be hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 10, the alkoxyl group of carbonatoms 1 ~ 10 independently of one another, be preferably the alkyl of hydrogen atom, carbonatoms 1 ~ 10, the particularly preferably alkyl of hydrogen atom, carbonatoms 1 ~ 4.As dihydroxyl aryl end polydiorganosiloxane (II) that the carbonic ether Component units above-mentioned formula (4) represented is derivative, such as, preferably use the compound shown in following formula (I).
Represent that p, q of the two organo-siloxane polymerization degree represent natural number respectively, p+q is the natural number of less than 150, preferably 4 ~ 120, more preferably 30 ~ 120, most preferably 30 ~ 100.
Polydiorganosiloxane component content accounts for the polycarbonate-polydiorganosiloxane copolymer resins gross weight used as B component of the present invention and is preferably 0.01 ~ 20.0 % by weight, be more preferably 0.01 ~ 10.0 % by weight, more preferably 2.0 ~ 10.0 % by weight, most preferably be 2.0 ~ 8.0 % by weight.If polydiorganosiloxane component content is lower than 0.01 % by weight, then in face, aberration improves effect deficiency, if more than 20.0 % by weight, then full light transmittance reduces sometimes, cannot obtain guide-lighting performance.Should illustrate, the above-mentioned two organo-siloxane polymerization degree, polydiorganosiloxane component content can pass through 1h-NMR measures and calculates.
Next, below the manufacture method of above-mentioned preferred polycarbonate-polydiorganosiloxane copolymer resins is described.
In advance in the mixed solution of water-insoluble organic solvent and alkaline aqueous solution, by the reaction of the chloro-formic ester formative compounds such as the chloro-formic ester of dihydric phenol (I) and phosgene or dihydric phenol (I), the chloro-formic ester of preparation containing dihydric phenol (I) and/or there is the mixing solutions of chloroformate compound of carbonate oligomer of dihydric phenol (I) of end chloroformic acid ester group.As chloro-formic ester formative compound, preferred phosgene.
When generating the chloroformate compound from dihydric phenol (I), once can add the total amount of the derivative dihydric phenol (I) of the carbonic ether Component units that above-mentioned formula (1) represented to form chloroformate compound, or, also its part can be added in the interfacial polycondensation reaction of back segment as reaction raw materials as rear interpolation monomer.Rear interpolation monomer is the monomer added to make the polycondensation of back segment carry out rapidly, need not add when there is no need.
The method of this chloroformate compound formation reaction is not particularly limited, usually preferred under the existence of acid binding agent, the mode of carrying out in a solvent.In addition, as required, the antioxidants such as a small amount of S-WAT and hydrogen sulfide can be added, preferably add.
For the usage ratio of chloro-formic ester formative compound, consider the stoichiometric ratio (equivalent) of reaction and suitably adjust.In addition, when being used as the phosgene of applicable chloro-formic ester formative compound, the method phosgene gasified being blown into reaction system can suitably be adopted.
As above-mentioned acid binding agent, such as, organic bases or their mixture etc. of the alkaline carbonates and pyridine and so on such as the alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, sodium carbonate and salt of wormwood can be used.
The usage ratio of acid binding agent is also considered the stoichiometric ratio (equivalent) of reaction as described above and suitably sets.Specifically, the dihydric phenol (I) 1 mole (usual 1 mole is equivalent to 2 equivalents) used in formation relative to the chloroformate compound of dihydric phenol (I), preferably use 2 equivalents or in contrast a little excessive acid binding agent.
As above-mentioned solvent, solvent used etc. can be used alone a kind or use with the form of mixed solvent to the inactive solvent of various reaction in the manufacture of known polycarbonate.Representatively property example, such as, can enumerate the hydrocarbon solvent of dimethylbenzene and so on and the halogenated hydrocarbon solvent etc. that is representative with methylene dichloride and chlorobenzene.Particularly preferably use the halogenated hydrocarbon solvent of methylene dichloride and so on.
Pressure in the formation reaction of chloroformate compound is not particularly limited, and normal pressure, pressurization or decompression, it is favourable for usually carrying out at ambient pressure reacting.Temperature of reaction is selected from the scope of-20 ~ 50 DEG C, in most cases, because with reaction heating, so preferably carry out water-cooled or ice-cold.Reaction times affects by other condition, therefore can not specify without exception, usually carries out with 0.2 ~ 10 hour.The pH scope of the formation reaction of chloroformate compound, can utilize known interfacial reaction conditions, pH is prepared as more than 10 usually.
In the manufacture of the polycarbonate-polydiorganosiloxane copolymer resins used as B component of the present invention, obtained like this chloro-formic ester containing dihydric phenol (I) and have end chloroformic acid ester group dihydric phenol (I) carbonate oligomer chloroformate compound mixing solutions after, stir this mixing solutions while add derivative dihydroxyl aryl end polydiorganosiloxane (II) of the carbonic ether Component units that formula (3) represented relative to the amount 1 mole of the dihydric phenol (I) added during this mixing solutions obtained with the speed of 0.01 mole/below min, this dihydroxyl aryl end polydiorganosiloxane (II) and this chloroformate compound is made to carry out interfacial polycondensation, obtain polycarbonate-polydiorganosiloxane copolymer resins thus.
As polycarbonate-polydiorganosiloxane copolymer resins that B component of the present invention uses, can by branching agent and dihydric phenol based compound and with making branching polycarbonate-polydiorganosiloxane copolymer resins.As multi-functional the aromatics more than trifunctional used in above-mentioned branched polycarbonate resin, Phloroglucinol can be enumerated, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, or 4,6-dimethyl-2,4,6-tri-(4-hydroxy phenyl) heptene-2, 2,4,6-trimethylammonium-2,4,6-tri-(4-hydroxy phenyl) heptane, 1,3,5-tri-(4-hydroxy phenyl) benzene, 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenol of 2,6-, 4-{4-[1,1-two (4-hydroxy phenyl) ethyl] benzene } trisphenol of-alpha, alpha-dimethylbenzyl phenol etc., four (4-hydroxy phenyl) methane, two (2,4-dihydroxy phenyl) ketone, Isosorbide-5-Nitrae-bis-(4,4-dihydroxyl trityl group) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acyl chlorides etc., wherein preferred 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, particularly preferably 1,1,1-tri-(4-hydroxy phenyl) ethane.
Method containing branching agent in its mixing solutions when the manufacture method of above-mentioned point of branching polycarbonate-polydiorganosiloxane copolymer resins can be the formation reaction of chloroformate compound, adds the method for branching agent when also can be the interfacial polycondensation reaction after this formation reaction terminates.Derive from the ratio of the carbonic ether Component units of branching agent, in the carbonic ether Component units total amount forming this copolymer resins, be preferably 0.005 ~ 1.5 % by mole, be more preferably 0.01 ~ 1.2 % by mole, be particularly preferably 0.05 ~ 1.0 % by mole.Should illustrate, above-mentioned branched structure amount can be passed through 1h-NMR measures and calculates.
Pressure in the system of polycondensation, decompression, normal pressure or pressurization, usually preferably carry out under the self-pressure degree of normal pressure or reaction system.Temperature of reaction is selected from the scope of-20 ~ 50 DEG C, in most cases, because with polymerization heating, so preferably carry out water-cooled or ice-cold.Reaction times is different according to other conditions such as temperature of reaction, therefore can not specify without exception, usually carries out with 0.5 ~ 10 hour.
According to circumstances, can suitably implement physical treatment (mixing, classification etc.) and/or chemical treatment (polymer reaction, crosslinking Treatment, decomposed process etc.) to the polycarbonate obtained-polydiorganosiloxane copolymer resins and obtain desired reducing viscosity [η sP/ c] polycarbonate-polydiorganosiloxane copolymer resins.
The resultant of reaction (thick resultant) obtained can be implemented the various aftertreatments such as known separation and purification method and reclaim the polycarbonate-polydiorganosiloxane copolymer resins of desired purity (refining degree).
The viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resins used as B component of the present invention is preferably 1.2 × 10 4~ 3.0 × 10 4scope, be more preferably 1.3 × 10 4~ 2.5 × 10 4scope, more preferably 1.5 × 10 4~ 2.5 × 10 4scope.Using the viscosity-average molecular weight as resin combination for 1.2 × 10 4~ 1.3 × 10 4the mode of scope use, if be this scope, then formability when thin molded article is shaping (formability) is particularly excellent, and in addition, physical strength is also good.
Should illustrate, the calculating of the viscosity-average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resins used as B component of the present invention is undertaken by following main points.First, formula viscometer difficult to understand is used to obtain by the solution at 20 DEG C of dissolved polycarbonates in methylene dichloride 100ml-polydiorganosiloxane copolymer resins 0.7g the specific viscosity (η be calculated as follows sP),
Specific viscosity (η sP)=(t-t 0)/t 0
[t 0for the drippage number of seconds of methylene dichloride, t is the drippage number of seconds of sample solution]
By the specific viscosity (η obtained sP) calculate viscosity-average molecular weight Mv by following mathematical expression.
η sP/ c=[η]+0.45 × [η] 2c (wherein, [η] is limiting viscosity)
[η]＝1.23×10 -4Mv 0.83
c＝0.7
The content of the polydiorganosiloxane block that the following formula (5) contained in the following formula (4) contained in B component represents with the gross weight of poly carbonate resin composition for benchmark, be preferably 0.001 ~ 1.0 % by weight, be more preferably 0.01 ~ 0.8 % by weight, more preferably 0.01 ~ 0.5 % by weight, be particularly preferably 0.01 ~ 0.3 % by weight, most preferably be 0.01 ~ 0.2 % by weight.If this ratio is less than 0.001 % by weight, then can not plays aberration in face and improve effect, if more than 1.0 % by weight, then full light transmittance reduces sometimes, cannot obtain guide-lighting performance, therefore not preferred.
(in above-mentioned formula (4), R 3, R 4, R 5, R 6, R 7and R 8be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or the aryl without replacement independently of one another, R 9and R 10be hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 10, the alkoxyl group of carbonatoms 1 ~ 10 independently of one another, p is natural number, and q is 0 or natural number, and p+q is the natural number of less than 150.X is the aliphatic divalent group of carbonatoms 2 ~ 8.)
(in above-mentioned formula (5), R 21, R 22, R 23, R 24, R 25and R 26be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or without the aryl replaced, r is natural number independently of one another, s is 0 or natural number, and r+s is the natural number of less than 150.)
The content of B component relative to polycarbonate resin (A composition) 100 weight parts, preferably 0.01 ~ 10 weight part, more preferably 0.01 ~ 8 weight part, further preferably 0.01 ~ 5 weight part, particularly preferably 0.1 ~ 3 weight part, most preferably 0.1 ~ 2 weight part.If B component is lower than 0.01 weight part, then in opposite, aberration improvement and light conductivity raising do not have effect, if more than 10 weight parts, then full light transmittance reduces sometimes, cannot obtain light conductivity.
(resin combination)
Resin combination of the present invention contains (A) polycarbonate resin (A composition) and (B) polycarbonate-polydiorganosiloxane copolymer resins (B component).
The viscosity-average molecular weight of resin combination of the present invention is 1.2 × 10 4~ 1.3 × 10 4scope, preferably 1.22 × 10 4~ 1.28 × 10 4scope.If viscosity-average molecular weight is more than 1.3 × 10 4, then formability when thin molded article is shaping (formability) is particularly poor, if viscosity-average molecular weight is less than 1.2 × 10 4, then bad mechanical strength.Should illustrate, said viscosity-average molecular weight in the present invention, first use formula viscometer difficult to understand to obtain by the solution at 20 DEG C of dissolving resin composition 0.7g in methylene dichloride 100ml the specific viscosity be calculated as follows, the specific viscosity obtained is substituted into following formula and obtains viscosity-average molecular weight M.
Specific viscosity (η sP)=(t-t 0)/t 0
[t 0for the drippage number of seconds of methylene dichloride, t is the drippage number of seconds of sample solution]
η sP/ c=[η]+0.45 × [η] 2c (wherein, [η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7
(phosphorus system stablizer)
Resin combination of the present invention preferably coordinates phosphorus system stablizer in the degree of not facilitation of hydrolysis.Above-mentioned phosphorus system stablizer improve when manufacturing or forming process time thermostability, improve mechanical characteristics, tone and forming stability.As phosphorus system stablizer, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc. can be illustrated.
In the present invention, in phosphorus system stablizer, preferably use the phosphorus system stablizer that following formula (1) represents.
(in formula (1), A 1, A 2be aryl or alkyl independently of one another, can be the same or different.)
In formula (1), A 1, A 2during for aryl, the aryl of preferred carbonatoms 6 ~ 30, the more preferably aryl of carbonatoms 6 ~ 20, the further aryl of preferred carbonatoms 6 ~ 10.Specifically, dinonylphenyl pentaerythritol diphosphites can be enumerated, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, 4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2, 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two (2, 4-dicumylphenyl) pentaerythritol diphosphites etc., wherein preferred pair (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites.
In formula (1), A 1, A 2during for alkyl, the alkyl of preferred carbonatoms 1 ~ 30, the more preferably alkyl of carbonatoms 6 ~ 30, the further alkyl of preferred carbonatoms 6 ~ 20.Specifically, dioctyl pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, two mountain Yu base pentaerythritol diphosphites etc. can be enumerated.Wherein, preferably distearyl pentaerythrityl diphosphite is used.As the stablizer that C composition of the present invention uses, separately or can be combined two or more and use.
The content of phosphorus system stablizer (C composition) is relative to polycarbonate resin (A composition) 100 weight parts, preferably 0.01 ~ 1.0 weight part, more preferably 0.01 ~ 0.5 weight part, preferred 0.01 ~ 0.3 weight part further, particularly preferably 0.01 ~ 0.1 weight part, most preferably 0.01 ~ 0.05.If the content of C composition is more than 1.0 weight parts, then have generation mold deposit, to cost also disadvantageous trend, in addition, when being less than 0.01 weight part, tone improves effect and diminishes sometimes.
(other additive)
In order to improve the flame retardant resistance of resin combination of the present invention, light diffusing, oxidation-resistance, light stability (UV stable), fluorescent brightening, release property and mould corrosion, advantageously use the additive used in these improvement.Below these additives are specifically described.
(I) fire retardant
Known various compounds can be coordinated in resin combination of the present invention as the fire retardant of polycarbonate resin.The cooperation of above-claimed cpd brings the raising of flame retardant resistance, in addition, based on the character of each compound, also brings the raising etc. of such as static resistance, mobility, rigidity and thermostability.As above-mentioned fire retardant, (i) organic metal salt flame retardant (such as organic sulfonic acid alkali (soil) metal-salt can be enumerated, organic boronic metal-salt flame retardant and organotin acid metal salt flame retardant etc.), (ii) organic phosphorus flame retardant (such as, containing the phosplate compound of organic group, phosphoric acid ester oligomer compounds, phosphonate oligomers compound, phosphazene oligomer compound and Phosphoramido compounds etc.), (iii) silicone flame retardant be made up of silicoorganic compound, (iv) fibrillation PTFE, wherein preferred organic metal salt flame retardant, organic phosphorus flame retardant.
(i) organic metal salt flame retardant
Organometalate compound be preferably carbonatoms 1 ~ 50, preferably 1 ~ 40 organic acid alkali (soil) metal-salt, be preferably organic sulfonic acid alkali (soil) metal-salt.The metal-salt of the fluorine substituted alkyl sulfonic acid of carbonatoms 1 ~ 10, the preferably perfluoro alkyl sulfonic acid of 2 ~ 8 and the metal-salt of basic metal or alkaline-earth metal and so on is comprised in this organic sulfonic acid alkali (soil) metal-salt, and the metal-salt of the aromatic sulphonic acid of carbonatoms 7 ~ 50, preferably 7 ~ 40 and basic metal or alkaline-earth metal.As the basic metal forming metal-salt, lithium, sodium, potassium, rubidium and caesium can be enumerated, as alkaline-earth metal, beryllium, magnesium, calcium, strontium and barium can be enumerated.Be more preferably basic metal.In above-mentioned basic metal, when the transparency requires higher, the rubidium that preferred ion radius is larger and caesium, on the other hand, these metals are not general and are difficult to refine, and therefore result is sometimes unfavorable in cost.On the other hand, the metal of the ionic radius that lithium and sodium etc. are less is contrary sometimes unfavorable in flame retardant resistance.Consider that these factors can use the basic metal in sulfonic acid alkali metal salts respectively, the most preferably sulfonic acid potassium salt of the balancing good of all aspect characteristics.Can be used together above-mentioned sylvite and the sulfonic acid alkali metal salts be made up of other basic metal.
As the concrete example of perfluoro alkyl sulfonic acid an alkali metal salt, can enumerate trifluoromethanesulfonic acid potassium, potassium perfluor butane sulfonate, the own potassium sulfonate of perfluor, perfluorooctane sulfonate potassium, five fluorine ethyl sulfonic acid sodium, perfluor fourth sodium sulfonate, perfluorooctane sulfonate sodium, trifluoromethanesulfonic acid lithium, perfluor fourth Sulfonic Lithium, perfluor Sulfonic Lithium in heptan, trifluoromethanesulfonic acid caesium, perfluor fourth sulfonic acid caesium, perfluorooctane sulfonate caesium, perfluor own sulfonic acid caesium, perfluor fourth sulfonic acid rubidium and the own sulfonic acid rubidium of perfluor etc., these can be used alone or in combination with two or more kinds.
Here the carbonatoms of perfluoroalkyl preferably 1 ~ 18 scope, the more preferably scope of 1 ~ 10, further preferably 1 ~ 8 scope.Wherein, particularly preferably potassium perfluor butane sulfonate.In perfluoro alkyl sulfonic acid alkali (soil) metal-salt be made up of basic metal, usually there are many fluoride ion (F -) be mixed into.The existence of above-mentioned fluoride ion may become the important factor reducing flame retardant resistance, preferably reduces as far as possible.The ratio of above-mentioned fluoride ion can pass through ion-chromatographic determination.Preferred below the 100ppm of content of fluoride ion, further preferred below 40ppm, particularly preferably below 10ppm.In addition, from the viewpoint of preferred more than the 0.2ppm of manufacture efficiency.Above-mentioned perfluoro alkyl sulfonic acid alkali (soil) metal-salt decreasing fluoride ion amount can manufacture by the following method: manufacture method can use known manufacture method, and reduces the method for the amount of the fluoride ion contained in raw material when manufacturing fluorine-containing organic metal salt; By reaction time produce gas, add the method for heat extraction by the hydrogen fluoride be obtained by reacting etc.; And use the process for purification such as recrystallization and redeposition to reduce the method etc. of the amount of fluoride ion when manufacturing fluorine-containing organic metal salt.Particularly because organic metal salt flame retardant ratio is easier to water-soluble, so can manufacture preferably by following operation, namely, use ion exchanged water, particularly meet the water that resistance value is about 0.55 below μ S/cm for 18M more than Ω cm i.e. specific conductivity, and make it dissolve at higher than the temperature of normal temperature to clean, cool thereafter and make its recrystallization.
As the concrete example of aromatic sulphonic acid alkali (soil) metal-salt, such as, can enumerate diphenylsulfide-4,4 '-disulfonate, diphenylsulfide-4,4 '-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalate, 1-methoxynaphthalene-4-calcium sulphonate, 4-dodecylphenyl ether disulfonate, poly-(2,6-dimethyl phenylate) many sodium of many sulfonic acid, the poly-many sodium of (1,3-phenylate) many sulfonic acid, the poly-many sodium of (Isosorbide-5-Nitrae-phenylate) many sulfonic acid, poly-(2,6-phenylbenzene phenylate) many potassium of many sulfonic acid, poly-(2-fluoro-6-butyl phenylate) many Sulfonic Lithiums, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, xenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, BP-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonate, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, the formaldehyde condensation products of sodium naphthalene sulfonate and the formaldehyde condensation products etc. of anthracene sulfonic acid sodium.In these aromatic sulphonic acid alkali (soil) metal-salts, particularly preferably sylvite.In these aromatic sulphonic acid alkali (soil) metal-salts, preferred sulfobenzide-3-potassium sulfonate and sulfobenzide-3,3 '-disulfonic acid dipotassium, particularly preferably their mixture (weight ratio of the former with the latter is 15/85 ~ 30/70).
As the organic metal salt beyond azochlorosulfonate acid alkali (soil) metal-salt, preferably illustrate alkali (soil) metal-salt of sulfuric ester and alkali (soil) metal-salt etc. of aromatic sulfonamide.As alkali (soil) metal-salt of sulfuric ester, alkali (soil) metal-salt of the sulfuric ester of unitary and/or polyalcohols can be enumerated especially, as above-mentioned unitary and/or polyalcohols sulfuric ester, can enumerate methylsulfuric acid ester, ethylsulfuric acid ester, lauryl sulfate ester, hexadecyl hydrosulfate ester, the sulfuric ester of polyoxy vinyl alkyl phenyl ether, tetramethylolmethane single, two, three, four sulfuric esters, the sulfuric ester of lauric monoglyceride, the sulfuric ester of hexadecanoic acid direactive glyceride and glyceryl monostearate sulfuric ester etc.As alkali (soil) metal-salt of these sulfuric esters, alkali (soil) metal-salt of lauryl sulfate ester preferably can be enumerated.As alkali (soil) metal-salt of aromatic sulfonamide, such as, can enumerate alkali (soil) metal-salt etc. of asccharin, N-(p-toluenesulfonyl)-tolysulfonyl imines, N-(N '-benzylaminocarbonyl) sulfanilyl-imines and N-(phenylcarboxy) sulfanilyl-imines.The content of organic metal salt flame retardant is relative to polycarbonate resin (A composition) 100 weight parts, be preferably 0.001 ~ 1 weight part, be more preferably 0.005 ~ 0.5 weight part, more preferably 0.01 ~ 0.3 weight part, be particularly preferably 0.03 ~ 0.15 weight part.
(ii) organic phosphorus flame retardant
As organic phosphorus flame retardant, preferred aryl groups phosphate compound.This is because this phosphate compound is all excellent hue.In addition, phosphate compound has plasticization effect, so be favourable in raising molding processibility.Above-mentioned phosphate compound, can use in the past as the known various phosphate compound of fire retardant.The use level of organic phosphorus flame retardant, relative to polycarbonate resin (A composition) 100 weight parts, is preferably 0.01 ~ 20 weight part, is more preferably 2 ~ 10 weight parts, more preferably 2 ~ 7 weight parts.
(iii) silicone flame retardant
As the silicoorganic compound that silicone flame retardant uses, improve flame retardant resistance by chemical reaction during burning.As this compound, can use in the past as the various compounds that the fire retardant of aromatic polycarbonate resin proposes.Think silicoorganic compound when it burns itself bonding or with the composition bonding deriving from resin and form structure, or reduction reaction when being formed by this structure, gives flame retardant effect to polycarbonate resin.Therefore the group that the activity preferably containing above-mentioned reaction is high, more specifically, at least a kind of group be selected from alkoxyl group and hydrogen (i.e. Si-H group) preferably containing specified amount.As above-mentioned group (alkoxyl group, Si-H yl) containing proportional, the preferably scope of 0.1 ~ 1.2mol/100g, the more preferably scope of 0.12 ~ 1mol/100g, the further scope of preferred 0.15 ~ 0.6mol/100g.Aforementioned proportion utility alkali decomposition method is obtained by the amount of the hydrogen or alcohol that measure the generation of silicoorganic compound per unit weight.Should illustrate, the alkoxyl group of the preferred carbonatoms 1 ~ 4 of alkoxyl group, particularly preferably methoxyl group.The structure of general silicoorganic compound is consisted of arbitrary combination 4 kinds of siloxane units shown below.That is, M unit: (CH 3) 3siO 1/2, H (CH 3) 2siO 1/2, H 2(CH 3) SiO 1/2, (CH 3) 2(CH 2=CH) SiO 1/2, (CH 3) 2(C 6h 5) SiO 1/2, (CH 3) (C 6h 5) (CH 2=CH) SiO 1/2deng 1 functional silicone's unit, D unit: (CH 3) 2siO, H (CH 3) SiO, H 2siO, H (C 6h 5) SiO, (CH 3) (CH 2=CH) SiO, (C 6h 5) 2siO etc. 2 functional silicone unit, T unit: (CH 3) SiO 3/2, (C 3h 7) SiO 3/2, HSiO 3/2, (CH 2=CH) SiO 3/2, (C 6h 5) SiO 3/2deng 3 functional silicone's unit, Q unit: SiO 2the 4 functional silicone's unit represented.The structure of the silicoorganic compound used in silicone flame retardant, specifically, can enumerate Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, DnTpQq as rational formula.Wherein the structure of preferred silicoorganic compound is MmDn, MmTp, MmDnTp, MmDnQq, and preferred structure is MmDn or MmDnTp.
Here, the Coefficient m in above-mentioned rational formula, n, p, q are the integer of more than 1 of the polymerization degree representing each siloxane unit, the mean polymerisation degree adding up to silicoorganic compound of the coefficient in each rational formula.This mean polymerisation degree is preferably the scope of 3 ~ 150, is more preferably the scope of 3 ~ 80, more preferably the scope of 3 ~ 60, is particularly preferably the scope of 4 ~ 40.In above-mentioned preferred scope, flame retardant resistance is more excellent.In addition, as described later, the transparency in the silicoorganic compound of the aromatic group containing specified amount, tone is also excellent.Its result obtains good reflected light.In addition, when any one in m, n, p, q is the numerical value of more than 2, the siloxane unit with this coefficient can be the hydrogen atom of bonding, siloxane unit of more than two kinds that organic residue is different.
Silicoorganic compound can be straight-chain, also can have branched structure.In addition, be preferably carbonatoms 1 ~ 30 with the organic residue of silicon atom bonding, be more preferably the organic residue of 1 ~ 20.As above-mentioned organic residue, specifically, the alkyl such as methyl, ethyl, propyl group, butyl, hexyl and decyl can be enumerated, the cycloalkyl of cyclohexyl and so on, the aralkyl of the aryl and tolyl and so on of phenyl and so on.The more preferably alkyl of carbonatoms 1 ~ 8, alkenyl or aryl.As alkyl, the particularly preferably alkyl of the carbonatoms 1 ~ 4 such as methyl, ethyl and propyl group.In addition, the silicoorganic compound used as silicone flame retardant preferably contain aryl.On the other hand, the aspect that never can obtain preferred effect containing aryl is considered, is distinguished clearly in its preferred mode as the silane compound of the organic surface treatment of TiO 2 pigment and silicone compounds and silicone flame retardant.The silicoorganic compound used as silicone flame retardant also can contain reactive group except above-mentioned Si-H base and alkoxyl group, as this reactive group, such as, can illustrate amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and methacryloxy etc.
The use level of silicone flame retardant, relative to polycarbonate resin (A composition) 100 weight parts, is preferably 0.01 ~ 20 weight part, is more preferably 0.5 ~ 10 weight part, more preferably 1 ~ 5 weight part.
(iv) there is the tetrafluoroethylene (fibrillation PTFE) of protofibril Forming ability
Fibrillation PTFE can be independent fibrillation PTFE, also can be the tetrafluoroethylene system mixture that namely the fibrillation PTFE of mixed style is made up of fibrillation PTFE particle and organic based polymer.Fibrillation PTFE has high molecular weight, shows and by external influences such as shearing forces, PTFE is bonded together and become fibrous trend.Its number-average molecular weight is 1,500,000 ~ several scope of ten million.Its lower limit is more preferably 3,000,000.This number-average molecular weight is disclosed in Japanese Unexamined Patent Publication 6-145520 publication, and the melt viscosity based on the tetrafluoroethylene at 380 DEG C calculates.That is, the melt viscosity of 380 DEG C utilizing the method recorded in above-mentioned publication to measure of the fibrillation PTFE of B component is the scope of 107 ~ 1013poise, is preferably the scope of 108 ~ 1012poise.Above-mentioned PTFE, except solid shape, can also use with aqueous liquid dispersion form.In addition, in order to improve the dispersiveness of above-mentioned fibrillation PTFE in resin, obtaining better flame retardant resistance and mechanical characteristics, also can use the PTFE mixture with the mixed style of other resin.In addition, have preferably utilizing disclosed in Japanese Unexamined Patent Publication 6-145520 publication with above-mentioned fibrillation PTFE be core, with the material of the low-molecular-weight tetrafluoroethylene structure that is shell.
As the commercially available product of above-mentioned fibrillation PTFE, such as can enumerate Polyflon MPA FA500, F-201L etc. of Teflon (registered trademark) 6J, Daikin Chemical Industry Co., Ltd. of Du Pont-Mitsui Fluorochemicals Co., Ltd..As the fibrillation PTFE of mixed style, the fibrillation PTFE obtained by the following method can be used, namely the aqueous liquid dispersion of fibrillation PTFE and the aqueous liquid dispersion of organic polymer or solution mix and carry out co-precipitation and obtain method (the Japanese Laid-Open Patent Publication 60-258263 publication of common cohesion mixture by (1), the method recorded in Japanese Laid-Open Patent Publication 63-154744 publication etc.), (2) aqueous liquid dispersion of fibrillation PTFE and the method (method recorded in Japanese Unexamined Patent Publication 4-272957 publication) of dry organic polymer particle is mixed, (3) by the aqueous liquid dispersion of fibrillation PTFE and the mixing of organic polymer particle dissolution homogeneity, remove method (the Japanese Unexamined Patent Publication 06-220210 publication of respective medium from this mixture simultaneously, the method recorded in Japanese Unexamined Patent Publication 08-188653 publication etc.), (4) method (method recorded in Japanese Unexamined Patent Publication 9-95583 publication) of the monomer polymerization of organic polymer will be formed with in the aqueous liquid dispersion of fibrillation PTFE, and (5) are by after the aqueous liquid dispersion of PTFE and organic polymeric disperse liquid Homogeneous phase mixing, again in this mixed dispersion liquid by ethene base system monomer polymerization, thereafter the method (method recorded in Japanese Unexamined Patent Publication 11-29679 publication etc.) of mixture is obtained.As the commercially available product of the fibrillation PTFE of these mixed styles, " METABLEN A3000 " (trade(brand)name) " METABLEN A3700 " (trade(brand)name), " METABLEN A3800 " METABLEN A series representated by (trade(brand)name) of Mitsubishi Rayon Co., Ltd. can be illustrated, the SN3300B7 (trade(brand)name) of Shine Polymer company, and GE Specialty Chemicals Inc. " BLENDEX B449 " (trade(brand)name) etc.
As the ratio of the fibrillation PTFE in mixed style, in said mixture 100 % by weight, preferred fibrillation PTFE is 1 % by weight ~ 95 % by weight, is more preferably 10 % by weight ~ 90 % by weight, most preferably is 20 % by weight ~ 80 % by weight.
The ratio of the fibrillation PTFE in mixed style, when above-mentioned scope, can realize the good dispersiveness of fibrillation PTFE.The use level of fibrillation PTFE, relative to polycarbonate resin (A composition) 100 weight parts, is preferably 0.001 ~ 0.2 weight part, is more preferably 0.01 ~ 0.2 weight part, more preferably 0.01 ~ 0.18 weight part.Should illustrate, the weight of mixture entirety when the weight part here represents that tetrafluoroethylene is mixed style (mixture).
(II) light diffusing agent
Can coordinate in resin combination of the present invention as the known various compounds of the light diffusing agent of polycarbonate resin.In addition, as light diffusing agent, can be the organic system particulate representated by high molecular particle and any one in inorganic system particulate.As high molecular particle, illustrate crosslinked particle non-crosslinked monomer and cross-linkable monomer polymerization obtained typically.Other that can also use beyond above-mentioned monomer can the monomer of copolymerization.
Wherein, preferred high molecular particle, particularly preferably uses crosslinked particle.In above-mentioned crosslinked particle, as the monomer being used as non-crosslinked monomer, non-crosslinked sex ethylene base system monomer and the olefinic monomers etc. such as acrylic monomer, styrenic monomers, acrylic monomer can be enumerated.
As acrylic monomer, following monomer can be used alone or as a mixture, that is, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-EHA, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate and phenyl methacrylate etc.Wherein particularly preferably methyl methacrylate.
In addition, as styrenic monomers, following monomer can be used, namely, the ring-alkylated styrenes such as vinylbenzene, alpha-methyl styrene, vinyl toluene (Vinyl toluene) and ethyl styrene, and the halogenated styrenes of brominated styrene and so on, particularly preferably vinylbenzene.
As acrylic monomer, vinyl cyanide and methacrylonitrile can be used.In addition, as olefinic monomers, ethene and various norbornene-type compounds etc. can be used.
Further, can other monomer of copolymerization as other, glycidyl methacrylate, N-methylmaleimido and maleic anhydride etc. can be illustrated.As a result, organic crosslinked particle of the present invention also can have the unit of N-polydimethyl glutarimide and so on.
On the other hand, as the cross-linkable monomer relative to above-mentioned non-crosslinked sex ethylene base system monomer, such as, Vinylstyrene can be enumerated, allyl methacrylate(AMA), triallyl cyanurate, isocyanic acid triallyl, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, propylene glycol (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, TriMethylolPropane(TMP) (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, bicyclopentyl two (methyl) acrylate, dicyclopentenyl two (methyl) acrylate and N-methylol (methyl) acrylamide etc.
The median size of the light diffusing agent used in the present invention is preferably 0.01 ~ 50 μm, is more preferably 1 ~ 30 μm, more preferably 2 ~ 30 μm.Median size is less than 0.01 μm or more than 50 μm, then light diffusing is not enough sometimes.Above-mentioned median size is the particle diameter represented by 50% value (D50) of the cumulative distribution of the granularity obtained by laser diffraction and scattering method.The distribution of particle diameter can be single also can be multiple.Namely can the different light diffusing agent of more than two kinds of combination average particle diameter.But its narrow diameter distribution of preferred light diffusing agent.More preferably there is the distribution containing more than 70 % by weight of particle in the scope of 2 μm, the front and back of median size.From the view point of light diffusing, the shape of light diffusing agent is preferably close to spherical, and more close just spherical form is more preferred.Above-mentionedly spherically comprise oval ball.
The specific refractory power of the light diffusing agent used in the present invention is preferably the scope of 1.30 ~ 1.80 usually, is more preferably 1.33 ~ 1.70, more preferably the scope of 1.35 ~ 1.65.They play sufficient light diffusion function being engaged under the state in resin combination.
The content of the light diffusing agent used in the present invention is relative to polycarbonate resin (A composition) 100 weight parts, be preferably 0.005 ~ 10.0 weight part, be more preferably 0.1 ~ 10.0 weight part, more preferably 0.1 ~ 5.0 weight part, be particularly preferably 0.1 ~ 2.0 weight.
(III) the phosphorus system stablizer beyond C composition
Resin combination of the present invention can coordinate the phosphorus system stablizer beyond C composition in the degree of not facilitation of hydrolysis.Above-mentioned phosphorus system stablizer improve when manufacturing or forming process time thermostability, improve mechanical characteristics, tone and forming stability.As phosphorus system stablizer, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc. can be illustrated.
Specifically, as bi-ester of phosphite, such as, triphenyl can be used, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite decyl ester, tricresyl phosphite octyl group ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid dioctyl list phenylester, phosphorous acid di-isopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, phosphorous acid list octyl diphenyl, 2, 2-methylene-bis (4, 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, tricresyl phosphite (diethyl phenyl) ester, tricresyl phosphite (diisopropyl phenyl) ester, tricresyl phosphite (di-n-butyl phenyl) ester, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, 6-di-tert-butyl-phenyl) ester, in addition, as other bi-ester of phosphite, can use and react with divalence phenols and there is the bi-ester of phosphite of ring texture.Such as, can 2 be enumerated, 2 '-methylene-bis (4,6-di-tert-butyl-phenyl) (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-ethylenebis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester etc.
As phosphate compound, tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl tolyl phosphate, diphenyl phosphate list adjacent Biphenyl Ester, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc. can be enumerated, preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound, four (2 can be enumerated, 4-di-tert-butyl-phenyl)-4, 4 '-biphenylen, four (2, 4-di-tert-butyl-phenyl)-4, 3 '-biphenylen, four (2, 4-di-tert-butyl-phenyl)-3, 3 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-4, 4 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-4, 3 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-3, 3 '-biphenylen, two (2, 4-di-tert-butyl-phenyl)-4-phenyl-phenyl phosphinate, two (2, 4-di-tert-butyl-phenyl)-3-phenyl-phenyl phosphinate, two (2, 6-di-n-butyl phenyl)-3-phenyl-phenyl phosphinate, two (2, 6-di-tert-butyl-phenyl)-4-phenyl-phenyl phosphinate, two (2, 6-di-tert-butyl-phenyl)-3-phenyl-phenyl phosphinate etc., preferably four (di-tert-butyl-phenyl)-biphenylen, two (di-tert-butyl-phenyl)-phenyl-phenyl phosphinate, more preferably four (2, 4-di-tert-butyl-phenyl)-biphenylen, two (2, 4-di-tert-butyl-phenyl)-phenyl-phenyl phosphinate.The bi-ester of phosphite that this phosphinate compound can have an aryl of replacement more than 2 alkyl with above-mentioned use, therefore preferably.
As phosphonate compound, phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc. can be enumerated.As tertiary phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutylphenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three p-methylphenyl phosphines, three naphthyl phosphines and diphenylbenzyl phosphine etc. can be illustrated.Particularly preferred tertiary phosphine is triphenylphosphine.Above-mentioned phosphorus system stablizer, not only can use a kind, can also mix two or more and use.The alkyl acid phosphate ester cpds representated by tricresyl phosphate methyl ester is preferably coordinated in above-mentioned phosphorus system stablizer.In addition, above-mentioned alkyl acid phosphate ester cpds and bi-ester of phosphite and/or phosphinate compound and with being also preferred mode.
(IV) hindered phenol system stablizer
Hindered phenol system stablizer can also be coordinated in resin combination of the present invention.Above-mentioned cooperation can play the effect of tone deterioration when such as suppressing forming process, the tone deterioration in long-time use etc.As hindered phenol system stablizer, such as, alpha-tocopherol can be illustrated, butylhydroxy toluene, sinapyl alcohol, vitamin-E, Octadecane base-β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 2,6-di-t-butyl-4-(N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester diethyl ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-methylene-bis (2,6 di t butyl phenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-dimethylene-bis-(6-Alpha-Methyl-benzyl-p-cresol) 2,2 '-ethylidene-bis-(4,6-DI-tert-butylphenol compounds), 2,2 '-butylidene-bis-(4-methyl-6-tert-butylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triethylene glycol-N-, 1,6-hexylene glycol two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two [the 2-tertiary butyl-4-methyl 6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, two { 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1,1 ,-dimethyl ethyl }-2,4,8,10-tetra-oxaspiro [5, the 5] undecanes of 3,9-, 4,4 '-thiobis (the 6-tertiary butyl-meta-cresol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, 4,4 '-two-thiobis (2,6 di t butyl phenol), 4,4 '-trithio two (2,6 di t butyl phenol), 2,2-thiodiethylene is two-and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two (n-octyl the sulphur)-6-of 2,4-(4-hydroxyl-3 ', 5 '-di-tert-butyl amido)-1,3,5-triazines, N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), N, N '-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 1,3,5-32 [3 (3,5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl isocyanurate and four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all easily obtain.Above-mentioned hindered phenol system stablizer separately or can combine two or more and use.
The use level of phosphorus system stablizer and hindered phenol system stablizer, relative to polycarbonate resin (A composition) 100 weight parts, is preferably 0.0001 ~ 1 weight part, is more preferably 0.001 ~ 0.5 weight part, more preferably 0.005 ~ 0.3 weight part.
(V) thermo-stabilizer other than the above
Other thermo-stabilizer beyond above-mentioned phosphorus system stablizer and hindered phenol system stablizer can be coordinated in resin combination of the present invention.As other thermo-stabilizer above-mentioned, such as, preferably illustrate the lactone system stablizer representated by resultant of reaction of 3-hydroxyl-5,7-di-t-butyls-furans-2-ketone and o-Xylol.The detailed content of aforementioned stable agent is documented in Japanese Unexamined Patent Publication 7-233160 publication.Above-claimed cpd has commercially available as Irganox HP-136 (trade mark, CIBA SPECIALTY CHEMICALS Inc.), can utilize this compound.In addition the stablizer that this compound and various bi-ester of phosphite and hindered phenol compound mix also is had commercially available.Such as preferably illustrate the IrganoxHP-2921 of above-mentioned Inc..The use level of lactone system stablizer is preferably 0.0005 ~ 0.05 weight part relative to polycarbonate resin (A composition) 100 weight parts, is more preferably 0.001 ~ 0.03 weight part.
In addition, as other stablizer, the sulphur-containing stabilizers such as tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl-thio propionic ester can be illustrated.The use level of above-mentioned sulphur-containing stabilizer is preferably 0.001 ~ 0.1 weight part relative to polycarbonate resin (A composition) 100 weight parts, is more preferably 0.01 ~ 0.08 weight part.
Epoxy compounds can be coordinated as required in resin combination of the present invention.This epoxy compounds coordinates for suppressing the object of mould corrosion, substantially can use all compounds with epoxy-functional.As the concrete example of preferred epoxy compounds, can 3 be enumerated, 4-epoxycyclohexyl-methyl-3 ', 4 '-epoxycyclohexyl manthanoate, 2, the multipolymer etc. of the multipolymer of 1,2-epoxy-4-(2-epoxy ethyl) hexanaphthene affixture, methyl methacrylate and the glycidyl methacrylate of two (the hydroxymethyl)-n-butyl alcohol of 2-, vinylbenzene and glycidyl methacrylate.As the addition of above-mentioned epoxy compounds, relative to polycarbonate resin (A composition) 100 weight parts, be preferably 0.003 ~ 0.2 weight part, be more preferably 0.004 ~ 0.15 weight part, more preferably 0.005 ~ 0.1 weight part.
(VI) UV light absorber
Can combined with ultraviolet radiation absorption agent for the purpose of photostabilization to give in resin combination of the present invention.As UV light absorber, specifically, in benzophenone series, such as, can 2 be illustrated, 4-dihydroxy benaophenonel, ESCALOL 567, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-behzyloxybenzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone, 2, 2 '-dihydroxyl-4-methoxy benzophenone, 2, 2 ', 4, 4 '-tetrahydroxybenzophenone, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-benzophenone, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-5-benzophenone sulfonic acids sodium, two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane, 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.
As UV light absorber, specifically, in benzotriazole system, such as, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole can be illustrated, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-) benzotriazole, 2-(2-hydroxyl-3,5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2,2 '-methylene-bis [4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol], 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-bis--tert-pentyl phenyl) benzotriazole, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2′ p phenylenebis (1,3-benzo piperazine-4-ketone) and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydric phthalimide methyl)-5-aminomethyl phenyl] benzotriazole and 2-(2 '-hydroxy-5-methyl base acryloyl-oxyethyl phenyl)-2H-benzotriazole with can with the multipolymer of the ethene base system monomer of this monomer copolymerization or 2-(2 '-hydroxyl-5-acryloyl-oxyethyl phenyl)-2H-benzotriazole with can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer etc. of the ethene base system monomer of this monomer copolymerization.
As UV light absorber, specifically, in hydroxyphenyltriazinuv system, such as, 2-(4 can be illustrated, 6-phenylbenzene-1,3,5-triazines-2-base)-5-hexyl oxygen base phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-methyl oxygen base phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-ethyl oxygen base phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-propyl group oxygen base phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-base)-5-butyl oxygen base phenol etc.The phenyl that also can illustrate the above-mentioned exemplary compounds such as 2-(two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-base of 4,6-)-5-hexyl oxygen base phenol becomes the compound of 2,4-3,5-dimethylphenyls.
As UV light absorber, specifically, in cyclic imide ester system, such as, can illustrate 2,2 '-TOPOT 2,2′ p phenylenebis (3,1-benzo piperazine-4-ketone), 2, two (3, the 1-benzo of 2 '-metaphenylene piperazine-4-ketone) and 2,2 '-p, p ' two (3, the 1-benzo of-diphenylene piperazine-4-ketone) etc.
In addition; as UV light absorber; specifically, in cyanoacrylate system, such as, can illustrate 1; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylacryloyl) oxygen base]-2,2-two [(2-cyano group-3,3-diphenylacryloyl) oxygen base] methyl) propane and 1; 3-pair-[(2-cyano group-3,3-diphenylacryloyl) oxygen base] benzene etc.
In addition, above-mentioned UV light absorber also can be the structure of the monomeric compound by obtaining free redical polymerization, thus makes the monomer of above-mentioned ultra-violet absorbing monomers and/or light stability monomer and alkyl (methyl) acrylate etc. carry out the UV light absorber of the polymer-type of copolymerization.As above-mentioned ultra-violet absorbing monomers, the compound containing benzotriazole skeleton, benzophenone skeletal, triazine skeleton, cyclic imide ester skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate preferably can be illustrated in.From the viewpoint of ultraviolet absorption ability, preferred benzotriazole system and hydroxyphenyltriazinuv system in above-claimed cpd, from the viewpoint of thermotolerance, tone, preferred cyclic imide ester system and cyanoacrylate system.Specifically, CHEMIPRO KASEI Co., Ltd. " KEMISORB 79 " etc. can such as be enumerated.Above-mentioned UV light absorber can be used alone or uses with mixture of more than two kinds.The use level of UV light absorber is preferably 0.01 ~ 2 weight part relative to polycarbonate resin (A composition) 100 weight parts, is more preferably 0.02 ~ 2 weight part, more preferably 0.03 ~ 1 weight part, is particularly preferably 0.05 ~ 0.5 weight part.
(VII) white dyes
As long as white dyes is just not particularly limited for the white dyes tone of resin etc. being improved as white or pearl opal in resin combination of the present invention, such as, can enumerate Stilbene system, benzoglyoxaline system, benzo azoles system, naphthalimide system, rhodamine system, coumarin series, piperazine based compound etc.Specifically, CI Fluorescent Brightener 219:1, Eastman Chemical Inc. EASTOBRITE OB-1, Hakkol Chemical Co., Ltd. system " Hakkol PSR " etc. can such as be enumerated.Here, white dyes has the energy of light-absorbing ultraviolet portion and is the effect of visible part by this power radiation.The content of white dyes, relative to polycarbonate resin (A composition) 100 weight parts, is preferably 0.001 ~ 0.1 weight part, is more preferably 0.001 ~ 0.05 weight part.Even if more than 0.1 weight part, the improved effect of the tone of said composition is also little.
(VIII) other
Than that described above, can small proportion coordinate for giving various function to products formed, improving itself known additive of characteristic in resin combination of the present invention.These additives only otherwise damage object of the present invention, can be just common use levels.As above-mentioned additive, strengthening weighting agent, antiseize paste (such as PTFE particle), tinting material, fluorescence dye, inorganic system fluor (being such as the fluor of parent crystal with aluminate), static inhibitor, nucleator, inorganic and organic antiseptic-germicide, photocatalyst system stain control agent (such as particulate titanium dioxide, particulate oxide zinc), releasing agent, flow ability modifying agent, free-radical generating agent, infrared absorbent (hot line absorption agent) and photochromic agent etc. can be enumerated.
Resin combination of the present invention, can use the forcing machine of single axle extruding machine, biaxial extruder and so on to carry out melting mixing and granulating.When making above-mentioned particle, above-mentioned various fire retardant, strengthening weighting agent, additive can be coordinated.Resin combination of the present invention can manufacture various goods by shaping for the injecting particles manufactured as mentioned above usually.Also sheet, film, special-shaped extrusion molding article, directly blow molding product and injection-molded article will can not directly be made with the resin of forcing machine melting mixing via particle in addition.In above-mentioned injection molding, be not only common forming method, suitably can also use injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprise utilize the injection of supercutical fluid to carry out shaping), shaping, the heat insulation mould molding of insert moulding, in-mould coating according to object, rapid heating cooling die is shaping, dual-color forming, sandwich are shaping and the injection moulding such as ultra-high speed injection molding obtains products formed.The advantage of these various methods of forming is widely known by the people.In addition, any one can selection in cold runner mode and hot runner mode shaping.In addition, resin combination of the present invention can be used with the form of various special-shaped extrusion molding article, sheet and film etc. by extrusion moulding.In addition, sheet, the shaping of film also can use inflation method, rolling process, casting etc.In addition, heat-shrinkable tube can be shaped to by applying specific stretched operation.In addition, can utilize rotoforming, blow molding etc. that resin combination of the present invention is made products formed.
(manufacture about resin combination)
When manufacturing resin combination of the present invention, arbitrary method can be adopted.Such as following methods can be enumerated; namely; by A composition, B component and arbitrarily other composition use V-Mixer, Henschel mixer, mechanochemistry device respectively, extrude after the ready-mixed modes such as mixing machine fully mix; extruding pelletization device, briquetting press etc. is utilized to carry out granulation as required; thereafter carry out melting mixing with the melting mixing machine representated by exhaust biaxial extruder, and utilize the machines such as tablets press to carry out granular method.
(manufacture of light guiding plate)
When manufacturing the light guiding plate be made up of resin combination of the present invention, arbitrary method can be adopted.Such as can with forcing machine, Banbury mixer and roller etc. this resin combination is carried out mixing after, shaping by known methods such as injection molding, extrusion moulding or compressed mouldings, obtain light guiding plate.In addition, light source can be set by least one side at this light guiding plate, at the one side of this light guiding plate, reflector be set to make surface light source unit.As the light source of above-mentioned light guiding plate and surface light source unit, except luminescent lamp, the self-luminous bodies such as cold-cathode tube, LED, laser diode, organic EL can also be used.Light guiding plate of the present invention and surface light source unit use in the lamp of mobile telephone, mobile terminal, photographic camera, clock and watch, notebook computer, indicating meter, illumination, signal, automobile, the display unit of household electrical appliances optical apparatus etc.Particularly as using when requiring flame retardant resistance etc. to peripheral equipment as the LED of motor goods as light source, preferred light guiding plate of the present invention and surface light source unit.
In the present invention, the above-mentioned aromatic copolycarbonate resin composition having guide-lighting performance highly and high workability concurrently can be used, utilize injection moulding by the forming light guide plate of the light guiding plate of thin-walled, particularly mobile telephone, mobile terminal etc.Specifically, can be 50 ~ 130mm by the length of the long side direction of light guiding plate, to account for the thickness in the region of at least 80% of light guiding plate be the forming light guide plate of 0.2 ~ 0.4mm.In addition, the shape of prism can be given in the one side of light guiding plate, the convex or concave shape in contrary face imparting arc-shaped.The excellence such as formability, products appearance, intensity, brightness of light guiding plate of the present invention.
Embodiment
Below enumerate embodiment to further illustrate, but the present invention is not limited thereto.Should illustrate, as the project below Evaluation operation.
1. the evaluation of polycarbonate-polydiorganosiloxane copolymer resins (B component)
(1) viscosity-average molecular weight (Mv)
Formula viscometer difficult to understand is used to be obtained the specific viscosity (η be calculated as follows by the solution at 20 DEG C of dissolved polycarbonate in methylene dichloride 100ml-polydiorganosiloxane copolymer resinses sP),
Specific viscosity (η sP)=(t-t 0)/t 0
[t 0for the drippage number of seconds of methylene dichloride, t is the drippage number of seconds of sample solution]
By the specific viscosity (η obtained sP) calculate viscosity-average molecular weight Mv by following mathematical expression.
η sP/ c=[η]+0.45 × [η] 2c (wherein, [η] is limiting viscosity)
[η]＝1.23×10 -4Mv 0.83
c＝0.7
Should illustrate, for the viscosity-average molecular weight (Mv) of polycarbonate resin (A composition) and resin combination, also utilize identical method to obtain.
(2) polydiorganosiloxane component content
Use Jeol Ltd. JNM-AL400 measures polycarbonate-polydiorganosiloxane copolymer resins 1h-NMR composes, and is calculated by the integration ratio at the integration ratio that compares the peak deriving from dihydric phenol (I) and the peak that derives from dihydroxyl aryl end polydiorganosiloxane (II).
Polydiorganosiloxane component content (wt%)=[A/ (A+B)] × 100
A: (of dihydroxyl aryl end polydiorganosiloxane (II) 1the integration ratio at the peak of H) × (molecular weight of polydiorganosiloxane part)
B: (of dihydric phenol (I) 1the integration ratio at the peak of H) × (molecular weight of dihydric phenol)
(3) mean sizes of polydiorganosiloxane structural domain
Polycarbonate-polydiorganosiloxane copolymer resins powder is utilized exhaust biaxial extruder (TECHNOVEL Co., Ltd. system, KZW15-25MG), carry out mixing temperature 260 DEG C, carry out granulating.By the particle that obtains 120 DEG C of warm air dryings after 5 hours, use injection moulding machine [Sumitomo Heavy Industries, Ltd SG150US-M IV], mold temperature 280 DEG C, die temperature 80 DEG C of compacted unders be width 50mm, length 90mm, thickness is the 3 segment type plates of 3.0mm (length 20mm), 2.0mm (length 45mm), 1.0mm (length 25mm) from cast gate side.Use this 3 segment type plate, use X-ray diffraction device (Rigaku Co., Ltd. RINT-TTRII) to measure the mean sizes of the polydiorganosiloxane structural domain of the point of intersection apart from end 5mm, distance sidepiece 5mm of thickness 1.0mm part.As x-ray source, use CuK α characteristic X-ray (wavelength 0.1541841nm), tube voltage 50kV, tube current 300mA.Small-angle scattering optics is Slit:1st 0.03mm, HS 10mm, SS 0.2mm, RS 0.1mm.Mensuration utilizes asymmetric scan mode method (2 θ scanning), implements under the condition of FT 0.01 ° of STEP, 4sec/step, sweep limit 0.06-3 °.The parsing of fitting of a curve uses the small-angle scattering of Rigaku Co., Ltd. to resolve software NANO-Solver (Ver.3.3).Resolve following enforcement: the coherent structure being assumed to the globular domain being dispersed with polydiorganosiloxane in the matrix of carbonate polymer, exists the fluctuation of size distribution, then the density of polycarbonate substrates is 1.2g/cm 3, the density of polydiorganosiloxane structural domain is 1.1g/cm 3, do not consider particle interphase interaction (disturbing between particle), adopt independent-particle model to implement.
2. the evaluation of resin combination
(1) tone
The particle that obtains will be made up of embodiment each 120 DEG C of dryings 5 hours with hot air circulation type drying machine, using injection moulding machine [Sumitomo Heavy Industries, Ltd SG150US-M IV], is the smooth surfaces plate of width 100mm, length 100mm, thickness 5.0mm at mold temperature 320 DEG C, die temperature 80 DEG C of compacted unders.The tone (YI value) of this smooth surfaces plate uses Gretag Macbeth Inc. Color-Eye7000A to measure.
(2) mean flow rate
The particle that obtains will be made up of embodiment each 120 DEG C of dryings 5 hours with hot air dryer, utilize injection moulding machine [Toshiba Machinery Co., Ltd. IS150EN-5Y] to be light guiding plate (100mm × 70mm × 4mm) (back side exists lines with 0.1mm interval) of brightness evaluation at barrel temperature 300 DEG C, die temperature 80 DEG C of compacted unders.Be that the mode of downside arranges above-mentioned light guiding plate with the back side, make light incident from the limit of 70mm × 4mm, use TOPCON Inc. BM-7 to measure brightness from the light of the surface launching of 100mm × 70mm.The measured value of total 9 positions of width 3 reference points, length 3 reference points is on average obtained mean flow rate.Should illustrate, as incident light, use and install as the device of the NS2W150 (Nichia Chemical Industries, Ltd's system) of LED as light source (current consumption is about 30W) using 18mm spacing.
(3) aberration in face
Be that the mode of downside arranges above-mentioned light guiding plate with the back side, make from the limit of 70mm × 4mm light incident, use TOPCON Inc. BM-7 to measure colourity (x, y) from the surface launching of 100mm × 70mm.In face, aberration (Δ (x, the y)) numerical value calculated by following formula (1) is evaluated.Should illustrate, in numerical value less meaning face, aberration is less.Should illustrate, as incident light, use and install as the device of the NS2W150 (Nichia Chemical Industries, Ltd's system) of LED as light source (current consumption is about 30W) using 18mm spacing.
Δ(x，y)＝[(x 2-x 1) 2+(y 2-y 1) 2] 1/2(1)
(x 1, y 1) apart from the colourity of the position of light source 80mm
(x 2, y 2) apart from the colourity of the position of light source 20mm
(4) formability
Use in drawer at movable side of mould one side the inserts be made up of minor face 65mm/ long limit 115mm steel imparting prism, the mould fixation side one side on inserts opposite gives arc-shaped matrix, is shaped to the flat light guiding plate of thickness 0.25mm.
The shape of prism utilizes the mould of prism width (or spacing) 70 μm, highly (or degree of depth) 10 μm to give.Arc-shaped convex (point) shape is according to radius 25 μm, the degree of depth 10 μm, point from the light source side end face of forming light guide plate product minor face to (long side direction) 3/8 is spaced apart 180 μm, be spaced apart 120 μm to this point of 3/8 ~ 5/8, be spaced apart 80 μm to this point of 5/8 ~ 7/8, be spaced apart to this point of 7/8 ~ 8/8 60 μm condition give.
Injection molding utilizes injection moulding machine [Toshiba Machinery Co., Ltd. IS150EN-5Y] at the condition compacted under of barrel temperature 360 DEG C, die temperature 115 DEG C.
Mould dirt settling when carrying out shaping under the condition of molding of afore mentioned rules, plastic property, product strength are evaluated by the benchmark shown in following table 1.
[table 1]
Evaluation result Mould dirt settling (※ 1) Plastic property Product strength (※ 2)
○ Mould inviolateness Figuration is good Be less than 5%
× Mould has a stain Figuration is bad More than 5%
The visual observation of the die surface after (※ 1) 1000 times (shot)
The crackle generation degree of goods when (※ 2) 100 demi continuities are shaping
[embodiment 1 ~ 17 and comparative example 1 ~ 8]
After A ~ C composition and various additive being mixed by each use level that table 1 and table 2 are recorded with mixing machine, use exhaust biaxial extruder to carry out melting mixing and obtain particle.The various additives used respectively with the concentration of 10 ~ 100 of use level times for benchmark, after making the pre-composition with polycarbonate resin in advance, carry out overall mixing with mixing machine.Exhaust biaxial extruder uses Corporation Japan Steel Works's system: TEX30 α (engaging completely, equidirectional rotation, 2 screw rods).Extrusion condition is the vacuum tightness 4kPa of output 25kg/h, screw speed 200rpm, exhaust, and in addition, it is 265 DEG C that extrusion temperature is set to from the first supplying opening to the second supplying opening, is 285 DEG C from the second supplying opening to die portion.Evaluation result is shown in table 2 and table 3.
[table 2]
[table 3]
Should illustrate, the details of each composition of use is as follows.
(A composition)
A-1: the polycarbonate resin powder of the molecular weight 12500 utilizing following method for making to obtain
Ion exchanged water 2340 parts, 25% aqueous sodium hydroxide solution 947 parts, sulfoxylate 0.7 part is loaded in the reactor of band thermometer, stirrer, reflux cooler, under agitation dissolve 2, after two 710 parts, (4-hydroxy phenyl) propane (hereinafter sometimes referred to " dihydroxyphenyl propane ") (dihydroxyphenyl propane solution) of 2-, add methylene dichloride 2299 parts and 48.5% aqueous sodium hydroxide solution 112 parts, be blown into 354 parts, phosgene at 15 ~ 25 DEG C with about 90 minutes, carry out phosgenation reaction.After phosgenation terminates, add dichloromethane solution 270 parts and 48.5% aqueous sodium hydroxide solution 88 parts of the p-tert-butylphenol of 11% concentration, stop stirring, standing separation is after 10 minutes, carrying out stirring makes its emulsification after 5 minutes, process under the condition of rotating speed 1200rpm, number of pass times 35 times with mixer for well-distribution (Tokushu Kika Kogyo K.K), obtain high emulsification rubber cement (dope).This high emulsification rubber cement, in polymerization tank (band stirrer), without under agitation condition, temperature 35 DEG C reaction 3 hours, terminates polymerization.After reaction terminates, be separated organic phase, after dchloromethane also washing, formation hydrochloric acid is acid, washing until the electric conductivity of aqueous phase reach almost identical with ion exchanged water after, put into and be equipped with in the kneader of warm water, make methylene dichloride evaporate while stirring, obtain the powder of polycarbonate.After dehydration, utilize hot air circulation type drying machine 120 DEG C of dryings 12 hours, obtain polycarbonate resin powder.
A-2: the polycarbonate resin powder of the viscosity-average molecular weight 12200 utilizing following method for making to obtain
Change to the dichloromethane solution 275 parts of the p-tert-butylphenol of 11% concentration, in addition, carry out in the same manner as the manufacture method of A-1, obtain polycarbonate resin powder.
A-3: the polycarbonate resin powder of the viscosity-average molecular weight 12800 utilizing following method for making to obtain
Change to the dichloromethane solution 264 parts of the p-tert-butylphenol of 11% concentration, in addition, carry out in the same manner as the manufacture method of A-1, obtain polycarbonate resin powder.
A-4: the polycarbonate resin powder of the viscosity-average molecular weight 13200 utilizing following method for making to obtain
Change to the dichloromethane solution 257 parts of the p-tert-butylphenol of 11% concentration, in addition, carry out in the same manner as the manufacture method of A-1, obtain polycarbonate resin powder.
A-5: the polycarbonate resin powder of the viscosity-average molecular weight 15200 utilizing following method for making to obtain
Change to the dichloromethane solution 225 parts of the p-tert-butylphenol of 11% concentration, in addition, carry out in the same manner as the manufacture method of A-1, obtain polycarbonate resin powder.
A-6: the polycarbonate resin powder of the viscosity-average molecular weight 11700 utilizing following method for making to obtain
Change to the dichloromethane solution 285 parts of the p-tert-butylphenol of 11% concentration, in addition, carry out in the same manner as the manufacture method of A-1, obtain polycarbonate resin powder.
(B component)
B-1: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 19100 utilizing following method for making to obtain
Ion exchanged water 21591 parts, 48.5% aqueous sodium hydroxide solution 3674 parts is added in the reactor of band thermometer, stirrer, reflux cooler, will as forming 2 of the dihydroxy compound (I) of carbonic ether Component units that above-mentioned formula (2) represent, after two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) 3880 parts of 2-and sulfoxylate 7.6 parts dissolve, add methylene dichloride 14565 parts (be 14 mole relative to dihydroxy compound (I) 1 mole), under stirring, be blown into 1900 parts, phosgene at 22 ~ 30 DEG C with 60 minutes.Next, add 48.5% aqueous sodium hydroxide solution 1131 parts, p-tert-butylphenol 108 parts is dissolved in the solution in methylene dichloride 800 parts, while stir, while the polydiorganosiloxane compound 204 parts that the following formula (10) being dihydroxyl aryl end polydiorganosiloxane (II) of about 37 by the averaged repeating numbers as the dimethyl siloxane units forming the carbonic ether Component units that above-mentioned formula (4) represents represents is dissolved in the solution in methylene dichloride 1600 parts, add relative to the speed that the amount of every 1 mole of dihydric phenol (I) is 0.0008 mole/min with dihydroxyl aryl end polydiorganosiloxane (II), after becoming emulsified state, vigorous stirring again.Under this stirring, the state being 26 DEG C with reaction solution adds triethylamine 4.3 parts and continues stirring 1 hour temperature 26 ~ 31 DEG C, terminates reaction.After reaction terminates, be separated organic phase, after dchloromethane also washing, be hydrochloric acid acidity, wash, until the electric conductivity of aqueous phase almost identical with ion exchanged water after, put into and be equipped with in the kneader of warm water, make methylene dichloride evaporate while stirring, obtain the powder of polycarbonate-polydiorganosiloxane copolymer resins.After dehydration, utilize hot air circulation type drying machine 120 DEG C of dryings 12 hours, obtain polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 4.1%, the mean sizes 10nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 19100)
B-2: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 19400 utilizing following method for making to obtain
Use the dihydroxyl aryl end polydiorganosiloxane 430 parts that the repeat number of the dimethyl siloxane units forming polycarbonate Component units is about 37, churning time is made to be 45 minutes, in addition, implement in the same manner as the manufacture method of B-1, obtain polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 8.2%, the mean sizes 13nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 19400)
B-3: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 19200 utilizing following method for making to obtain
The averaged repeating numbers making the dimethyl siloxane units of formation polycarbonate Component units is about 100, in addition, implements in the same manner as the manufacture method of B-1, obtains polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 4.2%, the mean sizes 25nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 19200)
B-4: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 19600 utilizing following method for making to obtain
The averaged repeating numbers making the dimethyl siloxane units of formation polycarbonate Component units is about 150, in addition, implements in the same manner as the manufacture method of B-1, obtains polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 4.2%, the mean sizes 38nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 19600)
B-5: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 18900 utilizing following method for making to obtain
The averaged repeating numbers making the dimethyl siloxane units of formation polycarbonate Component units is about 13, in addition, implements in the same manner as the manufacture method of B-1, obtains polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 4.2%, the mean sizes 1.0nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 18900)
B-6: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 19200 utilizing following method for making to obtain
The averaged repeating numbers of the dimethyl siloxane units of formation polycarbonate Component units is made to be 13, polydiorganosiloxane compound is made to be 2 parts, in addition, implement in the same manner as the manufacture method of B-1, obtain polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 0.04%, the mean sizes 0.3nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 19200)
B-7: the polycarbonate-polydiorganosiloxane copolymer resins powder of the viscosity-average molecular weight 18500 utilizing following method for making to obtain
The averaged repeating numbers making the dimethyl siloxane units of formation polycarbonate Component units is about 200, in addition, implements in the same manner as the manufacture method of B-1, obtains polycarbonate-polydiorganosiloxane copolymer resins powder.(polydiorganosiloxane component content 4.2%, the mean sizes 48nm of polydiorganosiloxane structural domain, viscosity-average molecular weight 18500)
(C composition)
C-1: two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s system: ADK STAB PEP-36)
C-2: two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites (Asahi Denka Co., Ltd.'s system: ADK STAB PEP-24G)
(other composition)
D-1: the phosphoric acid ester (Daihachi Chemical Industry Co., Ltd.'s system: PX-200 (trade(brand)name)) being principal constituent with Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester]
D-2: potassium perfluor butane sulfonate salt (Dainippon Ink and Chemicals, Inc's system: Megafac F-114P (trade(brand)name))
E-1: glyceryl monostearate (RIKEN VITAMIN Co., Ltd. system: RIKEMAL S-100A (trade(brand)name))
F-1: hindered phenol system antioxidant (Ciba Specialty Chemicals Inc.: Irganox1076 (trade(brand)name))
G-1:UV absorption agent (CHEMIPRO KASEI Co., Ltd. system: KEMISORB 79 (trade(brand)name))
H-1: white dyes (Hakkol Chemical Co., Ltd. system: Hakkol PSR (trade(brand)name))
Utilizability in industry
Resin combination of the present invention is useful as light guiding plate, surface light source unit.

Claims (12)

1. have a resin combination for guide-lighting performance, containing (A) polycarbonate resin and A composition and (B) polycarbonate-polydiorganosiloxane copolymer resins and B component, the viscosity-average molecular weight of this resin combination is 1.2 × 10 4~ 1.3 × 10 4scope, B component is in the matrix of carbonate polymer, there is polycarbonate-polydiorganosiloxane copolymer resins that mean sizes is the polydiorganosiloxane structural domain of 0.5 ~ 40nm.
2. the resin combination with guide-lighting performance according to claim 1, wherein, B component is polycarbonate-polydiorganosiloxane copolymer resins that polydiorganosiloxane block that the polycarbonate block that represented by following formula (2) and following formula (4) represent is formed
In described formula (2), R 1and R 2represent independently of one another and be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 18, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 3 ~ 14, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, group in cyano group and carboxyl, when existing multiple separately, they can be the same or different, e and f is respectively the integer of 1 ~ 4, W is singly-bound or at least 1 group in being selected from group that following formula (3) represents,
In described formula (3), R 11, R 12, R 13, R 14, R 15, R 16, R 17and R 18represent the group be selected from the aralkyl of hydrogen atom, the alkyl of carbonatoms 1 ~ 18, the aryl of carbonatoms 3 ~ 14 and carbonatoms 7 ~ 20 independently of one another, R 19and R 20represent the group be selected from hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 18, the alkoxyl group of carbonatoms 1 ~ 10, the cycloalkyl of carbonatoms 6 ~ 20, the cycloalkyloxy of carbonatoms 6 ~ 20, the alkenyl of carbonatoms 2 ~ 10, the aryl of carbonatoms 3 ~ 14, the aryloxy of carbonatoms 6 ~ 10, the aralkyl of carbonatoms 7 ~ 20, the aralkoxy of carbonatoms 7 ~ 20, nitro, aldehyde radical, cyano group and carboxyl independently of one another, when existing multiple, they can be the same or different, g is the integer of 1 ~ 10, h is the integer of 4 ~ 7
In described formula (4), R 3, R 4, R 5, R 6, R 7and R 8be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or the aryl without replacement independently of one another, R 9and R 10be hydrogen atom, halogen atom, the alkyl of carbonatoms 1 ~ 10, the alkoxyl group of carbonatoms 1 ~ 10 independently of one another, p is natural number, and q is 0 or natural number, and p+q is the natural number of less than 150, and X is the aliphatic divalent group of carbonatoms 2 ~ 8.
3. the resin combination with guide-lighting performance according to claim 1 and 2, wherein, with the gross weight of resin combination for benchmark, the content of the polydiorganosiloxane block that the following formula (5) contained in described formula (4) represents is 0.001 ~ 1.0 % by weight
In described formula (5), R 21, R 22, R 23, R 24, R 25and R 26be hydrogen atom, the alkyl of carbonatoms 1 ~ 12 or the replacement of carbonatoms 6 ~ 12 or without the aryl replaced, r is natural number independently of one another, s is 0 or natural number, and r+s is the natural number of less than 150.
4. the resin combination with guide-lighting performance according to any one of claims 1 to 3, wherein, with the gross weight of resin combination for benchmark, the content of the polydiorganosiloxane block that the described formula (5) contained in described formula (4) represents is 0.01 ~ 0.5 % by weight.
5. the resin combination with guide-lighting performance according to any one of Claims 1 to 4, it is characterized in that, B component is in the matrix of carbonate polymer, there is polycarbonate-polydiorganosiloxane copolymer resins that mean sizes is the polydiorganosiloxane structural domain of 0.5 ~ 18nm.
6. the resin combination with guide-lighting performance according to any one of Claims 1 to 5, wherein, relative to (A) polycarbonate resin and A composition 100 weight part, containing (B) polycarbonate-polydiorganosiloxane copolymer resins and B component 0.01 ~ 10 weight part.
7. the resin combination with guide-lighting performance according to any one of claim 1 ~ 6, wherein, relative to polycarbonate resin and A composition 100 weight part, the phosphorus system stablizer represented containing (C) following formula (1) and C composition 0.01 ~ 1.0 weight part
In formula (1), A 1, A 2be aryl or alkyl independently of one another, can be the same or different.
8. a light guiding plate is by shaping for the resin combination according to any one of claim 1 ~ 7.
9. light guiding plate according to claim 8, wherein, the length of the long side direction of light guiding plate is 50 ~ 130mm.
10. light guiding plate according to claim 8 or claim 9, wherein, the thickness accounting for the region of at least 80% of light guiding plate is the scope of 0.2 ~ 0.4mm.
Light guiding plate according to any one of 11. according to Claim 8 ~ 10, wherein, gives the shape of prism in the one side of light guiding plate, the convex or concave shape in contrary face imparting arc-shaped.
12. 1 kinds of surface light source units are that the one side of the light guiding plate according to any one of claim 8 ~ 11 arranges reflector.
CN201380029867.3A 2012-06-07 2013-05-29 Resin composition having light-guiding ability, and light guide plate and surface light source body comprising same Pending CN104334641A (en)

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KR20150023415A (en) 2015-03-05

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