CN101525483A

CN101525483A - Aromatic polycarbonate resin composition with light diffusibility

Info

Publication number: CN101525483A
Application number: CN200910118599A
Authority: CN
Inventors: 古屋和彦; 池松龙介
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2008-03-04
Filing date: 2009-03-04
Publication date: 2009-09-09
Anticipated expiration: 2029-03-04
Also published as: CN101525483B; JP2009209253A; JP5602992B2

Abstract

The objective of the present invention is to provide excellent thermostable aromatic polycarbonate resin composition with high light diffusibility and high light permeation rate simultaneously, without generation of silver plaque and resin speckle. The resin composition according to the invention has light diffusibility, relative to 100 parts by weight of aromatic polycarbonate resin (A ingredient), containing 0.01-3.0 parts by weight of crosslinking (methyl) acrylic polymer particles (B ingredient), which are not compatible with the aromatic polycarbonate resin, and reduces 5% of weight detected by calorimetry device when temperature is above 300 DEG C.

Description

Aromatic polycarbonate resin composition with light diffusibility

Technical field

The present invention relates to a kind of aromatic polycarbonate resin composition with light diffusibility, in more detail, relate to and a kind ofly can realize high light diffusing and high light line transmitance simultaneously, and have the aromatic polycarbonate resin composition with light diffusibility of the good thermostability that does not produce silver-colored spot, resin foxiness.In addition, relate to that to be suitable for injection moulding (extruding) moulding, to be particularly suited for the maximal projection area be 500～50000cm ²The aromatic polycarbonate resin composition with light diffusibility of large-scale injection moulding (extruding) moulding.

Background technology

In the past, the diffuser plate of using with light diffusing sheet, automobile instrument at various illumination covers, infiltration type indicating meter and various labels etc. require in the purposes of light diffusing, are widely used in the material that has disperseed the light diffusing agent of organism or inorganics on the transparent resin of aromatic polycarbonate resin, acrylic resin, styrene resin and vinyl chloride resin etc.In so transparent resin, not only mechanical characteristics, thermotolerance and weathering resistance are good owing to aromatic polycarbonate resin, and have the high light line transmitance, so be widely used.

As light diffusing agent, can enumerate the organic class particle with crosslinking structure of crosslink propylene acids particle, cross-linked silicone class particle and cross-linked styrene class particle etc.In addition, as light diffusing agent, can also utilize the inorganic fiber of the electrodeless class particle of lime carbonate, barium sulfate, aluminium hydroxide, silicon-dioxide, titanium oxide and Calcium Fluoride (Fluorspan) etc. or staple glass fibre etc.Especially, organic class particle is than electrodeless class particle, because the surface smoothing of its moulding product is good, can realize the moulding product outward appearance of height, so applicable in the purposes widely.

In addition, purposes as the material that is dispersed with light diffusing agent, for example in polycarbonate resin, can enumerate light diffusing sheet that electric light cover, lighting ball, vehicle mounted tachometer gage, billboard (especially internal irradiation), resin window glass and display unit use (for example, light diffusing sheet that uses in the light diffusing sheet that uses in the backlight module with liquid crystal indicator, the display screen as the projection display device of projection TV etc. etc. is representative) etc.The common important function is not reduce the light quantity of line source bodies such as pointolite body, luminescent lamp/cold-cathode tube such as electric light/LED as far as possible in these purposes, forms with the face surface light source unit of diffusion light equably.In this purposes, because electric light cover, lighting ball, billboard (especially internal irradiation), resin window glass etc. are equivalent to the exterior member of goods, therefore its moulding product require to have beautiful outward appearance (whiteness), when producing the bad order of yellowing, silver-colored spot, foxiness etc., lost value as goods.Similarly, in the light diffusing sheet that vehicle mounted tachometer gage and display unit are used etc., must from light source to the face of light source opposition side on launch diffusion light equably, so produced the molding that becomes colourity worsens, light covers reason silver-colored spot, foxiness etc., become the goods of low value equally.Further, in recent years, liquid crystal indicator etc. have been obtained obvious improvement in maximization, slimming, and the thermal history to resin during moulding is also increasing, and the necessity of thermostability becomes more and more higher.

As the aromatic copolycarbonate resin composition of such good heat stability, known aromatic polycarbonate resin is arranged, be the phosphinate of high molecular particle, ad hoc structure of representative and/or phosphorous acid ester, trialkylphosphate with the silicone crosslinked particle, the light-diffusing resin composition (referring to Patent Document 1,2) that forms with the pentaerythritol diphosphites and the hindered phenol of specific ratios.In addition, the known aromatic copolycarbonate resin composition (patent documentation 3) that good heat stability when making large-scale injection moulding product is arranged.

But, in view of the opinion of putting down in writing in these documents, even suppressed the yellowing of the resin in the high-temperature molding self, but, under the low situation of the decomposition temperature of particles self such as crosslink propylene acid particles, in surpassing 300 ℃ high-temperature molding, can fully suppress the generation of silver-colored spot, foxiness hardly.

Further, known have the crosslink propylene acids particle self that uses as high molecular particle is carried out the method (with reference to patent documentation 3) that thermostabilization is handled.In described document, to infer when high-temperature molding, the crosslink propylene acid particles that uses as light diffusing agent decomposes, under the influence of its decomposition product, polycarbonate resin is colored, with respect to this, by in crosslink propylene acids particle, adding specific Phosphorus stablizer, prevented painted.But, in surpassing 300 ℃ high-temperature molding, still can fully suppress the generation of silver-colored spot, foxiness hardly, only crosslink propylene acid particles self is implemented heat stabilisation process, under the situation of considering resin combination integral body, thermostability is still insufficient.

Patent documentation 1: TOHKEMY 2001-214049 communique

Patent documentation 2: TOHKEMY 2001-323149 communique

Patent documentation 3: TOHKEMY 2006-307140 communique

Summary of the invention

The objective of the invention is to, provide a kind of and have high light diffusing and high light line transmitance, and have the light-diffusing resin composition of the good thermostability that does not produce silver-colored spot, resin foxiness.

The inventor has carried out concentrated research in order to achieve the above object, found that, with respect to (A) aromatic polycarbonate resin (A composition) 100 weight parts, containing the temperature that weight that (B) measured by the calorimetric measurement device reduces at 5% o'clock is more than 300 ℃, and the light-diffusing resin composition of crosslinked (methyl) acrylic polymers particle (B composition) 0.01～3.0 weight part that mixes with above-mentioned aromatic polycarbonate resin not, in injection moulding (extruding) moulding, be 500～50000cm especially at the maximal projection area ²Large-scale injection moulding (extruding) moulding in, demonstrate do not have silver-colored spot, resin burns black thermostability, thereby finished the present invention.

Above-mentioned purpose of the present invention realizes in the following manner.

(1) a kind of light-diffusing resin composition, its aromatic polycarbonate resin (A composition) with respect to 100 weight parts, crosslinked (methyl) acrylic polymers particle (B composition) that contains 0.01～3.0 weight part, wherein, the temperature that the weight of being measured by the calorimetric measurement device of described crosslinked (methyl) acrylic polymers particle (B composition) reduces at 5% o'clock is more than 300 ℃, and does not mix with above-mentioned aromatic polycarbonate resin.That is, main points of the present invention are that crosslinked (methyl) acrylic polymers particle that will have the temperature that reduces at 5% o'clock than higher in the past weight is coupled in the aromatic polycarbonate resin, realize above-mentioned problem thus.

One of preferred example of the present invention is that (2) are as above-mentioned (1) described light diffusing aromatic carbonate ester resin composition, wherein, the B composition is in polymerization process, crosslinked (methyl) acrylic particles that in crosslinked particle, has cooperated stablizer, described stablizer is at least a stablizer that is selected from the group of being made up of Phosphorus compound, hindered phenol compound and sulphur class antioxidant, and with respect to the B composition of 100 weight parts, the use level of described stablizer is 0.005～2.0 weight part

One of preferred example of the present invention be (3) as above-mentioned (2) described light-diffusing resin composition, wherein, the Phosphorus compound that contains in the B composition for following formula (I)～(III) expression phosphorous acid class stablizer,

(in the formula (I), Ar ₁For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl);

(in the formula (II), Ar ₂For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl);

(in the formula (III), Ar ₃For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl).

One of preferred example of the present invention is that (4) are as each described light-diffusing resin composition in above-mentioned (1)～(3), wherein, with respect to the A composition of 100 weight parts, be combined with the Phosphorus stablizer (C composition) of 0.0001～1 weight part and/or the hindered phenol compound (D composition) of 0.001～1 weight part.

By cooperating described stablizer, especially can improve the thermostability of aromatic polycarbonate resin self, can provide to have the more light-diffusing resin composition of favorable luminance.

One of preferred example of the present invention is that (5) are as in each described light-diffusing resin composition in above-mentioned (1)～(4), wherein, with respect to the aromatic polycarbonate resin of 100 weight parts, be combined with the white dyes (E composition) of 0.0005～0.5 weight part as the A composition.

Improved brightness by mixing described composition, can providing, perhaps the aromatic polycarbonate resin composition with light diffusibility with low uncertainty of the color and luster in the life-time service.

One of preferred example of the present invention is illumination cover, vehicle lamp cover and the light diffusing sheet that (6) are formed by each described light-diffusing resin composition in above-mentioned (1)～(5).

One of preferred example of the present invention is (7) light diffusing sheet described in above-mentioned (6), and it is that the maximal projection area is 500～50000cm ², and the light diffusing sheet by injection moulding extrusion molding manufactured.

Description of drawings

Fig. 1 is the synoptic diagram of the measuring method of dispersity among expression the present invention.

Fig. 2 is the synoptic diagram of the large-scale injection moulding extrusion molding product of moulding among expression the present invention.As shown in the figure, these large-scale moulding product have the 3D shape that is made of level and smooth curved surface.[1-A] represents front view (projection is in the figure of pressing plate (platen) face during moulding), the side-view of [1-B] expression length direction, and [1-C] expression is from the side-view of flow end side.

The explanation of Reference numeral:

A test piece (tabular)

The B light source

γ diffusion luminosity angle

(thickness of body is 5mm to 11 moulding product bodies, and the maximal projection area is about 11000cm ²)

12 parts corresponding to the hot-runner nozzle front end

The cast gate of 13 moulding product (this cast gate is that thickness is the tabular of 5mm)

14 moulding product water the length (maximum width that is equivalent to the moulding product is 1000mm) of oral-lateral

The length (900mm) of 15 moulding product flow end sides

The length (1240mm) of 16 moulding product bodies

17 comprise the total length (1350mm) of the moulding product of gate part

The height of 18 moulding product (90mm)

19 installation claws

Embodiment

Below, describe the present invention in detail.

＜for the A composition 〉

A composition of the present invention is the aromatic polycarbonate resin that becomes the resin combination principal constituent.As representational aromatic polycarbonate resin (below, abbreviate " polycarbonate " sometimes as) is binary phenol and carbonic ether presoma to be reacted and the resin that obtains.As reaction method, can enumerate the solid phase ester-interchange method of interface polycondensation, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

Object lesson as above-mentioned binary phenol, can enumerate quinhydrones, Resorcinol, 4,4 '-bis-phenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (being referred to as " dihydroxyphenyl propane " usually) of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane, two (3,5-two bromo-4-hydroxy phenyls) sulfone, two (4-hydroxy-3-methyl phenyl) sulfide, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Wherein, general is two (4-hydroxy phenyl) paraffinic hydrocarbonss, especially general dihydroxyphenyl propane (being designated hereinafter simply as " BPA ").

In the present invention, except dihydroxyphenyl propane class polycarbonate, can also use the special polycarbonate of making by other binary phenol as the A composition as general polycarbonate.

For example, as part or all of binary phenol composition, use 4,4 '-(metaphenylene diisopropylidene) diphenol (following abbreviate as sometimes " BPM "), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane (following abbreviate as sometimes " Bis-TMC "), 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (the 4-hydroxy-3-methyl phenyl) fluorenes (following abbreviate as sometimes " BCF ") of 9-, the dimensional change or the shape stability that are suitable for suction is caused require on the strict especially purposes.These binary phenol except BPA, preferred 5 moles of the binary phenol composition total amount that constitutes this polycarbonate of using especially preferably use 10 moles more than the % more than the %.

Especially, under the situation that requires to have high rigidity and better hydrolytic resistance, the A composition that especially preferably constitutes resin combination is the Copolycarbonate of following (1)～(3).

(1) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPM is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably) and BCF be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %);

(2) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPA is 10～95 moles of % (50～90 moles of % more preferably, 60～85 moles of % more preferably) and BCF be the Copolycarbonate of 5～90 moles of % (more preferably 10～50 moles of %, more preferably 15～40 moles of %);

(3) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPM is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably) and Bis-TMC be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %).

These special polycarbonate both can use separately, also can two or morely suitably mix and use.In addition, also these can be mixed use with general bisphenol A polycarbonate.

About the manufacture method and the characteristic of these special polycarbonate, for example in the flat 6-172508 communique of TOHKEMY, the flat 8-27370 communique of TOHKEMY, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc., detailed record is arranged.

In addition, in above-mentioned various polycarbonate, by adjusting multipolymer composition etc. water-intake rate and Tg (second-order transition temperature) are adjusted at polycarbonate in the following ranges, the hydrolytic resistance of its polymkeric substance self is good, and the low bendability after the moulding is also excellent especially, therefore, be particularly suitable for requiring to have in the field of shape stability.

(i) water-intake rate is 0.05～0.15%, is preferably 0.06～0.13%; And Tg is 120～180 ℃ a polycarbonate; Perhaps

(ii) Tg is 160～250 ℃, is preferably 170～230 ℃; And water-intake rate is 0.10～0.30%, be preferably 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.

At this, the water-intake rate of polycarbonate is to utilize diameter for 45mm, the thickness discoideus test piece for 3.0mm, according to ISO62-1980, be determined at dipping in 23 ℃ the water after 24 hours moisture content and the numerical value that obtains.In addition, Tg (second-order transition temperature) is according to JIS K7121, the numerical value of trying to achieve with differential scanning calorimeter (DSC) mensuration.

On the one hand, as the carbonic ether precursor, use carbonylic halide (Carbonyl halide), carbonic ether or haloformate (Ha ロホ Le メ one ト) etc., specifically, can enumerate the bishaloformate of carbonyl chloride (Phosgene), diphenyl carbonate or binary phenol etc.

When by interfacial polymerization, when making aromatic polycarbonate resin, also can use catalyzer, end to stop agent, antioxidant etc. as required by above-mentioned binary phenol and carbonic ether precursor, wherein antioxidant is in order to prevent the oxidation of binary phenol.In addition, the aromatic polycarbonate resin can be with the branched polycarbonate resin of copolymerization in addition of the polyfunctionality aromatics more than the three-functionality-degree.At this, as the polyfunctionality aromatics more than the employed three-functionality-degree, can enumerate 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane etc.

Under the situation that contains the polyfunctionality compound that produces branched polycarbonate, its content is 0.001～1 mole of % in the polycarbonate total amount, is preferably 0.005～0.9 mole of %, is preferably 0.01～0.8 mole of % especially.In addition, particularly adopt under the situation of melt transesterification process, sometimes produce branched structure as side reaction, about the content of this branched structure, in the polycarbonate total amount, also be preferably 0.001～1 mole of %, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially.In addition, the ratio of above-mentioned branched structure can pass through ¹H-NMR measures and calculates.

In addition, polycarbonate of the present invention also can be with two functionality carboxylic acids of fragrant family or aliphatics (the comprising ester ring type) polyestercarbonate of copolymerization in addition, with two functionality alcohol (the comprising ester ring type) copolymerization polycarbonate of copolymerization in addition, and with this two functionality carboxylic acid and the two functionality alcohol polyestercarbonate of copolymerization in addition.In addition, also can be the mixture that has mixed two or more resulting polycarbonate.

As aliphatics two functionality carboxylic acids as used herein, preferably enumerate alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, for example, preferably can enumerate straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid; And the alicyclic dicarboxylic acid of cyclohexane dicarboxylic acid etc.As two functionality alcohol, be preferably alicyclic diol, for example can enumerate cyclohexanedimethanol, cyclohexane diol, tristane dimethanol etc.

In addition, in the present invention,, can also use the polyorganosiloxane units polycarbonate-poly organo alkyl copolymer of copolymerization in addition as the A composition.

The polycarbonate of A composition, also the blended polycarbonate in addition of two kinds in the various polycarbonate such as polycarbonate that can above-mentioned binary phenol is different, the polycarbonate that contains branched-chain component, polyestercarbonate, polycarbonate-poly organo alkyl copolymer.Further, also can use and mixed the polycarbonate that the different polycarbonate of two or more manufacture method, end stop different polycarbonate of agent etc.

As the reactive modes such as ring-opening polymerization method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer solid phase ester-interchange method and the cyclic polycarbonates compound of polycarbonate resin making method, be by known methods such as various documents and patent gazettes.Viscosity-average molecular weight to the aromatic polycarbonate resin of A composition is unqualified.But, if viscosity-average molecular weight less than 1 * 10 ⁴, then reduction such as intensity is if surpass 5 * 10 ⁴, then forming process reduction is so be preferably 1 * 10 ⁴～5 * 10 ⁴Scope, more preferably 1.2 * 10 ⁴～3 * 10 ⁴Scope, more preferably 1.5 * 10 ⁴～2.8 * 10 ⁴At this moment, in the scope that can keep formability etc., can also mix viscosity-average molecular weight at above-mentioned extraneous polycarbonate.For example, can mix viscosity-average molecular weight and surpass 5 * 10 ⁴The high-molecular-weight polycarbonate composition.

The said viscosity-average molecular weight of the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g aromatic copolycarbonate is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity (η by following formula _Sp):

Specific viscosity (η _Sp)=(t-t ₀)/t ₀

[t ₀Be dropping number second of methylene dichloride, dropping number second that t is sample solution];

According to resulting specific viscosity (η _Sp), calculate viscosity-average molecular weight M by following formula:

η _Sp/ c=[η]+0.45 * [η] ²C ([η] is limiting viscosity)

[η]＝1.23×10 ^-4M ^0.83

c＝0.7。

In addition, having used the calculating of the resin combination medium viscosity molecular-weight average of A composition is to carry out according to following method.That is, this resin combination is mixed with 20～30 times methylene dichloride of its weight, thus the solvable composition in the dissolving resin composition.Obtain this solvable composition by diatomite filtration.Then, the solvent in the removal gained solution.Solid behind the removal solvent is carried out thorough drying, obtain to be dissolved in the solids component of methylene dichloride.The solution that obtains from this solid of 0.7g is dissolved in the 100ml methylene dichloride, obtain specific viscosity under 20 ℃ with above-mentioned same operation, and, obtain viscosity-average molecular weight M with above-mentioned same operation from this specific viscosity.

＜about the B composition 〉

B composition of the present invention is, the temperature that the weight of measuring by the calorimetric measurement method reduces at 5% o'clock (following simply be recited as " 5% weight reduces temperature ") is crosslinked (methyl) acrylic polymers particle more than 300 ℃, that do not mix with the A composition.Cooperating the main purpose of described crosslinked (methyl) acrylic polymers particle, is not omit through light as far as possible, obtains high diffusion light.

Crosslinked (methyl) acrylic polymers particle (B composition) that uses among the present invention is than general crosslinked (methyl) acrylic polymers particle was [for example in light-diffusing resin composition in the past, テ Network Port リマ one MBX-5 (trade(brand)name, 5% weight reduce 250 ℃ of temperature, ponding changes into product industry (strain) manufacturing)], it is significantly high that its 5% weight reduces temperature, be more than 300 ℃, be preferably more than 320 ℃, more preferably more than 340 ℃.When 5% weight reduced temperature and is lower than 300 ℃, the silver-colored spot of generation, resin foxiness not only damaged outward appearance in the goods that obtain by injection moulding (extruding) moulding, also are difficult to realize simultaneously high light diffusing and high light line transmitance.In addition, the upper limit that 5% weight is reduced temperature has no particular limits, but is preferably below 450 ℃.

Be speculated as the amount of the resolvent that produces when being this crosslinked particle of thermolysis owing to seeing through of causing of the characteristic of the crosslink propylene acid particles reason that light quantity, color and luster, brightness and silver-colored spot, foxiness etc. produce difference in appearance.Be considered to described pyrolysate when melt-processed and polycarbonate resin produce side reaction, thus to seeing through light quantity, color and luster, brightness and silver-colored spot, burning outward appearance such as black and produce bad influence.On the one hand, the bad phenomenon of light, color and luster, brightness and the silver-colored spot that 5% weight of crosslinked (methyl) acrylic particles produces when reducing temperature and melt-processed, foxiness etc. has confidential relation, can be described as the useful index that is used to show thermostability.In addition, the mensuration that 5% weight among the present invention reduces temperature is based on JIS K7120, adopts the TGA determinator, and in nitrogen environment, with from 23 ℃ to 900 ℃ temperature range, and the condition determination of 20 ℃/minute heat-up rate is finished.Reduce in the movement in described weight, the temperature when confirming to reduce by 5% weight is that 5% weight reduces temperature.

The specific refractory power of crosslinked (methyl) acrylic polymers particle (B composition) that uses among the present invention is preferably below 1.55, more preferably below 1.53, more preferably below 1.50.Under specific refractory power surpasses 1.55 situation, because little, cause the refraction of light to die down with the difference of the specific refractory power of polycarbonate resin, thus can't obtain the light scattering effect expected, thus not preferred.In addition, specific refractory power is to measure by commercially available Abbe formula refractometer (2T type Abbe formula refractometer, (strain) ア go are made).

Further, the median size of crosslinked (methyl) acrylic polymers particle that uses among the present invention is preferably 1～50 μ m, more preferably 1～30 μ m, more preferably 1～10 μ m.Under the situation of particle diameter less than 1 μ m, though can access light diffusing, photopermeability is poor, thereby not preferred, when greater than 50 μ m, in order to obtain light diffusing, needs heavy addition, causes that thus intensity reduction etc. exerts an influence to rerum natura, thereby not preferred.In addition, median size is measured by following method.That is, in the pore of aperture 50～280 μ m, fill electrolyte solution, change from the electric conductivity of the electrolyte solution of particle during and obtain volume, calculate median size by this electrolyte solution.The median size of being measured is the volume average particle size of being measured by the Multisizer Multisizer II that beckmancoulter company makes.

Concrete measuring method is as follows.At first, in commercially available glass test tube, 0.1g particle and 0.1% nonionic class surfactant soln 10ml pack into, after the touch mixing machine TOUCHMIXER MT-31 that makes with YAMATO science (strain) mixes 2 seconds, test tube is put into Ultrasonic Cleaners-ULTRASONIC CLEANER VS-150 that commercially available VELVO CLEANER company makes, solution is carried out the pre-dispersed of 10 seconds.Then, stir on one side slowly on one side this drips of solution to be added to and be installed on the body and filled up ISOTON2 (beckmancoulter company makes with dropping pipette, measure and to use electrolytic solution) flask in, thereby the indicating value of the densitometer of body picture is adjusted at 10% left back.Then,, measure to the input of Multisizer II body according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) with manual (manual).In the mensuration, the degree that can not enter in the flask with bubble in advance slowly stirs, and can finish to measure after having measured 100,000 particles.

Crosslinked (methyl) acrylic polymers particle can adopt the known method of letex polymerization, suspension polymerization, seeding polymerization to make.

Crosslinked (methyl) acrylic polymers particle (B composition) that uses among the present invention in its polymerization process, can add at least a stablizer that is selected from the group of being made up of Phosphorus compound, hindered phenol compound and sulphur class antioxidant.

The Phosphorus compound of crosslinked as being added into (methyl) acrylic polymers (B composition), the effect height of the phosphorous acid class stablizer of following formula (I)～(III) expression, the preferred use.

(in the formula (I), Ar ₁For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl.)

(in the formula (II), Ar ₂For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl.)

(in the formula (III), Ar ₃For the alkyl of carbonatoms 6～20 or can contain the aromatic series base of the carbonatoms 6～20 of alkyl.)

Object lesson as the phosphorous acid class stablizer of following formula (I) expression, for example can enumerate the tricresyl phosphite phenylester, three (nonyl phenyl) phosphorous acid ester, the tricresyl phosphite decyl ester, tricresyl phosphite octyl group ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester, three (diethyl phenyl) phosphorous acid ester etc.

Object lesson as the phosphorous acid class stablizer of following formula (II) expression; for example can enumerate distearyl acyl group pentaerythritol diphosphites; two (2; the 4-di-tert-butyl-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, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites; phenyl double A pentaerythritol diphosphites; two (nonyl phenyl) pentaerythritol diphosphites; and the dicyclohexyl pentaerythritol diphosphites etc.

As the object lesson of the phosphorous acid class stablizer of following formula (III) expression, for example can enumerate 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.

Further, as other bi-ester of phosphite, can use the bi-ester of phosphite that reacts and have ring texture with the binary phenol.For example can enumerate 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) octyl group phosphorous acid ester etc.

Wherein, preferably have the phosphorons acid compound of phenol OH base, wherein, 6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) phenoxy group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] dioxathion suberane can access good especially effect.

As hindered phenol compound; for example can enumerate alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; 5-di-t-butyl-4 hydroxy 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; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-methylene radical-two (6-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-two (3 methy 6 tert butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; [3-(3 for 6-hexylene glycol-two; the 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; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 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 butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; 4; 4 '-dithio two (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-trithio two (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-divinyl is two-and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (n-octyl sulfo-)-6-(the 4-hydroxyls-3 of 4-; 5-di-t-butyl phenylamino)-1; 3; the 5-triazine; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; and four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.Wherein, preferred octadecyl-3-(3,5-di-t-butyl-4 hydroxy phenyl) propionic ester (Irganox1076 (trade(brand)name) that the manufacturing of CIBA SPECILATY CHEMICALS company is arranged as representational commercially available product).Above-mentioned hindered phenol anti-oxidants is in one's handsly all easy, and these may be used singly or two or more in combination.

Further; as sulphur class antioxidant; dilauryl-3 can be enumerated in example sentence; 3 '-thiodipropionate, myristyl-3; 3 '-thiodipropionate, distearyl acyl group-3; 3 '-thiodipropionate, tetramethylolmethane-four (3-lauryl thiopropionate), two (tridecyl)-3,3 '-thiodipropionate etc.

Above-mentioned sulphur class antioxidant all obtains easily, and they can use separately or two or more mixing is used.

The above-mentioned addition that is selected from least a stablizer in the group of forming by Phosphorus compound, hindered phenol compound and sulfur type antioxidant, B composition with 100 weight parts is a benchmark, be preferably 0.005～2.0 weight part, more preferably 0.05～1.0 weight part, 0.05～0.5 weight part more preferably.Under the situation of addition less than 0.005 weight part, antioxidant effect is little, causes thermolysis, color and luster aging etc. of resin, and when greater than 2.0 weight parts, oxidation inhibitor inherent color produces bad influence to the color and luster of composition in its entirety, thereby not preferred.

The content of B composition is benchmark with the A composition of 100 weight parts, is preferably 0.01～3.0 weight part, more preferably 0.05～2.0 weight part, 0.05～1.0 weight part more preferably.When less than 0.01 weight part, can't obtain gratifying light diffusing, if surpass 3 weight parts,, see through light and significantly reduce though then light diffusing is abundant.

＜about the C composition 〉

C composition of the present invention is various Phosphorus stablizers.Thermostability when the main purpose that cooperates described Phosphorus stablizer is the machine-shaping that improves resin combination obtains having the diffusion light of good colour.As described Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.

As concrete phosphorous acid ester (phosphite) compound; for example can enumerate; triphenyl phosphite; three (nonyl phenyl) phosphorous acid ester; the tricresyl phosphite decyl ester; tricresyl phosphite octyl group ester; three (octadecyl) phosphorous acid ester; didecyl list phenyl phosphites; dioctyl list phenyl phosphites; di-isopropyl list phenyl phosphites; monobutyl phenylbenzene phosphorous acid ester; single decyl phenylbenzene phosphorous acid ester; single octyl group phenylbenzene phosphorous acid ester; 2; 2-methylene-bis (4; the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester; three (diethyl phenyl) phosphorous acid ester; three (diisopropyl phenyl) phosphorous acid ester; three (di-n-butyl phenyl) phosphorous acid ester; three (2; the 4-di-tert-butyl-phenyl) phosphorous acid ester; three (2; the 6-di-tert-butyl-phenyl) phosphorous acid ester; distearyl acyl group pentaerythritol diphosphites; two (2; the 4-di-tert-butyl-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, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites; phenyl dihydroxyphenyl propane pentaerythritol diphosphites; two (nonyl phenyl) pentaerythritol diphosphites; and the dicyclohexyl pentaerythritol diphosphites etc.

Further, as other bi-ester of phosphite, can use the bi-ester of phosphite that reacts and have ring texture with the binary phenol.For example, can enumerate 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) octyl group phosphorous acid ester etc.

As phosphoric acid ester (phosphate) compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphoric acid ester, triethyl phosphate, diphenylmethyl benzenephosphonic acid ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list, three butoxyethyl group phosphoric acid ester, dibutyl phosphate, dioctylphosphoric acid ester and diisopropyl phosphate etc.Preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound (phosphonite), can enumerate four (2, the 4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite esters, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite esters, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, and two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite esters etc.Wherein, preferred four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates and two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with abovementioned alkyl, and preferably adopts this mode.

As phosphonate compound (phosphonate), can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.

As tertiary phosphine, can enumerate triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three pairs of toluene phosphines, three naphthyl phosphines and phenylbenzene benzyl phosphines etc.Particularly preferred tertiary phosphine is a triphenylphosphine.

Above-mentioned Phosphorus stablizer both can be used alone, and also can two or more mixing use.In above-mentioned Phosphorus stablizer, preferred bi-ester of phosphite or phosphinate compound.Most preferred bi-ester of phosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Be preferably four (2, the 4-di-tert-butyl-phenyl)-4 as phosphinate compound, 4 '-xenyl, two phosphinates and two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester and their mixture, wherein their mixture most preferably.Both part by weight (the former/latter) be preferably 90/10～70/30,85/15～75/25 the scope of electing as is more arranged.In addition, also preferably with these compounds and phosphate compound and usefulness.

The use level of C composition is a benchmark with the A composition of 100 weight parts, is preferably 0.0001～1 weight part, more preferably 0.01～1 weight part, more preferably 0.02～0.5 weight part.When less than 0.0001 weight part, can't obtain refractory and melt discolouration, if surpass 1 weight part, then cause the rotten of light-diffusing resin composition of the present invention.

＜about the D composition 〉

D composition of the present invention is the Hinered phenols stablizer.The main purpose that cooperates this Hinered phenols stablizer is to improve thermostability, heat-resistant aging and the ultraviolet resistance of light-diffusing resin composition when machine-shaping.As the Hinered phenols stablizer; for example can enumerate alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; 5-di-t-butyl-4 hydroxy 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; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-methylene-bis (6-α-Jia Jibianji-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-two (3 methy 6 tert butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; [3-(3 for 6-hexylene glycol-two; the 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; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 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 butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; 4; 4 '-dithio two (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-trithio two (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-divinyl-two [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (n-octyl sulfo-)-6-(the 4-hydroxyls-3 of 4-; 5-di-t-butyl phenylamino)-1; 3; the 5-triazine; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; and four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.Wherein, preferred octadecyl-3-(3,5-di-t-butyl-4 hydroxy phenyl) propionic ester (Irganox1076 (trade(brand)name) that representational commercially available product has CIBA SPECILATY CHEMICALS company to make).Above-mentioned hindered phenol anti-oxidants is in one's handsly all easy, and these hindered phenol anti-oxidants promptly can use separately, also can be used in combination.

The use level of D composition is a benchmark with the A composition of 100 weight parts, is preferably 0.001～1 weight part, more preferably 0.005～0.8 weight part, more preferably 0.001～0.5 weight part.When this use level less than 0.001 weight part, refractory be can't obtain and discolouration or dry heat resistance discolouration melted, if surpass 1 weight part, then brightness reduces.

Described C composition and D composition can be distinguished mixing separately, perhaps two or more combined hybrid.Especially preferably the C composition is contained as neccessary composition.

＜about the E composition 〉

E composition of the present invention is a white dyes.The main purpose that cooperates described white dyes is the brightness that improves diffusion light, and regulates the color and luster of diffusion light.White dyes is the energy with light-absorbing ultraviolet portion, and with the effect of this energy with the viewable portion radiation.As white dyes, can utilize known dibenzoxazine, tonka bean camphor and two (vinylbenzene) biphenyl etc.Wherein preferred coumarins white dyes.As the coumarins white dyes, can enumerate triazine-phenyl tonka bean camphor, benzotriazole-phenyl tonka bean camphor and naphthalene triazole-phenyl tonka bean camphor etc.The use level of E composition is a benchmark with the A composition of 100 weight parts, is 0.0005～0.5 weight part, is preferably 0.0005～0.3 weight part.If surpass 0.5 weight part, the effect of then improving the said composition color and luster is little.

＜about other compositions 〉

In light-diffusing resin composition of the present invention, in the scope of performance effect of the present invention, can also cooperate other habitual additives.For example, can cooperate fluorescence dye, the static inhibitor beyond the fire retardant, photostabilizer, releasing agent, Antidrip agent, flame retardant, dyestuff, pigment, light-storing paint, white dyes, the modification agent that flows, crystallization nucleating agent, inorganic and organic antibacterial agent, photochemical catalysis class stain control agent (titanium oxide microparticle, zinc oxide fine particles etc.), be conflict modification agent, infrared absorbent and the photochromic agent etc. of representative with the graft rubber.

Under than situation about using under the intense light source, the preferred mostly fire retardant that cooperates.As fire retardant of the present invention, can enumerate oligopolymer, brominated bisphenol based epoxy resin, brominated bisphenol class phenoxy resin, brominated bisphenol class polycarbonate, brominated Polystyrene, bromination crosslinked polystyrene, brominated polyphenylether, poly-dibromobenzene aether, the decabrominated dipheny base oxygen bis-phenol condenses of tetrabromo-bisphenol, tetrabromo-bisphenol and contain the halogen fire retardant that halophosphate is representative; As the Triphenyl phosphate of phosplate compound, as condensed phosphoric acid esters Resorcinol two (xylyl phosphoric acid ester), dihydroxyphenyl propane two (diphenyl phosphoester) and dihydroxyphenyl propane two (xylyl phosphoric acid ester), other are the organophosphate based flame retardant of representative with tetramethylolmethane phenylbenzene bisphosphate etc.; Hydrate, zinc borate, methyl-boron-dihydroxide zinc, magnesium oxide, molybdenum oxide, scandium oxide, stannic oxide, the weisspiessglanz of the inorganic metal compound of the mineral-type phosphoric acid salt of polyphosphoric acid ammonium salt, ammonium phosphate, phosphoric acid pick etc., aluminium hydroxide, magnesium hydroxide etc. are the mineral-type fire retardant of representative; Perfluor fourth potassium sulfonate, perfluor fourth calcium sulphonate, perfluor fourth sulfonic acid caesium, hexichol sulfo group-3-potassium sulfonate, hexichol sulfo group-3,3 '-disulfonic acid potassium, sodium formalin condenses are organic bases (alkaline earth) the metallic salt fire retardant of representative; Contain (gathering) organosilicone compounds of phenyl and the multipolymer of (gathering) organo-siloxane and polycarbonate resin; Phenoxy phosphazene oligopolymer or ring-type phenoxy phosphazene oligopolymer are the phosphazene flame retardant of representative etc.

As flame retardant, can enumerate sodium antimonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.As Antidrip agent, can enumerate have protofibril form can tetrafluoroethylene etc.Further, the form when cooperating, preferred described tetrafluoroethylene is aqueous for disperseing, solidify etc. the lining shape thing that obtains etc. altogether by dispersion liquid and other polymkeric substance and can form the loose tetrafluoroethylene of state of differential.Usually the A composition with 100 weight parts is a benchmark, and the use level of fire retardant, flame retardant and Antidrip agent is preferably 0.01～10 weight part.

The preferred releasing agent that uses is the above releasing agent for being made up of the ester of the ester of monohydroxy-alcohol and unary fatty acid and/or polyvalent alcohol and lipid acid of its 90% weight among the present invention.The ester of the saturated fatty acid of the monohydroxy-alcohol of the preferred carbonatoms 1～20 of described ester or polyvalent alcohol and carbonatoms 5～30.Ester as described monohydroxy-alcohol or polyvalent alcohol and saturated fatty acid, can enumerate stearyl stearate, palmityl cetylate, butyl stearate, Laurate methyl, different propionyl cetylate, 2-ethylhexyl stearate, glyceryl monostearate, glycerol stearate, sorbitan SUNSOFT Q-182S, pentaerythritol tetrastearate, tetramethylolmethane four pelargonates, propylene glycol SUNSOFT Q-182S etc., these can use or use two or more mixtures separately.Wherein, preferably use glyceryl monostearate, glycerol stearate, stearyl stearate, pentaerythritol tetrastearate.When using described releasing agent, its use level can be according to purpose and difference, but is benchmark with the A composition of 100 weight parts, is preferably 0.02～1 weight part.

Further, in light-diffusing resin composition of the present invention, can also cooperate with anthraquinone dyes, perylene class dyestuff, coumarins dyestuff, thioindigo class dyestuff, thioxanthene ketone dyestuff etc. is representative, and sends the fluorescence dye except that white dyes of green, yellow and redness etc.In addition, can also mix the yellow prussiate of Prussian blue grade, purple cyclic ketones class dyestuff, quinoline dyestuff, quinoline a word used for translation ketone dyestuff, dioxazines dyestuff, isoindoline ketone dyestuff and phthalocyanines dye etc. and be organic class dyestuff of representative.The use level of these dyestuffs is a benchmark with the A composition of 100 weight parts, is preferably 0.0001～2 weight part.

Under the situation about using under use or the intense light source,, more preferably cooperate UV light absorber without as photostabilizer.As UV light absorber of the present invention, specifically can enumerate benzophenone, for example can enumerate 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base Trihydride benzophenone (2-ヒ De ロキシ-4-メトキシ-5-ス Le ホキシトリ Ha イ De ライ De レイトベ Application ゾ Off エノ Application), 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-sulphur oxygen acid sodium benzophenone, two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane, 2-hydroxyl-4-positive 12-alkoxy benzophenone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.

In benzotriazole category, can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) 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 (1,3-benzoxazine-4-ketone), and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole etc.In addition, other can also be enumerated as 2, the cyclic imide base ester class UV light absorber of 2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone) etc.; 1,3-is two-[(2 '-cyano group-3 ', 3 '-diphenylprop enoyl-) oxygen]-2, two [(2-cyano group-3, the 3-diphenylprop enoyl-) oxygen] methyl of 2-) the cyanoacrylate UV light absorber and the triazines UV light absorber of propane etc.These also can be from the ultraviolet-absorbing polymer of monomers, can use a kind of or two or more and usefulness.The use level of described UV light absorber is a benchmark with the A composition of 100 weight parts, is preferably 0.001～2 weight part, more preferably 0.05～1 weight part.

＜about the manufacture method of resin combination 〉

When making light-diffusing resin composition of the present invention, its manufacture method is not done special qualification.But the preferable production process of resin combination of the present invention is for adopting forcing machine to each composition method of melting mixing in addition.Described method can realize the good dispersion of crosslinked (methyl) acrylic polymers particle.

As the preferred especially biaxial extruder of forcing machine.As its representative example, can enumerate ZSK (trade(brand)name, Werner ﹠amp; Pfleiderer company makes).In this ZSK type biaxial extruder, its screw rod is complete meshing type, and screw rod is made up of length various screw portions and the different various kneading disks (kneader disc) (or the mixing part of using suitable with it) of width different with spacing.

In biaxial extruder, preferred mode is as described below.The screw rod shape can adopt the helical screw (ネジス Network リユ one) of simple helix, duplex and triple helical, preferably especially uses the transporting power of molten resin or shears all wide duplex screw rod of the two aspect scope of applications of mixing ability.The ratio (L/D) of spiro rod length in the biaxial extruder (L) and diameter (D) is preferably 20～45, and more preferably 28～42.The L/D value is big more reaches uniform dispersion state easily more, but when too big, is easy to generate the decomposition of resin because of thermal ageing.Screw rod must have more than one mixing district, preferably has 1～3, and wherein, described mixing district is made up of the kneading disk part (perhaps suitable with it mixing part) that is used to improve mixing property.

Further, as forcing machine, the preferred forcing machine that uses with the venting port that can remove the moisture in the raw material or the volatile gases that produces by the melting mixing resin.Preferably be provided with and be used for the vacuum pump that the moisture that produced or volatilization gas drained into the forcing machine outside effectively from venting port.In addition, be provided with in the zone before forcing machine mould portion and be used to remove the filtering net of sneaking into, also impurity can be removed from resin combination thus extruding impurities in raw materials etc.As this filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.

And, to with B composition, C composition, D composition, E composition and other additives (in the following illustration, only be called " additive ") there is no particular limitation to supply with the method for forcing machine, but can enumerate following method as its representational example: the method for (i) additive and A composition resin being supplied with independently forcing machine respectively; (ii) adopt the mixing machine of super mixing machine etc., in advance additive and A composition toner are carried out pre-mixing after, resupply the method for forcing machine; And (iii) in advance additive and A composition resin are carried out melting mixing, make the method for host grain (マス one ペレ Star ト).

Aforesaid method one of (ii), for needed starting material all being carried out resupply after the pre-mixing method of forcing machine.The additive method of method beyond (ii) be for being combined with the host (マス one drug) of additive earlier with making high density, this host is further carried out pre-mixing individually or with the resin that is left after, resupply the method for forcing machine.In addition, this host can be selected arbitrary shape Powdered and that this powder has been carried out compression granulation etc.In addition,, for example can enumerate Nautamixer, V-type mixing tank, Henschel mixing tank, chemomotive force device and extrude mixing tank etc. as other pre-mixing device, but the mixing tank of the high-speed stirring type of preferred as super mixing tank etc.Further, other pre-blend approach for example is that resin and additive are dispersed in solvent and after being mixed with solution, remove the method for this solvent again.

By the resin that forcing machine is extruded, can directly cut off and carry out granulating, or after forming strand, this strand is cut off with tablets press and carried out granulating.In addition, outside during when being necessary to reduce as the influencing of dust etc., preferably the environmental gas around the forcing machine carry out cleaningization.Further, in this particulate is made, can by at CD with the whole bag of tricks that polycarbonate resin or optics have proposed in the closed chain olefin resin, suitably carry out the minimizing of the bubble (bubbles of vacuum) that the minimizing of narrow and smallization that particle shape distributes, the short small powder of cutting minimizing, the transportation of thing (ミスカ Star ト thing) or producing when carrying and strand or granule interior produce.According to these methods, the generation ratio that can carry out the height circulationization of moulding and reduce the bad phenomenon of silver-colored spot (シ Le バ one) etc.In addition, coating of particles can be the general shape of cylindrical, corner post shape, sphere etc., and is more preferably cylindrical.The diameter of preferred this cylinder is 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.

＜moulding product〉about forming by resin combination of the present invention

The light-diffusing resin composition of the present invention that obtains as mentioned above can produce various products by the particle of making is as mentioned above carried out injection moulding usually.And, also can be without granulation, with forcing machine directly with the resin manufacture slabbing behind the melting mixing, film like, special-shaped extrusion molding article, blowing (direct blow) moulding product and injection moulding product.

In described injection moulding, not only can adopt common forming method, can also be according to purpose, suitably adopt compression molding, injection moulding extrusion molding, gas assistant injection molding, foaming (comprising the moulding of injecting), insert moulding by supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection molding method of heating cooling mould molding, dual-color forming, interlayer moulding and ultra-high speed injection moulding etc. rapidly, thereby obtain the moulding product.The advantage of these various forming methods is all known.In addition, moulding can be selected any in cold runner mode and the hot runner mode.Wherein about large-scale moulding product, preferred injection moulding extrusion molding.

The injection moulding extrinsion pressing can provide the moulding product that have good dimensional precision and reduced deformation.The reduction of deformation is played very important effect to the homogeneity of printing opacity.In addition, the reduction of deformation can bring the use of the higher hard coat agent of tackiness.On the one hand, the injection moulding extrinsion pressing from the feature of its forming method, can be filled into jumbo resin in the mold from the few cast gate of quantity at high speed.Its result applies excessive thermal load easily on the resin when moulding, therefore need the higher resin combination of thermostability.In addition, injection moulding product of the present invention by carrying out being processed as with thermal flexure the secondary processing operation of representative, can be shaped to the shape of regulation after injection moulding.

In addition, resin combination of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet, film like and be used by extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting method etc.And, by implementing specific stretching operation, also can be shaped to heat-shrinkable tube.In addition, also can resin combination of the present invention be manufactured the moulding product by rotoforming or blow molding etc.

The moulding product of the light-diffusing resin composition of the diffusion light with color and luster excellence so, can be provided.That is, according to the present invention, provide light-diffusing resin composition melt molding and the moulding product that form in addition, described light-diffusing resin composition contains B composition and other additives of 0.01～3 weight part with respect to the A composition of 100 weight parts.

＜about the illumination cover 〉

Light-diffusing resin composition of the present invention has good light transmission, color and luster and brightness, and thermostability is also very good, so be suitable for illumination with covering.

Light-diffusing resin composition of the present invention is because of the randomness of shape in forming process or be that the flame resistivity material of purpose is widely used to suppress burning in home fire.As light source, can use bulb, luminescent lamp, White LED and arrange red, green and blue three-color LED combination etc.As the function that is used for diffusion light of script purpose, because in various illuminations, difference such as distance between light and the light source-cover, so can cover the thickness of moulding product by adjusting, perhaps diffusion particle concentration can access desirable diffusion light.

＜cover with illumination about vehicle

Light-diffusing resin composition of the present invention, when its light transmission, color and luster and brightness were good, thermostability was also good, covered with illumination so be suitable for vehicle.Identical with described illumination with cover, but because randomness, the aesthetic appearance of the machining shape of light-diffusing resin composition of the present invention in forming process are good, so can be widely used.About the inside components of vehicle, placing without vehicle interior temperature summer has and surpasses 100 ℃ situation, so the resin combination of excellent heat resistance very preferably.In addition, as light source, can use bulb, luminescent lamp, White LED and arrange red, green and blue trichromatic LED combination etc.As the function that is used for diffusion light of script purpose, in various illuminations, because the differences such as distance between light and the light source-cover, so can be by regulating cover moulding product thickness, perhaps diffusion particle concentration can access desirable diffusion light.

＜about light diffusing sheet 〉

Light-diffusing resin composition of the present invention, when its light transmission, color and luster and brightness were good, thermostability was also good.Therefore, be suitable for the big light diffusing sheet of area.As better purposes, can enumerate the maximal projection area is 500～50000cm ²Light diffusing sheet.The preferred maximal projection area of light diffusing sheet is 1000～25000cm ², preferred thickness is 0.3～3mm.Therefore,, can provide by above-mentioned light-diffusing resin composition to form, have described maximal projection area according to the present invention, and the good light diffusing sheet of light transmission, color and luster and brightness.

As further preferred form, can provide by above-mentioned light-diffusing resin composition according to the present invention to form, area is 500～50000cm ²(1000～25000cm more preferably ²) the display unit light diffusing sheet.As the display unit light diffusing sheet, can enumerate the light diffusing sheet that uses in the display screen of the such projection display device of the light diffusing sheet that uses in the backlight module of liquid crystal indicator and projection TV.Wherein, preferred Staight downward type backlight light diffusing sheet.Can use various light sources in the backlight module, can use cold-cathode tube, White LED and arrange red, green and blue trichromatic LED combination.

The light diffusing sheet that forms by light-diffusing resin composition of the present invention, also can be the light diffusing sheet that its surface has the concave-convex surface shape of Fresnel Lenses shape, cylindrical mirror shape, bright spot DOT shape and prism shape etc., perhaps also can be with other materials in addition stacked the plywood of described shape.When light-diffusing resin composition of the present invention is directly given Fresnel Lenses shape or cylindrical mirror shape, can be desired shape with the forming method machine-shaping of described resin combination by injection moulding, compressed moulding and extrusion moulding etc.Further, as forming concavo-convex method from the teeth outwards by injection moulding, compressed moulding and extrusion moulding etc., can enumerate (1) on mold surface or transfer roll surface, be provided with corresponding with described shape concavo-convex, the described concavo-convex method that is transferred to the synthetic resin surface; And (2) will be provided with the concavo-convex other materials corresponding with described shape and be inserted in the mold, when perhaps extruding stacked and become one with synthetic resin after, remove described other materials, thereby on the synthetic resin surface, concavo-convex method etc. is set.

In addition, as required, described screen can by stacked have photoluminescent pigment the layer, thereby can omit the lens that form by concave-convex surface.Further, display unit of the present invention in order to prevent from the light source reflection of light, can form various optical reflection films with in the light diffusing sheet at its light source side (face opposite with the viewer).

＜about other purposes 〉

Further, light-diffusing resin composition of the present invention, except that above-mentioned light diffusing sheet, also useful in various electronics/electrical equipments, OA equipment, the various uses of vehicle with exterior member, vehicle interior member, mechanical part, other Agricultural Materials, fishery material, transport container, packaging vessel and groceries etc.With the purposes beyond the light diffusing sheet, for example can enumerate electric light cover, instrument, billboard (especially internal irradiation), resin window glass, image read-out, vehicle ceiling material, boats and ships ceiling material, dwelling house roof Material and solar cell housing etc. as display unit.

Further, to the moulding product that form by light-diffusing resin composition of the present invention, can also carry out various surface treatments.In this said surface treatment, be meant that the surface at synthetic resin of evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (plating, plated by electroless plating, fusion plating etc.), application, coating and printing (containing the transfer printing type lamination) etc. forms the processing of new coating, can use the method that is generally used for polycarbonate resin.As surface treatment, can enumerate the various surface treatments of hard coat, hydrophobic/the oleophobic coating, ultraviolet radiation absorption coating, infrared ray absorption coating and metallic coating (evaporation) etc. particularly.Hard coat is when using without, as preferred and necessary surface treatment.

Embodiment

The present inventor thinks preferred forms of the present invention at present, and the embodiment for the preferable range that satisfies above-mentioned each important document for example, is recorded in its typical example among the following embodiment.Certainly, the present invention is not limited to these embodiments.

Each characteristic value is measured according to following method.

(1) 5% weight reduces temperature

Based on JIS K7120, adopt the TGA determinator, in nitrogen environment, in 23 ℃ to 900 ℃ temperature range and under the condition determination of 20 ℃/minute heat-up rate, measuring.In described weight minimizing process, when confirming to reduce by 5% weight, temperature is at this moment reduced temperature as 5% weight.

(2) total light transmittance

Under 280 ℃ of barrel temperatures and condition described later, the making length of side is the test piece of 50mm, thickness 2mm, adopts the mist shadow instrument HR-100 that color technical institute makes in (strain) village, measures the transmittance of thickness direction based on ASTMD1003.

(3) dispersity

Under 280 ℃ of barrel temperatures and condition described later, the making length of side is the test piece of 50mm, thickness 2mm, adopts the varied angle meter GP-200 that color technical institute makes in (strain) village to measure.

Fig. 1 represents the summary of measuring method.In Fig. 1, from the top vertically when test piece surface irradiation light, if γ=0 degree see through light quantity as 100, then it sees through light quantity becomes the angle (degree) of 50 o'clock γ as dispersity.

(4) color and luster of diffusion light (YI, Δ YI)

Under 340 ℃ of barrel temperatures and condition described later, by continuously shaped, the making length of side is the test piece of 150mm, thickness 2mm, and with it as " test piece A ".In addition, under same temperature condition, resin is detained 10 minutes in barrel after, the beginning moulding, the test piece that is obtained by the injection moulding second time is as " test piece B ".To these test pieces,, measure the YI value by the illuminant-C reflection method by colour measurement instrument (Z-1001DP that Japanese electric look industry (strain) is made).

As YI, the value of YI value that perhaps the YI value of test piece B is deducted test piece A is as Δ YI with the YI value of test piece A.

(5) silver-colored spot

About having or not of silver-colored spot, the moulding product of the above-mentioned test piece A of visual observation, B surface, and according to following judgement implementation evaluation.

Zero: test piece A, B all do not have silver-colored spot

△: do not find silver-colored spot among the test film A, but produced silver-colored spot among the test film B

*: test film A, B all produce silver-colored spot

(6) the thermostability evaluation of large-scale injection moulding extrusion molding product

By the injection moulding extrinsion pressing, and with the aftermentioned condition, the moulding product of moulding thickness 5mm shown in Figure 2 are confirmed its outward appearance.Moulding is after determining to purify injection rate fully, carries out 20 injection mouldings continuously, behind to be formed the stablizing, amounts to 10 with the 11st～20 time moulding product, and visual observation has or not silver-colored spot, according to following judgement implementation evaluation.

Zero: all moulding product all do not have silver-colored spot

△: produce silver-colored spot in the part moulding product

*: all moulding product all produce silver-colored spot

(7) remaining quantity of antioxidant

By the antioxidant in the solvent extraction polymer particle, adopt high-speed liquid chromatography (HPLC) and ¹H-NMR carries out quantitatively.

Embodiment 1～39, comparative example 1～17

[Production Example of diffusion particle]

(preparation of PMMA-1)

In the polymerizer of band stirrer, thermometer, deionized water 500 weight parts of packing into and being dissolved with 0.1 weight part Sodium Lauryl Sulphate BP/USP, and to wherein disperseing uncle's calcium phosphate 50 weight parts.Again to wherein, put into prepared beforehand good at methyl methacrylate 90 weight parts, dissolved benzoyl peroxide 0.5 weight part in the polymerizable monomer composition of Viscoat 295 10 weight parts, Diisopropyl azodicarboxylate 0.5 weight part, mixed solution as アデカス Block PEP-24G (rising sun electrochemical industry (strain) manufacturing) 0.5 weight part of phosphite antioxidant, stirred 10 minutes with 10000rpm with T.K homogeneous stirrer, be modulated into after drop directly is approximately 3 μ m, as antioxidant, add アデカス Block PEP-24G (rising sun electrochemical industry (strain) manufacturing) 3.0 weight parts.Then, polymerizer is heated to 65 ℃, while stir carry out suspension polymerization after, be cooled to room temperature.Filter, wash, behind the suspension that obtains thus, be dried, thereby obtain becoming crosslinked (methyl) acrylic polymers particle that contains the phosphorous acid esters antioxidant (PMMA-1, specific refractory power 1.49,5% weight reduce 340 ℃ of temperature, median size 3.0 μ m) of light diffusing agent.

(preparation of PMMA-2)

Except adopted アデカス Block PEP-24G (rising sun electrochemical industry (strain) manufacturing) 1.0 weight parts as oxidation inhibitor, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-2, specific refractory power 1.49,5% weight reduce 350 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(modulation of PMMA-3)

Except adopt イ Le ガ Off オス 168 (manufacturings of チバガイギ one company) 0.5 weight part as antioxidant, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-3, specific refractory power 1.49,5% weight reduce 330 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-4)

Except adopting アデカス Block HP-10 (rising sun electrochemical industry (strain) manufacturing) 0.5 weight part as antioxidant, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-4, specific refractory power 1.49,5% weight reduce 340 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-5)

Except adopt イ Le ガノ Star Network ス 1076 (manufacturings of チバガイギ one company) 0.1 weight part as antioxidant, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-5, specific refractory power 1.49,5% weight reduce 330 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-6)

Except adopting スミライザ one TP-D (Sumitomo Chemical (strain) manufacturing) 0.5 weight part as oxidation inhibitor, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-6, specific refractory power 1.49,5% weight reduce 330 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-7)

The amount of Sodium Lauryl Sulphate BP/USP is adjusted into 0.05 weight part, and the revolution of T.K homogeneous stirrer is adjusted into 3000rpm, drop directly is adjusted into beyond the 15 μ m, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-7, specific refractory power 1.49,5% weight reduce 340 ℃ of temperature, median size 14.5 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-8)

The amount of Sodium Lauryl Sulphate BP/USP is adjusted into 0.05 weight part, and the revolution of T.K homogeneous stirrer is adjusted into 2000rpm, drop directly is adjusted into beyond the 31 μ m, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-8, specific refractory power 1.49,5% weight reduce 340 ℃ of temperature, median size 30.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-9)

In the polymerizer that has stirrer, thermometer, deionized water 500 weight parts of packing into and being dissolved with Sodium Lauryl Sulphate BP/USP 0.1 weight part are again to wherein disperseing uncle's calcium phosphate 50 weight parts.And to wherein, the polymerizable monomer composition of putting into the good methyl methacrylate of prepared beforehand 90 weight parts, Viscoat 295 10 weight parts has dissolved the mixed solution of benzoyl peroxide 0.5 weight part, Diisopropyl azodicarboxylate 0.5 weight part, stirred 10 minutes with 10000rpm with T.K homogeneous stirrer, being modulated into the drop footpath approximately becomes 3 μ m.Then, polymerizer is heated to 65 ℃, while stir carry out suspension polymerization after, be cooled to room temperature.Behind the suspension that filter, washing obtains thus, be dried, obtain becoming crosslinked (methyl) acrylic polymers particle that contains the phosphorous acid esters antioxidant (PMMA-9, specific refractory power 1.49,5% weight reduce 254 ℃ of temperature, median size 3.0 μ m) of light diffusing agent.

(preparation of PMMA-10)

Except adopting アデカス Block PEP-24G (rising sun electrochemical industry (strain) manufacturing) 0.01 weight part as antioxidant, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-10, specific refractory power 1.49,5% weight reduce 270 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

(preparation of PMMA-11)

Except adopting Sandstab P-EPQ (Network ラリア Application トジヤパ Application (strain) manufacturing) 0.5 weight part as antioxidant, operate in the same manner with the preparation of PMMA-1, obtain containing crosslinked (methyl) acrylic polymers particle (PMMA-11, specific refractory power 1.49,5% weight reduce 280 ℃ of temperature, median size 3.0 μ m) of phosphorous acid esters antioxidant.

The median size of the usage quantity of the antioxidant that uses in the manufacturing about diffusion particle, its remaining quantity, light diffusing agent is illustrated in the table 1.

In addition, the antioxidant that uses in the manufacturing of diffusion particle is represented following material.

(antioxidant that uses in the manufacturing of diffusion particle)

アデカス Block PEP-24G: two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites

168: three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters of イ Le ガ Off オス

アデカス Block HP-10:2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester

イ Le ガノ Star Network ス 1076: octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester

スミライザ one TP-D: tetramethylolmethane four (3-lauryl thiopropionate)

Sandstab P-EPQ: four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates

(light diffusing polycarbonate resin composition particle and by the formed body Production Example of this resin composition pellet moulding)

(i) making of molding material

The various additives of table 1 and table 2 record are engaged in polycarbonate resin 100 weight parts with separately use level, and adopt the mixing machine uniform mixing.Resulting mixture is supplied in forcing machine the screw rod root first supplying opening and extrude.Forcing machine use be equipped with diameter 30mm Φ screw rod, and can the deflated biaxial extruder (TEX30 α (meshing fully, rotation, two screw-type screw rods) in the same way, (strain) JSW makes).Adopted the screw-rod structure that in front of venting port, has a mixing district.Extrusion condition is extrusion capacity 25kg/h, screw rod revolution 150rpm, exhaust portion vacuum tightness 3kPa, and in addition, the barrel temperature of forcing machine is that first supplying opening is that 270 ℃, mold are 280 ℃.The distribution of barrel temperature is shown every section impartial increasing greatly and is distributed.Resulting strand is sheared and obtained particle.

The (ii) manufacturing of test piece

Adopt hot air dryer, under 120 ℃ temperature, the above-mentioned particle that obtains carried out 5 hours drying.Institute's dry granules is supplied to injection moulding machine (SG260M-HP, Sumitomo heavy-duty machine tool industry (strain) is made), injection moulding test piece.Condition of molding is: with barrel temperature be adjusted into each estimate in temperature, the die temperature of regulation be 80 ℃, injection moulding speed be 20mm/ second, the 50MPa that keep-ups pressure, cooling time 30s.

The manufacturing of (iii) large-scale injection moulding extrusion molding product

To the above-mentioned particle that obtains, employing has large-scale shaper (MDIP2100, the maximum clamping force 33540kN four concurrent control mechanisms, that can carry out the injection moulding extrusion molding of pressing plate, (strain) name mechanism is done manufacturing) carry out injection moulding, obtain large-scale moulding product shown in Figure 1.Under 120 ℃ of temperature, particle carried out 5 hours drying by incidental Hopper Dryer.Condition of molding is: barrel temperature is 300 ℃, 280 ℃ of hot runner design temperatures, 110 ℃ of fixed side mold temperature, 100 ℃ of movable side mold temperature, injection moulding speed 16mm/s, filling time 31s, be 3.0mm, cooling time to be that 230s and shaping cycle are 310s as the pressure stroke of the stroke from middle matched moulds position to final matched moulds position.In addition, the joint face of movable side mold does not contact with the joint face of fixed side mold in final progressive position.Runner adopts the hot runner (gate diameter is 7mm Φ) of the valve gate type of モ one Le De マス one ズ company manufacturing, beginning mould compression when being about to finish filling, finish fill after valve-off cast gate at once, thereby can be not condition to the barrel adverse current with molten resin from cast gate.

Each evaluation result of resulting profiled sheeting is shown in table 2～table 4.In addition, the mark of each composition of record is represented following material in table 2～table 4.

(A composition)

PC-1: the p-tert-butylphenol and the carbonyl chloride that stop agent by dihydroxyphenyl propane, as end, by interface polycondensation synthetic straight chain shape aromatic polycarbonate resin powder (パ Application ライト L-1225WP (trade(brand)name), viscosity-average molecular weight 22500, Supreme Being people changes into (strain) and makes)

PC-2: straight chain shape aromatic polycarbonate resin powder (パ Application ライト L-1225WX (trade(brand)name), viscosity-average molecular weight 19700, Supreme Being people changes into (strain) and makes)

(B composition)

PMMA-1～9: by the crosslink propylene acid particles of method for preparing

(C composition)

P-1: four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates (Sandstab P-EPQ (trade(brand)name), Network ラリア Application トジヤパ Application (strain) is made)

P-2: two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites (アデカス Block PEP-24G (trade(brand)name), rising sun electrochemical industry (strain) is made)

P-3: trimethyl phosphate (TMP (trade(brand)name), big eight chemical industry (strain) are made)

(D composition)

HP-1: octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (イ Le ガノ Star Network ス 1076 (trade(brand)names), チバガイギ one company makes :)

HP-2:3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane (アデカス Block AO-80 (trade(brand)name), rising sun electrochemical industry (strain) is made)

(E composition)

E-1: coumarins white dyes [Ha Star コ one Le PSR (trade(brand)name), Ha Star コ one Le ケミカ Le (strain) is made]

E-2: white dyes [カヤライト OS (trade(brand)name), Japanese chemical drug (strain) is made]

Industrial utilizability

Light-diffusing resin composition of the present invention is to have simultaneously high light diffusing and the Gao Guang that did not in the past have Line transmitance, and the resin combination with the good heat endurance that does not produce silver-colored spot, resin foxiness. Owing to have than in the past better heat endurance, so be particularly suitable as the light that large-scale display device is used Diffuser plate (for example, be used for the backlight module such as liquid crystal indicator light diffusing sheet, be used for projection TV etc. The light diffusing sheet of the display screen of projection display device etc.). In addition, described characteristic is used except display unit Beyond the light diffusing sheet, for example be used for electric light cover, instrument, billboard (especially internal irradiation type), resin window glass (described parts are with in the vehicle for glass, image read-out, vehicle ceiling material, vehicle interior member Dress illumination is representative with cover), boats and ships with ceiling material, dwelling house roof Material, solar cell housing, Various electronics/electric equipments, OA equipment, vehicle part, mechanical part, other agriculture goods, materials and equipments, fishing Industry goods, materials and equipments, cask, packing container and comprise in the wide spectrum of groceries the product that it reaches Industry is worth high.

Claims

1. light-diffusing resin composition, it is characterized in that, comprise as the aromatic polycarbonate resin of A composition with as crosslinked (methyl) acrylic polymers particle of B composition, wherein, described B composition is to be crosslinked (methyl) acrylic polymers particle that more than 300 ℃ and does not mix with described aromatic polycarbonate resin by the temperature that the weight that the calorimetric measurement device is measured reduces at 5% o'clock, and with respect to the A composition of 100 weight parts, the B composition is 0.01～3.0 weight part.

2. light-diffusing resin composition as claimed in claim 1, it is characterized in that, the B composition is crosslinked (methyl) acrylic polymers particle that has cooperated stablizer in polymerization process in crosslinked particle, described stablizer is at least a stablizer of selecting from the group that Phosphorus compound, hindered phenol compound and sulphur class antioxidant are formed, and with respect to the B composition of 100 weight parts, described stablizer is 0.005～2.0 weight part.

3. light-diffusing resin composition as claimed in claim 2 is characterized in that, the Phosphorus compound that the B composition contains is the phosphorous acid class stablizer of following formula (I)～(III) expression,

In the formula (I), Ar ₁For the alkyl of carbonatoms 6～20 or contain alkyl or do not contain the aromatic series base of the carbonatoms 6～20 of alkyl;

In the formula (II), Ar ₂For the alkyl of carbonatoms 6～20 or contain alkyl or do not contain the aromatic series base of the carbonatoms 6～20 of alkyl;

In the formula (III), Ar ₃For the alkyl of carbonatoms 6～20 or contain alkyl or do not contain the aromatic series base of the carbonatoms 6～20 of alkyl.

4. as any described light-diffusing resin composition in the claim 1 to 3, it is characterized in that, contain as the Phosphorus stablizer of C composition and/or as the hindered phenol compound of D composition, and with respect to the A composition of 100 weight parts, the C composition is that 0.0001～1 weight part, D composition are 0.001～1 weight part.

5. as any described light-diffusing resin composition in the claim 1 to 4, it is characterized in that, contain the white dyes as the E composition, wherein, with respect to the A composition of 100 weight parts, the E composition is 0.0005～0.5 weight part.

6. an illumination is characterized in that with cover, is the illumination cover that is formed by any described light-diffusing resin composition in the claim 1 to 5.

7. a vehicle lamp cover is characterized in that, is the vehicle lamp cover that is formed by any described light-diffusing resin composition in the claim 1 to 5.

8. a light diffusing sheet is characterized in that, is by any light diffusing sheet that described light-diffusing resin composition forms in the claim 1 to 5.

9. a Staight downward type backlight light diffusing sheet is characterized in that, is the Staight downward type backlight light diffusing sheet that is formed by any described light-diffusing resin composition in the claim 1 to 5.

10. light diffusing sheet as claimed in claim 8 is characterized in that, it is that the maximal projection area is 500～50000cm ², and by the light diffusing sheet of injection moulding extrusion molding manufactured.