CN101434750A - Polycarbonate resin composition - Google Patents

Abstract

The invention aims at providing polycarbonate resin material with improved liquidity, transparency and durability. The invention provides a resin composition which contains polycarbonate resin (component A) and polycarbonate oligomer (component B); relative to 100 weight parts of the component A, component B has 0.1-20 weight parts, wherein, the component A consists of polycarbonate-polysiloxane copolymer (component A1) containing polysiloxane units with 10-60 of number-average degree of polymerization, or consists of polycarbonate of the component A1 and polycarbonate of component other than the component A1; besides, content of the polysiloxane units in 100 weight percent of the component A is 0.1-20 weight percent; average degree of polymerization of the component B is 3-15.

Description

Poly carbonate resin composition

Technical field

The present invention relates to improve the poly carbonate resin composition of flowability, the transparency and weather resistance.In more detail, the present invention relates to by resin combination that has improved above-mentioned characteristic by specific organopolysiloxane-Copolycarbonate of combination and polycarbonate oligomer and the moulding product that form by above-mentioned resin combination with thin-walled.

Background technology

Polycarbonate resin from the advantageous characteristic of the physical strength and the transparency, can use at mechanical part, trolley part, electric. in the multiple use of electronic unit etc.In recent years, along with mobile phone, smart phone and removable computer are the miniaturization of carrying intelligent terminal (comprising thin-walled property) and the light-weighted progress of representative, various resin components become thin-walled state (for example with reference to patent documentation 1).Therefore,, need high workability, need the weather resistance of thin molded article in practicality on the other hand so that form thin-walled for the resin material that forms such parts.And then the button parts that carries key in the parts of intelligent terminal in formation utilizes transparent hard resin sometimes.In such parts,, be to use transparent polycarbonate resin from the transparency, physical strength and weather resistance viewpoint.Because above-mentioned thin-walled property trend, for such part requirement when keeping the good transparency, the compressive strength repeatedly in the time of also will taking into account the input of thin-walled and button.Therefore, the polycarbonate resin material of often needed such improvement mobile, the transparency and weather resistance.

As the button parts material that carries intelligent terminal that forms from poly carbonate resin composition, once proposed to use in viscosity-average molecular weight 16, the key that the carries intelligent terminal resin combination (with reference to patent documentation 2) that adds the phosphoric acid ester of oligomeric in 000～22,000 the polycarbonate resin.The intelligent terminal key moulding product (with reference to patent documentation 3) that carry of the resin combination formation of polycarbonate resin and vinylbenzene-acrylonitrile copolymer (AS) resin (weight-average molecular weight of the resin of embodiment about 78,000) composition have also been proposed in addition.In addition, proposed in addition to use that the solvable composition 2 weight % of acetone are following, the polycarbonate resin of extension fracture appearance transition tem below 15 ℃ carry out moulding carry intelligent terminal with key moulding product (with reference to patent documentation 4).What in addition, proposed the poly carbonate resin composition moulding that is made of polycarbonate resin, phosphazene compound, thermo-stabilizer and releasing agent in addition carries intelligent terminal with key moulding product (with reference to patent documentation 5).And then, be good for moulding product (with reference to patent documentation 6) as the intelligent terminal usefulness of carrying that known document has organopolysiloxane-Copolycarbonate and releasing agent to constitute.

On the other hand, disclose in polycarbonate-based material and to cooperate the polycarbonate oligomer to keep the transparency, improve the technology (with reference to patent documentation 7 and 8) of flow characteristics.And, also disclose and use Banbury mixer organopolysiloxane-polycarbonate-copolymerized zoarium, polycarbonate resin, polycarbonate oligomer and resin combination (with reference to patent documentation 9) through obtaining by extruding after montmorillonite (montmorillonite) mixing of the processing that organises.But, the fiting effect of the polycarbonate oligomer of this resin combination only limit to some cold impact values on go up.

2007-No. 048602 communique of (patent documentation 1) TOHKEMY

2004-No. 346112 communiques of (patent documentation 2) TOHKEMY

2005-No. 044130 communique of (patent documentation 3) TOHKEMY

2006-No. 092951 communique of (patent documentation 4) TOHKEMY

2007-No. 045909 communique of (patent documentation 5) TOHKEMY

(patent documentation 6) TOHKEMY is put down 11-No. 045139 communique

2006-No. 188594 communiques of (patent documentation 7) TOHKEMY

Clear 61-No. 123658 communiques of (patent documentation 8) TOHKEMY

Special table 2007-No. 514854 communique of (patent documentation 9) JP

Summary of the invention

As mentioned above, at the present situation of the polycarbonate resin material of, the transparency mobile and weather resistance in order to have improved, above-mentioned prior art, with the improvement of plasticity as main purpose, but do not take into full account weather resistance when using.Purpose of the present invention, the polycarbonate resin material of be to provide a kind of improvement that improves the aspect that does not take into full account in the prior art mobile, the transparency and weather resistance.In order to reach such purpose, the inventor etc. are through meticulous continuous research, and it found that Copolycarbonate and the combination of polycarbonate oligomer by containing specific poly organo alkyl structure can reach above-mentioned purpose.Known polycarbonate oligomer mainly produces effect to the polycarbonate resin of general bisphenol A-type, but it also can obtain the good transparency equally for the polycarbonate resin that contains polycarbonate-poly organo alkyl copolymer, does not have very big decline but also be surprised to find the good weather resistance that this polycarbonate resin has.According to above-mentioned opinion, we have finished the present invention.

The purpose of the invention described above is to finish in the following way.

(1) a kind of resin combination, it contains polycarbonate resin (A composition) and polycarbonate oligomer (B composition), with respect to 100 weight part A compositions, the B composition is 0.1～20 weight part, wherein, the A composition is made up of the polycarbonate-poly organo alkyl copolymer (A1 composition) of the polyorganosiloxane units that contains useful following general formula (α 1) expression, or be made up of the polycarbonate beyond this A1 composition and the A1 composition, and polyorganosiloxane units content is 0.1～20 weight % in the 100 weight %A compositions; The mean polymerisation degree of B composition is 3～15.

(in the formula, R ₁, R ₂, R ₃And R ₄The alkyl or phenyl of expression carbonatoms 1～6, identical or different; R ₅Expression is from organic residue of the divalence of aliphatics or aromatics; N represents the unitary repeat number in the parantheses, and the mean value of repeat number is 10～60; Structural unit in the parantheses is the mixture more than 2 kinds or is not mixture more than 2 kinds.)

The transparency and excellent in te pins of durability as the polycarbonate resin of A composition.Therefore the intermiscibility excellence of B composition and A composition, from this on the one hand, can keep the transparency and favorable durability.

The proportion of composing of A composition and this B composition is that with respect to 100 weight part A compositions, the B composition is 0.1～20 weight part, is preferably 1～15 weight part, more preferably 2～9 weight parts.

One of suitable embodiment of the present invention, (2) a kind of resin combination, it is the resin combination of above-mentioned (1), wherein, as the polycarbonate-poly organo alkyl copolymer of above-mentioned A1 composition, have as the structural unit of the following general formula (α 2) of general formula (α 1) and have structural unit with following general formula (i) expression.

(in the formula, R ₁, R ₂, R ₃And R ₄And n is identical with above-mentioned general formula (α 1); R ₁₁And R ₁₂The alkylidene group of expression carbonatoms 2～6, these groups are identical or different; Y is illustrated in and phenyl ring bonded R ₁₁, R ₁₂And the hydrogen atom or the alkoxyl group that replace on Sauerstoffatom (O) different positions.)

(A represents organic residue, the singly-bound of at least a kind divalence selecting from the group of being made up of following formula (i-1)～(i-3) and (i-5) or the key of being selected by following formula (i-4) arbitrarily; S and t are respectively 0 or 1～4 integer independently; R ₁₃And R ₁₄Organic residue of selecting in the group of representing independently respectively to form by the aralkoxy of the aryloxy of the aralkyl of the aryl of the cycloalkyloxy of the cycloalkyl of the alkoxyl group of the alkyl of halogen atom or carbonatoms 1～10, carbonatoms 1～10, carbonatoms 6～20, carbonatoms 6～20, carbonatoms 6～10, carbonatoms 7～20, carbonatoms 6～10 and carbonatoms 7～20.)

(in the formula (i-1), R ₁₅, R ₁₆, R ₁₇And R ₁₈The alkyl of representing hydrogen atom, halogen atom or carbonatoms 1～3 respectively independently.)

(in the formula (i-2), R ₁₉And R ₂₀The alkyl of representing hydrogen atom, halogen atom or carbonatoms 1～3 respectively independently.)

(in above-mentioned formula (i-3), u represents 4～11 integer, these a plurality of R ₂₁And R ₂₂The group of selecting in the group of representing independently respectively to form by the alkyl of hydrogen atom, halogen atom and carbonatoms 1～3.)

(in the formula, in (i-5), R ₂₃And R ₂₄The alkyl of representing hydrogen atom, halogen atom or carbonatoms 1～10 respectively independently.)

Above-mentioned α 2 can obtain having good, the resin combination of excellent durability more of hydrolytic resistance.

One of suitable embodiment of the present invention, (3) a kind of resin combination, it is the resin combination of above-mentioned (1)～(2), wherein, the viscosity-average molecular weight of above-mentioned A composition is 16,000～25,000 scope.A composition viscosity-average molecular weight (M) less than 10,, in a lot of fields, be difficult to obtain the physical strength in the practicality, at 000 o'clock if surpass 50,000, the melt viscosity height of resin combination generally needs high forming process temperature, so, the viscosity-average molecular weight of A composition, 10,000～50,000 scope is suitable.And then as above-mentioned thin molded article, in requiring the parts of its weather resistance, the viscosity-average molecular weight of A composition is 16,000～25,000, more preferably 17,000～21,000.

In addition, one of suitable embodiment of the present invention, (4) a kind of resin combination, it is the resin combination of above-mentioned (3), wherein, the viscosity-average molecular weight of above-mentioned A1 composition is 16,000～25,000 scope.The viscosity-average molecular weight of the A composition of the present invention in above-mentioned (3) also can by will this extraneous A1 composition and the A1 composition beyond the mixing of polycarbonate modulate.Therefore, for example, mix the A composition that can obtain viscosity-average molecular weight 20,000 by other polycarbonate resin with the A1 composition of viscosity-average molecular weight 100,000 and viscosity-average molecular weight 15,000.But, the mixing of the composition that the viscosity-average molecular weight difference is very big, the general easy transparency that causes reduces, so the A1 composition preferably also is in the scope of the viscosity-average molecular weight of above-mentioned A composition.Therefore, according to these (4), can provide the transparency more superior resin combination.

One of suitable embodiment of the present invention, (5) a kind of resin combination, it is the resin combination of above-mentioned (1)～(4), wherein, above-mentioned A composition, the unit content of the organopolysiloxane that contains in the 100 weight %A1 compositions is 1～20 weight %, and the unit content of the organopolysiloxane in the 100 weight %A compositions is 0.5～5 weight %.Though the unit content of the organopolysiloxane that contains in the 100 weight %A1 compositions has no particular limits, when too high, make the transparency of resin combination reduce easily, so in the scope of 0.1～40 weight %, be suitable.This content is 1～20 weight % preferably, more preferably 2～12 weight %, further preferably 3～10 weight %.Be lower than this OK range following in limited time the setting range of the organopolysiloxane concentration in the A composition is restricted, production efficiency variation, but surpass going up in limited time of this suitable scope, the performance that the transparency can not be stable causes the productivity variation thus.In addition, the unit content of the organopolysiloxane in the 100 weight %A compositions is 0.1～20 weight %, preferably 0.5～5 weight %, more preferably 1.5～4.5 weight %, the most preferably scope of 2～4 weight %.Above-mentioned (5) are to use the A1 composition of the unit content with this suitable organopolysiloxane, and the unit content of the organopolysiloxane that contains in the 100 weight %A compositions is controlled at this more suitably scope and constituting.The resin combination that can provide the transparency and weather resistance to take into account thus.

One of suitable embodiment of the present invention, (6) a kind of resin combination, it is the resin combination of above-mentioned (1)～(5), wherein, the n in the above-mentioned general formula (α 1) is 16～50 scope.The n of the polymerization degree that represents this organopolysiloxane then can not give resin combination sufficient weather resistance less than 10 o'clock, surpassed at 60 o'clock on the other hand, transparent variation.From transparent aspect, need differential to loose, from the weather resistance aspect, it is favourable that layer has the separation of certain degree.More suitably, this n is 16～50,20～40 scope that further suitable is.According to these (6), can take into account and obtain the better transparency and weather resistance.

As one of suitable embodiment of the present invention, (7) a kind of resin combination, it is the resin combination of above-mentioned (1)～(6), wherein, above-mentioned B composition is the oligomer that the structural unit by following general formula (β 1) forms.

(in the formula (β 1), A, s, t, R ₁₃And R ₁₄All expressions and same group, atom or the numerical value of above-mentioned formula (i).)

By the oligomer that the said structure unit forms, its excellent heat stability needing to be suitable for the shaping thin wall of high-temperature molding.Especially the embodiment that is more suitable for is, (8) a kind of resin combination, and it is the resin combination in above-mentioned (7), wherein, above-mentioned B composition is the oligomer of following general formula (β 2) expression.

(in the formula (β 2), A, s, t, R ₁₃And R ₁₄All expressions and same group, atom or the numerical value of above-mentioned formula (i); Z be carbonatoms that the part of hydrogen atom, hydrogen atom is replaced by fluorine atom or do not replaced by fluorine atom be 1～9 straight chain or branched-chain alkyl or phenyl substituted alkyl, carbonatoms be 10～50 chain alkyl, Siliciumatom amount be 4～40 polysiloxane chain or-X-C _mH _2m+1, wherein, X is-R-O-,-R-CO-O-or-R-O-CO-, this R represents that singly-bound or carbonatoms are 1～10 dibasic aliphatic alkyl; M represents 10～50 integer, and r represents 1～5 integer, and p represents 3～15 integer.)

By having this end structure, can obtain better thermostability, the resin material that is fit to high-temperature molding is provided.And because of this better thermostability, injection-molded article can obtain favorable durability.

One of suitable embodiment of the present invention, (9) a kind of resin combination, it is the resin combination of above-mentioned (1)～(8), its mist value with the 2mm thickness that JIS K7105 measures is 0.3～20%.And then according to other mode, (10) a kind of transparent resin moulding product are the transparent resin moulding product by resin combination injection molding is obtained.One of embodiment that this is suitable, (11) a kind of transparent resin moulding product, it is the transparent resin moulding product of above-mentioned (10), wherein, the wall thickness of above-mentioned injection-molded article is mainly formed by the part of 0.05～0.5mm.At this, said transparent resin moulding product, its mist value is 0.1～20%, preferably 0.2～4%, more preferably 0.2～2% moulding product.

Description of drawings

Fig. 1 is the front view for so-called "＜" shape test piece of estimating the fatigability use.In addition, the thickness of test piece is 3mm.At the part in the hole of symbol 4 expression anchor clamps, add that in the vertical direction of representing with symbol 3 load of regulation is tested by trier.

Reference numeral:

1: the body of "＜" shape test piece

2: the dotted line of the binding site of expression "＜" shape part and circular arc portion

3: the direction of on the fatigue test body, test piece being loaded

4: anchor clamps erection opening (circle of diameter 3mm)

5: the central angle (60 of the position of expression anchor clamps erection opening ⁰), its with the intersection point of symbol 7 as the center

6: the symmetry axis of test piece (on the figure, symmetry) up and down

7: the intersection point of the dotted line of symbol 2 and symmetry axis 6

8: the angle (90 of "＜" shape part ⁰)

9: the R face (R1.5: radius 1.5mm) of the inside part of "＜" shape part

10: the R face (R10: radius 10mm) of the Outboard Sections of "＜" shape part

11: the width (10mm) of "＜" shape part

Embodiment

Below, illustrate in greater detail the present invention

(A1 composition: polycarbonate-poly organo alkyl copolymer)

As mentioned above, A1 composition of the present invention contains the polyorganosiloxane units shown in the general formula (α 1).As the R in this general formula (α 1) ₁, R ₂, R ₃And R ₄Object lesson, can preferably enumerate methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, amyl group, heptyl and phenyl etc., particularly preferably be methyl.R5 represents the organic residue from the divalence of aliphatics or aromatics.-Si-R ₅-in, when contain-during Si-O-key, R ₅Can enumerate various ester ring type diol residue and divalent phenol residue.As this ester ring type glycol and divalent phenol, can utilize and identical polycarbonate described later.-Si-R ₅In, when have-during Si-C-key, R ₅Preferably can enumerate o-allyl phenol residue, para hydroxybenzene ethene residue, 4-allyl group-2-methoxyphenol residue and isopropenyl phenol residue etc., particularly preferably be the o-allyl phenol residue.That is, as mentioned above, preferred A1 composition has the structural unit shown in the general formula (α 2) as general formula (α 1).This R ₁₁And R ₁₂Can enumerate ethane-1,2-two bases, propane-1,3-two bases, propane-1,2-two bases, butane-1,4-two bases and butane-2,3-two bases etc., wherein, preferably ethane-1,2-two bases and propane-1,3-two bases, particularly preferably be propane-1,3-two bases.

In the polycarbonate-poly organo alkyl copolymer of A1 composition, have no particular limits for polycarbonate unit with the polyorganosiloxane units copolymerization.That is, can have the various carbonate units that make the two functionalities alcohol of divalent phenol and/or aliphatics and/or ester ring type be reacted and obtain with the carbonic ether presoma.Preferably from divalent phenol deutero-carbonate unit.Particularly preferably be the structural unit of using general formula (i) expression as mentioned above.On the other hand, as two functionality alcohol of the structural unit of the polycarbonate of deriving, more preferably the ester ring type glycol for example, can be enumerated cyclohexanedimethanol, cyclohexane diol, three ring (5.2.1.0 ^2.6) decane dimethanol, norbornane dimethanol, perhydronaphthalene-2,6-dimethanol, volution ethylene glycol, 1,4; 3,6-two dehydration-D-sorbitols, 1,4; 3,6-two dehydration-D-N.F,USP MANNITOL and 1,4; 3,6-two dehydration-L-iditols.

Concrete example according to the object lesson explanation general formula (i) of the dihydroxy compound of this structural unit of deriving.

Compound when being singly-bound as the A in the formula (i) can enumerate 4,4 '-xenol and 4,4 '-two (2,6-dimethyl) biphenol etc.

Compound when being formula (i-1) as A, can enumerate α, α '-two (4-hydroxy phenyl)-adjacent diisopropyl benzene, α, α '-two (4-hydroxy phenyl)-diisopropyl benzene (being commonly referred to " bis-phenol M ") and α, α '-two (4-hydroxy phenyl)-to diisopropyl benzene etc.

Compound when being formula (i-2) as A can be enumerated 9,9-two (4-hydroxy phenyl) fluorenes and 9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes etc.

Compound when being formula (i-3) as A, can enumerate 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane, 1,1-two (4-hydroxyl-3-aminomethyl phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-4-normenthanes and 1,1-two (3-cyclohexyl-4-hydroxy phenyl) hexanaphthene etc.

Compound when being any in the formula (i-4) as A, can enumerate 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl ether, 4,4 '-dihydroxy-diphenyl sulfone, 2,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl diphenylsulfide, 3,3 '-dimethyl-4,4 '-dihydroxyl diphenylsulfide and two (3,5-dimethyl-4-hydroxy phenyl) sulfones etc.

Compound when being any in the formula (i-5) as A, can enumerate 1,1-two (4-hydroxy phenyl) methane, 2,4 '-dihydroxyl ditan, two (2-hydroxy phenyl) methane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, two (4-hydroxyls-2,6-dimethyl-3-p-methoxy-phenyl) methane, two (4-hydroxy phenyl) cyclohexyl-methane, two (4-hydroxy phenyl) ditan, 1,1-two (4-hydroxy phenyl) ethane, 1,1-two (4-hydroxyl-2-phenyl)-1-diphenylphosphino ethanes, 1,1-two (4-hydroxyl-2-chloro-phenyl-) ethane, 2,2-two (4-hydroxy phenyl) propane (being commonly referred to " dihydroxyphenyl propane "), 2,2-two (4-hydroxyl-3-aminomethyl phenyl) propane (being commonly referred to " bisphenol-c "), 2,2-two (3-phenyl-4-hydroxy phenyl) propane, 2,2-two (4-hydroxyl-3-aminomethyl phenyl) propane, 2,2-two (4-hydroxyl-3-ethylphenyl) propane, 2,2-two (4-hydroxyl-3-isopropyl phenyl) propane, 2,2-two (3-tertiary butyl-4-hydroxy phenyl) propane, 2,2-two (3-bromine-4-hydroxy phenyl) propane, 2,2-two (3,5-dibromo-4-hydroxy phenyl) propane, 2,2-two (4-hydroxy phenyl)-1-phenyl-propanes, 2,2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa, 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxy phenyl) pentanes, 2,2-two (4-hydroxy phenyl) butane, 4,4-two (4-hydroxy phenyl) heptane, 2,2-two (4-hydroxy phenyl) octanes, 1,1-two (4-hydroxy phenyl) decane, 1,1-two (3-methyl-4-hydroxy phenyl) decane and 1,1-two (2,3-dimethyl-4-hydroxy phenyl) decane etc.

And then, dihydric phenol as the formula of deriving (i) structural unit in addition, preferred 2,6-dihydroxy naphthlene, quinhydrones, Resorcinol, by carbonatoms is the Resorcinol that 1～3 alkyl replaces, 3-(4-hydroxy phenyl)-1,1,3-trimethylammonium indane-5-alcohol, 1-(4-hydroxy phenyl)-1,3,3-trimethylammonium indane-5-alcohol, 6,6 '-dihydroxyl-3,3,3 ', 3 '-tetramethyl-spiral shell indane, 1-methyl-1,3-two (4-hydroxy phenyl)-3-normenthane, 1-methyl-2-(4-hydroxy phenyl)-3-[1-(4-hydroxy phenyl) sec.-propyl] hexanaphthene, 1,6-two (4-hydroxy phenyl)-1,6-hexanediones and ethylene glycol bis (4-hydroxy phenyl) ether etc.

In the above-mentioned dihydric phenol, bis-phenol M preferably in formula (i-1); 9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes preferably in the formula (i-2); Preferably 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxyl-3-aminomethyl phenyl) hexanaphthenes, 1,1-two (4-hydroxy phenyl)-3,3 in the formula (i-3), 5-trimethyl-cyclohexane; In the formula (i-4) preferably 3,3 '-dimethyl-4,4 '-dihydroxyl diphenylsulfide; And in formula (i-5) preferably dihydroxyphenyl propane, bisphenol-c and 1,1-two (4-hydroxy phenyl) decane.Wherein, most preferably good strength and dihydroxyphenyl propane with favorable durability.

Polycarbonate-poly organo alkyl copolymer can be made by known the whole bag of tricks.Preferred method is to make by the group with phenol hydroxyl to seal the organopolysiloxane of two ends and the method that carbonate oligomer is reacted.As other method, can enumerate will seal by group with phenol hydroxyl the state of the organopolysiloxane of two ends and dihydric phenol or the aliphatic diol coexistence method of being reacted with the carbonic ether precursor down, and will have the organopolysiloxane of chlorine atom and method that carbonate oligomer reacts etc. endways.In addition, in this reaction, can use the condition identical, about the then narration later on of polymerizing condition of polycarbonate with the polymerization of common polycarbonate.That is to say that in the A1 composition, it is created conditions, end stops agent and the composition of chain component agent etc. can be utilized the polycarbonate beyond the A1 composition described later equally.

In addition, in this polycarbonate-poly organo alkyl copolymer, even contain many not with the free organopolysiloxane polycarbonate bonding, that use as polymer raw material or on organopolysiloxane bonding carbonate unit or the terminal carbonate unit that stops agent, but they are not sufficient composition (below, be called " free organopolysiloxane etc. ").This free organopolysiloxane etc. can be by calculating its amount with the extraction treatment of normal hexane.

Become the reason that reduces the resin combination transparency after the cohesions such as free organopolysiloxane easily.Therefore, in A1 composition of the present invention, containing of this free organopolysiloxane etc. is proportional, the ratio of n-hexane extraction amount just, with respect to the organopolysiloxane composition that contains in this A1 composition is below the 10 weight %, is preferably below the 3 weight %, more preferably below the 2 weight %.On the other hand, consider that this contains proportional lower limit is appropriate about 0.1 weight % from practicality.In addition, the calculating of this n-hexane extraction amount is the multipolymer sample of weighing to be carried out Soxhlet extractron by superfine normal hexane handle and calculate.It is to implement 3 hours to be about 20 times/hour average period that this Soxhlet extractron is handled, and removes normal hexane and calculate from handle back solution.In order to reduce free organopolysiloxane etc., regulate adding ratio, emulsified state, temperature and the agitation condition of raw material or polymerization promotor, so that the monomer class in the reaction system is fully reacted.

(polycarbonate)

A composition of the present invention both can be made of separately the A1 composition, also can be the mixture of the polycarbonate beyond A1 composition and the A1 composition.Polycarbonate beyond this A1 composition can adopt by the pure and mild carbonic ether precursor of two functionalities with dihydric phenol and/or aliphatics and/or ester ring type and be reacted polycarbonate that obtain, known.Method as reaction can be enumerated 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.When adopting interface polycondensation, usually use the end of monobasic phenols to stop agent, as mentioned above, the polycarbonate of A composition also can be to add dihydric phenol or alcohol to, thereby polymerization the branch branched polycarbonate of trifunctional composition, and then also can be with aliphatic dicarboxylic acid or aromatic dicarboxylic acid and the vinyl monomer copolymerization polycarbonate of copolymerization in addition.

In the polycarbonate beyond this A1 composition, preferably has the polycarbonate of the structural unit shown in the following formula (i).This concrete example reaches preferred embodiment also as mentioned above, is preferably dihydroxyphenyl propane especially.About other detailed contents of polycarbonate, for example be documented on WO03/080728 brochure, flat 6-No. 172508 communiques of TOHKEMY, TOHKEMY flat 8-No. 27370 communiques, 2001-No. 55435 communiques of TOHKEMY and 2002-No. 117580 communiques of TOHKEMY etc.In addition, derive polycarbonate structural unit two functionality alcohol concrete example also with the A1 composition in identical.

Polycarbonate can contain branched-chain component, can enumerate 4,6-dimethyl-2,4 as the multi-functional aromatics more than the trifunctional that is used for branched polycarbonate, 6-three (4-hydroxy diphenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2,6-two (2-hydroxyl-5-methyl-benzyl)-4-methylphenols, and 4-{ 4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, the triphenol of α-dimethyl benzyl phenol etc.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane.By this multi-functional aromatics deutero-structural unit, its with 100 moles of % of total of structural unit of divalent component from other in, be preferably 0.03～1 mole of %, more preferably 0.07～0.7 mole of % is preferably 0.1～0.4 mole of % especially.In addition, the branched structure unit is not only by multi-functional aromatics and is derived, and the side reaction in the time of can also be as melting state transesterification reaction is not used multi-functional aromatics and derived.In addition, can pass through for the ratio of branched structure ¹H-NMR measures and calculates.As mentioned above, in the A1 composition, also can contain branched-chain component.

Polycarbonate comprises two functionality carboxylic acids of aromatic series or aliphatics (the comprising ester ring type) polyestercarbonate of copolymerization in addition.Aliphatic two functionality carboxylic acids are preferably α, ω-dicarboxylic acid.As the carboxylic acid of aliphatic two functionalities, for example can preferably enumerate the ester ring type diacid of the straight chain saturated aliphatic dicarboxylic acids of sebacic acid (sebacic acid), dodecanedioic acid, 14 carbon diacid, 18 carbon diacid and 20 carbon diacid etc. and cyclohexane dicarboxylic acid etc.In the A1 composition, also can contain the unit that derives by this dicarboxylic acid.

The viscosity-average molecular weight of A composition and A1 composition is for as mentioned above, and still, polycarbonate also can be the polycarbonate beyond its scope is mixed and to obtain.Particularly, have the polycarbonate that surpasses 50000 viscosity-average molecular weight, the fusion tension force of resin combination is increased, can improve forming process based on this characteristic.Its upper limit is preferably 300,000.Can be that target proportion is mixed in the A composition, to account for 20 weight % with this high-molecular-weight polycarbonate, and be adjusted into the molecular weight ranges that satisfies regulation, can seek the improvement of forming process thus.

In the polyreaction of polycarbonate, the normally reaction of binary phenol photoreactive gas of reaction by interface polycondensation reacts it in the presence of acid binding agent and organic solvent.As acid binding agent, preferably use the amine compound of the alkali metal hydroxide of sodium hydroxide, potassium hydroxide etc. or pyridine etc.As organic solvent, preferably use the halon of methylene dichloride, chlorobenzene etc.In addition, in order to promote reaction, also can use the catalyzer of the tertiary amine, quaternary ammonium compound, quaternary phosphonium compound etc. of triethylamine, tetra-n-butyl ammonium bromide, Si Zheng Ding Ji Phosphonium bromide etc.At this moment, preferable reaction temperature is 0～40 ℃ usually, and the reaction times is about 10 minutes～5 hours, and the pH value in the reaction is more than 9.

In addition, in this polyreaction, use end to stop agent usually.Stop agent as this end and can use the simple function phenols.As the simple function phenols, preferably use phenol, p-tert-butylphenol, to the simple function phenols of cumyl phenol etc.

To the organic solvent solution of the polycarbonate that obtains with interface polycondensation, implement washing usually.In this washing step, the electric conductivity of preferably using ion exchanged water etc. is following, the following water of 1 μ S/cm more preferably of 10 μ S/cm.After in the washing step above-mentioned organic solvent solution and water being mixed, stir, leave standstill or use separating centrifuge etc. to make organic solvent solution mutually and the water separatory, taking-up organic solvent solution phase is carried out aforesaid operations repeatedly, removes water-soluble impurity thus.By washing, can remove water-soluble impurity effectively, thereby make the form and aspect of resulting polycarbonate good with highly purified water.In addition, in order to remove the impurity of catalyzer etc., also can be preferably the organic solvent solution of above-mentioned polycarbonate be carried out pickling or alkali cleaning.

In addition, preferably above-mentioned organic solvent solution is removed foreign matter as insoluble impurities.Remove the method for foreign matter as this, the method that preferably adopts filtering method or handle with separating centrifuge.

Implemented the organic solvent solution of above-mentioned washing, next, be used for obtaining the operation of polycarbonate resin powder body except that desolvating.

As the method that obtains polycarbonate resin powder body (granulating working procedure), from operation or aftertreatment easy, employing is in the prilling granulator that has polycarbonate powder body and warm water (about 65～90 ℃) to exist, while stirring the organic solvent solution of supplying with polycarbonate continuously, by making the evaporation of this solvent, thereby make the method for slurry.As this prilling granulator, can use the mixing machine of steel basin or kneader etc.The slurry that is generated is discharged continuously from the top or the bottom of prilling granulator.Then also can carry out hot-water cure to the slurry of discharging.The hot-water cure operation is to supply to slurry in the hot-water cure container of the hot water that is equipped with 90～100 ℃ or after supplying with, and by being blown into steam etc. water temperature is adjusted into 90～100 ℃, thereby removes the organic solvent that contains in slurry.

To the slurries of in granulating working procedure, discharging or the slurry amount after the hot-water cure, can preferably remove and anhydrate and organic solvent by filtration, centrifugation etc., then in addition dry, thus obtain polycarbonate resin powder body (powder or sheet).As drying machine, both can be the conduction heating mode, also can be the hot blast type of heating, polycarbonate resin powder body both can have been left standstill, transfer also can be to be stirred.Wherein, preferably grooved or the cylindrical drier that polycarbonate resin powder body is stirred in the conduction heating mode is preferably tank-type drier especially.Drying temperature preferably adopts 130 ℃～150 ℃ scope.

Melting state transesterification reaction is generally the transesterification reaction of dihydric phenol and carbonic ether, in the presence of rare gas element, while by heating dihydric phenol and carbonic ether are mixed, distills out the alcohol that generated or the method for phenol and carries out.Temperature of reaction is according to the boiling point of alcohol that is generated or phenol etc. and different, still, and nearly all in 120～350 ℃ scope.Later stage in reaction reduces pressure 1.33 * 10 with the pressure of reaction system ³About～13.3Pa so that carry out easily the distillation of the alcohol that generates or phenol.Reaction times is normally about 1～4 hour.

As above-mentioned carbonic ether, can enumerate that to have or do not have substituent carbonatoms be that 6～10 aryl, aralkyl or carbonatoms are the ester of 1～4 alkyl etc., wherein, preferred diphenyl carbonate.To the melt polycarbonate that obtains by melt transesterification process, can use to melt extrude machine and carry out granulating.This particle can offer moulding and use.

The mixing of A1 composition and other polycarbonate can be carried out for the method for representative with following (i)～(iv), but is not limited to this.That is,

(i) utilize the disclosed technology of the flat 05-306336 communique of TOHKEMY, the emulsion that will be used for the emulsion of polycarbonate synthesis-poly organo alkyl copolymer and be used for synthetic other polycarbonate is all kept at same reactive tank and is mixed under the condition of emulsified state and it is left standstill and promote polymerization, reclaims method as the polycarbonate resin of A composition from the emulsion that becomes one;

(ii) the solution of polycarbonate-poly organo alkyl copolymer and other polycarbonate solution are mixed, from the method for this mixing solutions recovery as the polycarbonate resin of A composition;

(iii) with the powder body of polycarbonate-poly organo alkyl copolymer with other polycarbonate powder body is mixed and after integrated, mix the method for B composition; And

(iv) the powder body of polycarbonate-poly organo alkyl copolymer, other the polycarbonate powder body and the powder body of B composition are supplied to forcing machine etc. and blended method etc. in addition.

The polycarbonate resin of the A composition of making like this, preferably its C1 amount is that the terminal amount of 0.1～100ppm and OH is 1～30eq/ton.C1 amount in this polycarbonate resin can be measured by combustion method.After the sample weighing, it is burnt in the mixed airflow of argon gas and oxygen, measure with the electric charge amount of movement of silver electrode.As determinator, can enumerate the system TOX-2100H of Mitsubishi Chemical's (strain).In addition, the terminal amount of this OH can calculate with NMR method, IR method and volumetry.By satisfying this characteristic, can obtain excellent heat stability, formed material and moulding product that variable color is few, thus, resin combination of the present invention is more suitable in the thin molded article of high temperature and high-voltage load compacted under.

The viscosity-average molecular weight of the polycarbonate of A composition and A1 composition is obtained in accordance with the following methods.That is, at first under 20 ℃, the 0.7g polycarbonate is dissolved in the 100ml methylene dichloride and the solution that obtains, uses oersted watt moral viscometer to obtain the specific viscosity (η that calculates with following formula _Sp),

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

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

From the specific viscosity (η that obtains _Sp) calculate viscosity-average molecular weight (M) with following mathematical expression,

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

[η]＝1.23×10 ^-4M ^0.83

C＝0.7

In addition, in the resin combination of the present invention, the calculating of viscosity-average molecular weight is to carry out according to following method.That is, said composition is mixed with 20～30 times methylene dichloride of its weight, thus the solvable composition in the dissolved composition.Obtain this solvable composition by diatomite filtration.Then, the solvent in the removal gained solution.Solid behind the removal solvent is carried out sufficient drying, obtain being dissolved in the solid of methylene dichloride composition.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.

(B composition)

As mentioned above, the B composition among the present invention is that mean polymerisation degree is 3～15 polycarbonate oligomer.This polycarbonate is to be made of the structure unit identical with above-mentioned polycarbonate.That is, the polycarbonate oligomer of B composition is that binary phenol by reacting more than one and/or more than one aliphatics and/or the pure and mild carbonic ether presoma of ester ring type two functionalities obtain.Here, the structure of polycarbonate oligomer can be the arbitrary shape in straight chain shape, a chain (comprise and highly prop up chain) and the ring-type.Consider preferred straight chain shape from productivity and production stability aspect.

As two functionality alcohol in the polycarbonate oligomer of B composition, preferred ester ring type glycol, its preferred embodiment is also identical as above-mentioned A composition (A1 composition).

In addition, as mentioned above, the oligomer that the B composition preferably is made of the structure unit that represents in the above-mentioned general formula (β 1) among the present invention.The B composition is more preferably the oligomer of expression in the above-mentioned general formula (β 2).In this general formula, induce the preferred form of binary phenol of this repeating unit identical with the situation of above-mentioned polycarbonate.Wherein, preferred dihydroxyphenyl propane.And, as the object lesson of the monofunctional phenol class of inducing the molecule chain end in the above-mentioned general formula (β 2), can enumerate phenol, p-tert-butylphenol, to cumyl phenol, isooctyl phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol, triacontyl phenol, Para Hydroxy Benzoic Acid ester in the last of the ten Heavenly stems, Para Hydroxy Benzoic Acid dodecane ester, Para Hydroxy Benzoic Acid tetradecane ester, Para Hydroxy Benzoic Acid n-Hexadecane ester, Para Hydroxy Benzoic Acid eicosane ester, Para Hydroxy Benzoic Acid docosane ester and Para Hydroxy Benzoic Acid triacontane ester.The short more transparency of the chain length of this molecule chain end is excellent more, longly more can improve flowability more.With reference to this point, can select the structure of molecule chain end.When considering the transparency, thermostability and weather resistance, preferred carbonatoms is 1～9 alkyl substituted benzene phenols, particularly preferred p-tert-butylphenol.

The manufacture method of polycarbonate oligomer is by as well known to those skilled in the art, for example, adopt the reaction of the binary oxybenzene compound of interface polycondensation and phosgene, the polycondensation of inductive bischloroformate and binary phenol or aliphatic diol (comprising the ester ring type glycol) and two aromatic carbon acid esters and binary phenol or aliphatic diol (comprising the ester ring type glycol) carry out from binary phenol melt polycondensation reaction under the polymerizing catalyst condition.

The mean polymerisation degree of B composition is 3～15, and is preferred 3～12, more preferably 4～10.This mean polymerisation degree can be by calculating combinations such as GPC mensuration and NMR mensuration, and this method has been a known technology with respect to those skilled in the art.

(C composition: releasing agent)

In resin combination of the present invention, can also cooperate releasing agent as required, and preferably adopt this mode.This is because in shaping thin wall, because the mold temperature height, and is filled by high pressure, so the moulding product cause the cause that the demoulding is bad easily easily attached on the metal die.This demoulding is bad, the crackle when causing moulding, considers that on weather resistance its residual stress becomes the starting point of crackle easily, is unfavorable as a rule therefore.

Can use known releasing agent as releasing agent of the present invention.For example, can enumerate fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymers etc. also can use the compound of the functional group by containing sour modification etc. to be able to the polyolefin wax of modification), silicon compound, fluorine cpd (with poly-fluoroalkyl ether as the fluorocarbon oil of representative etc.), paraffin, beeswax etc.Wherein, be easy to get calmly and the preferred fat acid esters is considered in the transparent aspect of release property and resin combination.With respect to the polycarbonate resin of 100 weight parts as the A composition, this releasing agent is preferably 0.005～1 weight part, 0.01～0.3 weight part more preferably, and more preferably 0.03～0.2 weight part is preferably 0.07～0.15 weight part especially.When the lower value of the not enough above-mentioned scope of addition, release property to improve effect insufficient, if surpass higher limit, the thermostability deterioration of resin combination then, forming stability variation.And then, according to the kind difference of releasing agent,, in the moulding product, produce the solvent crackle sometimes because of being deposited in the releasing agent on the mould.

In above-mentioned,, can enumerate fatty acid ester (C-1 composition) as preferred releasing agent.This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This fatty alcohol both can be monohydroxy-alcohol, also can be the above polyvalent alcohol of binary.In addition, as this pure carbonatoms in 3～32 scope, 5～30 scope more preferably.As this monohydroxy-alcohol, for example can enumerate 12 carbon alcohol, ten four carbon alcohols, 16 carbon alcohol, octadecanol, eicosanol, tetracosa carbon alcohol, 26 carbon alcohol and 30 carbon alcohol etc.As this polyvalent alcohol, can enumerate tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Polyglycerine (triglycerin alcohol～six glyceryl alcohols), two TriMethylolPropane(TMP)s, Xylitol, Sorbitol Powder and mannitol etc.In fatty acid ester of the present invention, polyvalent alcohol more preferably.

On the other hand, the carbonatoms of preferred aliphat carboxylic acid is 3～32, particularly preferably is carbonatoms and is 10～22 aliphatic carboxylic acid.As this aliphatic carboxylic acid, for example can enumerate capric acid, hendecoic acid, lauric acid, ficocerylic acid, ten tetra-carbonics, 15 carbonic acid, 16 carbonic acid (palmitinic acid), 17 carbonic acid, 18 carbonic acid (stearic acid), 19 carbonic acid, 20 carbonic acid and behenic acid (docosoic) etc. representative examples of saturated aliphatic carboxylic and the unsaturated aliphatic carboxylic acid of Zoomeric acid, oleic acid, linolic acid, linolenic acid, eicosenoic acid, timnodonic acid and cetoleic acid etc.In above-mentioned, as the preferred carbonatoms of aliphatic carboxylic acid 14～20 aliphatic carboxylic acid.Wherein, representative examples of saturated aliphatic carboxylic preferably.Because this aliphatic carboxylic acid is normally made by the natural oil lipid of animal raw fat (shea butter and pig fat etc.) or vegetative grease (palm wet goods) etc., so these aliphatic carboxylic acids normally contain other different carboxylic acid compositions of carbonatoms mixture.Therefore, in the manufacturing of C of the present invention-1 composition, also by these natural lipid manufacturings, for containing other carboxylic acid compositions' mixture mode.The acid number of preferred fat acid esters is (can get 0 in fact) below 20.But, when being full ester (full ester),, preferably contain a lot of free lipid acid in order to improve release property, consider that from this point the acid number in the full ester is preferably 3～15 scope.In addition, the iodine number of fatty acid ester is preferably below 10 and (can gets 0 in fact).These characteristics can be tried to achieve by the method for regulation among the JIS K 0070.

Fatty acid ester of the present invention can be any in part ester and the full ester, but on good release property and weather resistance, preferred part ester.Wherein, monoglyceride preferably.The principal constituent of monoglyceride is the monoesters of glycerine and lipid acid, can enumerate the saturated fatty acid of stearic acid, palmitinic acid, docosoic, eicosanoic acid, 28 carbonic acid and lauric acid etc. or the unsaturated fatty acids of oleic acid, linolic acid and sorb saccharic acid etc. as preferred lipid acid, particularly preferably be the monoglyceride of stearic acid, docosoic and palmitinic acid lipid acid as principal constituent.In addition, this lipid acid is by natural lipid acid synthetic, for as above-mentioned mixture.Monoglyceride can with full ester of other releasing agent, particularly lipid acid and usefulness, even but and the situation of usefulness under, also preferably with monoglyceride as principal constituent.That is preferably be more than the 60 weight % in the releasing agent of 100 weight %.

In addition, part ester great majority on thermostability are poorer than full ester.In order to improve the thermostability of this part ester, preferred part ester contain be lower than 20ppm, more preferably less than 5ppm, further preferably be lower than the sodium metal of 1ppm.The fatty acid part ester of the not enough 1ppm of sodium metal content is after making the fatty acid part ester with usual method, makes with extra care by molecular distillation etc. and makes.

Specifically, following method is arranged, promptly, after removing gas and low-boiling point material by the nozzle-type de-gassing vessel, use the falling film type water distilling apparatus, the polyhydroxy reactant of deglycerizin etc. under the condition of 120～150 ℃ of distillation temperatures, vacuum tightness 0.01～0.03kpa, and then, use the centrifugal molecular distillating device, under the condition of 160～230 ℃ of distillation temperatures, vacuum tightness 0.01～0.2Torr, method that highly purified fatty acid part ester is obtained as cut etc., the sodium metal can be used as distillation residue and removes.By resulting cut being carried out distillation repeatedly, can further improve purity, can access sodium metal content fatty acid part ester still less.In addition, use suitable method in advance,, prevent that thus the sneaking into of sodium metal ingredient from outside atmosphere from also being very important by improving resistance to air loss etc. to fully washing in the molecular distillation apparatus.This fatty acid ester can obtain from special enterprise (for example reason is ground VITAMIN (strain)).

(about other additive)

Resin combination of the present invention except above-mentioned A composition～C composition, also can contain the various additives that are engaged in usually in the polycarbonate resin.

(i) Phosphorus stablizer

In the resin combination of the present invention, the thermostability when improving its forming process preferably cooperates various Phosphorus stablizers as main purpose.As this Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and these sour esters etc.And then this Phosphorus stablizer comprises tertiary phosphine.

As concrete phosphorous acid ester (phosphite) compound, for example can enumerate triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three decyl phosphorous acid esters, the trioctylphosphine phosphorous acid 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 (4,6-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 (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (2,6-di-tert-butyl-phenyl) phosphorous acid ester, the distearyl pentaerythritol diphosphites, two (2,4-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, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, 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, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-ethylenebis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester etc.

As 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, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound (phosphonite), can enumerate four (2,4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2,4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc.Wherein, preferred four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2,4-di-tert-butyl-phenyl)-diphenylene two phosphinates, two (2,4-di-tert-butyl-phenyls)-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 only use a kind of, also can two or more mixing use.In above-mentioned Phosphorus stablizer, preferred bi-ester of phosphite or phosphinate compound.Preferred especially three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, four (2,4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates and two (2,4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.In addition, also preferably these and phosphate compound are also used.

(ii) Hinered phenols stablizer

Thermostability, heat-resistant aging and ultraviolet resistance when improving its forming process are main purpose, can also cooperate the Hinered phenols stablizer in resin combination of the present invention.As this Hinered phenols stablizer; for example can enumerate alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; Octadecane base-β-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; 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 '-dimethylene two (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-tert-butyl amido)-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) chlorinated isocyanurates; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) chlorinated isocyanurates; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl chlorinated isocyanurates; and four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all are easy to obtain.Above-mentioned Hinered phenols stablizer both can use separately, also can be used in combination.

With respect to the polycarbonate resin (A composition) of 100 weight parts, above-mentioned (i) Phosphorus stablizer and (ii) the content of Hinered phenols stablizer be 0.0001～1 weight part, be preferably 0.001～0.1 weight part, 0.005～0.1 weight part more preferably.Cross when stabiliser content and to be less than when stating scope, be difficult to obtain the satisfactory stability effect, when having served as, can cause that then the physical properties of composition descends more than above-mentioned scope.

In order further to stablize the form and aspect of moulding product when the thermal treatment, in resin combination of the present invention, except above-mentioned Hinered phenols stablizer, can also use other stablizer.As these other stablizer, can enumerate for example tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate etc.The usage quantity of these other stablizer is preferably 0.001～0.05 weight part with respect to 100 weight parts as the polycarbonate resin of A composition.

(iii) UV light absorber

As UV light absorber, can enumerate benzophenone particularly, for example can enumerate 2,4 dihydroxyl benzophenone, 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The 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 and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.

Benzotriazole category as UV light absorber, can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole particularly, 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), 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole, 2-(2 '-hydroxy-5-methyl base acrylyl oxy-ethyl phenyl)-2H-benzotriazole and can and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer of the vinyl monomer of this monomer copolymerizable or 2-(2 '-hydroxyl-5-acrylyl oxy-ethyl phenyl)-2H-benzotriazole with the multipolymer of the vinyl monomer of this monomer copolymerizable etc.

As the hydroxyphenyltriazinuv class of UV light absorber, for example, can enumerate 2-(4 particularly, 6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-ethyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propyl group oxy phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butyl oxy phenol etc.Further, the phenyl that can also enumerate in 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-above-mentioned example compound such as 5-hexyl oxy phenol becomes 2, the compound of 4-3,5-dimethylphenyl.

As the cyclic imide base ester class of UV light absorber, for example can enumerate 2 particularly, 2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine 4-ketone) and 2,2 '-(2, the 6-naphthyl) two (3,1-benzoxazine 4-ketone) etc.

In addition; cyanoacrylate as UV light absorber; for example can enumerate 1 particularly; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen]-2,2-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methylpropane and 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] benzene etc.

Further, above-mentioned UV light absorber also can be, by adopting the monomeric compound structure to carry out radical polymerization, the monomer of this ultraviolet-absorbing monomer and/or light stability monomer and (methyl) alkyl acrylate etc. carried out copolymerization and the aggretion type UV light absorber that obtains.As above-mentioned UV light absorber monomer, can preferably enumerate the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imino ester skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.

In above-mentioned, when considering ultraviolet absorption ability, preferably adopt benzotriazole category and hydroxyphenyltriazinuv class, and when considering thermotolerance and form and aspect (transparency), then preferably adopt cyclic imino ester class and cyanoacrylate.Above-mentioned UV light absorber both can be used separately, can also use two or more mixtures.

With respect to the polycarbonate resin (A composition) of 100 weight parts, the use level of UV light absorber is 0.01～2 weight part, is preferably 0.02～2 weight part, more preferably 0.03～1 weight part, more preferably 0.05～0.5 weight part.

(iv) photostabilizer

In addition, resin combination of the present invention can also contain with two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, poly-{ [6-(1,1,3,3-tetramethyl butyl) amino-1,3,5-triazine-2,4-two bases] [(2,2,6,6-tetramethyl-piperidyl) imino-] hexa-methylene [(2,2,6,6-tetramethyl-piperidyl) imino-], and poly-methyl-propyl-3-oxygen-[4-(2,2,6,6-tetramethyl-) piperidyl] hindered amine light stabilizer of representative such as siloxanes.

Above-mentioned photostabilizer may be used alone, or two or more mixed.With respect to the polycarbonate resin (A composition) of 100 weight parts, the usage quantity of photostabilizer is preferably 0.0005～3 weight part, more preferably 0.01～2 weight part, more preferably 0.02～1 weight part.

(v) blueing agent

Composition of the present invention, and then preferably in resin combination, contain the blueing agent of 0.05～3.0ppm (part by weight).In resin combination of the present invention, yellow in order further to reduce, and give the transparent feel of nature to moulding product, the use blueing agent is very effective.Be meant by absorbing orange or xanchromatic light at this said blueing agent, present the tinting material of blueness or purple, particularly preferably be dyestuff.By cooperating blueing agent, poly carbonate resin composition of the present invention can obtain better form and aspect.When the amount of blueing agent is lower than 0.05ppm, form and aspect to improve effect insufficient sometimes, on the other hand, when the amount of blueing agent surpassed 3.0ppm, then the transmitance of light descended, thereby not preferred.The amount of preferred blueing agent is to be the scope of 0.2～2.0ppm in resin combination.As the typical example of blueing agent, can enumerate doubly red (マ Network ロ レ Star Network ス バ イ オ レ Star ト) B, Ma Kulu lux indigo plant (the マ Network ロ レ Star Network ス Block Le-) RR in Ma Kulu lux of Baeyer (Bayer) company and hot this indigo plant (the Port リ シ Application ス レ シ Block Le-) RLS in Pori of Clariant company etc.

(vi) fluorescence dye

Because resin combination of the present invention has the good transparency, so by further containing white dyes, can give the transparent feel of higher photopermeability and nature, and, can give the appearance effect of effectively utilizing illuminant colour thus by containing white dyes or the luminous fluorescent dyestuff beyond it.

As the fluorescence dye (comprising white dyes) that the present invention uses, can enumerate for example coumarins fluorescence dye, chromene fluorochrome, perylene fluorochrome, anthraquinone fluorochrome, thioindigo fluorochrome, xanthene fluorochrome, xanthone fluorochrome, sulfo-xanthene fluorochrome, thio-xanthene-one fluorochrome, thiazides fluorescence dye and diaminostilbene fluorochrome etc.In these, the coumarins fluorescence dye that preferred thermotolerance is good and degradation is little when the forming process of polycarbonate resin, chromene fluorochrome are to reach the perylene fluorochrome.Wherein because the coumarins fluorescence dye, promptly the fluorescence dye that constitutes by coumarin derivatives with the combination of B composition of the present invention in also can keep good characteristic, thereby preferred.The use level of fluorescence dye (comprising white dyes), polycarbonate resin (A composition) with respect to 100 weight parts is 0.0001～3 weight part, be preferably 0.0005～1 weight part, 0.0005～0.5 weight part more preferably, more preferably 0.001～0.5 weight part is preferably 0.001～0.1 weight part especially.In this scope, can take into account more good ultraviolet resistance and form and aspect, thermostability and light transmission rate.

(vii) static inhibitor

To resin combination of the present invention, require it to have static resistance (for example, the dust when preventing to print adhere to etc.) sometimes, preferably contain static inhibitor in this case.As this static inhibitor, that for example can enumerate fragrant basic sulfonic acid phosphonium salt that (i) ten dialkyl benzene sulfonic acid phosphonium salts are representative, alkane base sulfonic acid phosphonium salt etc. has a machine sulfonic acid phosphonium salt, and as the boron acid phosphonium salt of four fluorine boron acid phosphonium salt etc.Proportion of composing with respect to Gai phosphonium salt of A composition ， of 100 weight parts is below 5 weight parts, is preferably 0.05～5 weight part, more preferably 1～3.5 weight part, more preferably 1.5～3 weight parts.

For example can enumerate (ii) organic sulfonic acid alkali (alkali earths) metal-salt of organic sulfonic acid lithium, organic sulfonic acid sodium, organic sulfonic acid potassium, organic sulfonic acid caesium, organic sulfonic acid rubidium, organic sulfonic acid calcium, organic sulfonic acid magnesium, organic sulfonic acid barium etc. as static inhibitor.Concrete can enumerate for example metal-salt of Witco 1298 Soft Acid and the metal-salt of perfluoroalkane sulfonic acid etc.The proportion of composing of organic sulfonic acid alkali (alkali earths) metal-salt is below 0.5 weight part with respect to the A composition of 100 weight parts, preferably 0.001～0.3 weight part, more preferably 0.005～0.2 weight part.Particularly preferably be an alkali metal salt of potassium, caesium and rubidium etc.

For example can enumerate the (iii) organic sulfonic acid ammonium salt of alkylsulphonic acid ammonium salt and aryl sulfonic acid ammonium salt etc. as static inhibitor.The proportion of composing of this ammonium salt is preferably below 0.05 weight part with respect to the A composition of 100 weight parts.To gather the polymkeric substance that (oxyalkylene) diol component contains as its constituent as what static inhibitor for example can be enumerated (iV) polyether ester amides etc.This polymer phase is preferably below 5 weight parts for the A composition of 100 weight parts.

(viii) hydrolysis modifying agent

In order to improve the hydrolytic resistance of A composition, in the scope of not damaging the object of the invention, can add various hydrolysis modifying agents to resin combination of the present invention.As this compound, can enumerate epoxy compounds, trimethylene oxide, silane compound and phosphinic acid compounds etc.Particularly preferably be epoxy compounds and oxetane compound.As epoxy compounds, preferably can enumerate with 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters be representative the alicyclic epoxy compound, and be the epoxy compounds that contains Siliciumatom of representative with 3-glycidyl propoxy--triethoxyl silane.The content of these hydrolysis modifying agents is preferably the scope of 0.01～1 weight part with respect to the A composition of 100 weight parts.

(ix) has the compound that hot line absorbs energy

For resin combination of the present invention, in the scope of not damaging the object of the invention, can use to have the compound that hot line absorbs energy.As this compound, preferably can enumerate the good various metallic compounds and the carbon filler of near-infrared absorbing such as metal boride class near infrared ray absorption energy of metal oxide-type near infrared ray absorption, lanthanum boride, cerium boride and the tungsten boride etc. of phthalocyanines near infrared ray absorption, ATO, ITO, iridium oxide and ruthenium oxide etc.As carbon filler, can enumerate carbon black, graphite (comprises any kind in natural graphite and the electrographite, and then also comprise brilliant Shall), carbon fiber (comprising carbon fiber), carbon nanotube and soccerballene (fullerene) etc., preferably carbon black and graphite according to vapor growth method.These both may be used alone, used in two or more.With respect to the polycarbonate resin (A composition) of 100 weight parts, the phthalocyanines near infrared ray absorption is preferably 0.0005～0.2 weight part, more preferably 0.0008～0.1 weight part, more preferably 0.001～0.07 weight part.Metal oxide-type near infrared ray absorption, metal boride class near infrared ray absorption and carbon filler are preferably the scope of 0.1～200ppm (weight ratio) in resin combination of the present invention, more preferably the scope of 0.5～100ppm (weight ratio).

(x) other dyestuff and/or pigment

In resin combination of the present invention, in the scope of the effect that performance is invented, can use above-mentioned blueing agent and fluorescence dye various dyestuffs and/or pigment in addition.Particularly, from the viewpoint littler, preferably use dyestuff to the infringement of the transparency.On the other hand, also can obtain the good metal color by cooperating dark color or metallic pigment.

As dyestuff, can Ju Chu perylene class dyestuff, coumarins dyestuff, thioindigo class dyestuff, anthraquinone dyes, thio-xanthene-one class dyestuff, Prussian blue (Cyanosis green grass or young crops) etc. Ferrocyanide salt, purple cyclic ketones class dyestuff, quinoline dyestuff, quinoline a word used for translation ketone dyestuff, dioxazines dyestuff, isoindoline ketone dye well phthalocyanines dye etc.The usage quantity of these dyestuffs is preferably 0.0001～1 weight part with respect to the polycarbonate resin of 100 weight parts as the A composition, more preferably 0.0005～0.5 weight part.

In the scope of not damaging the object of the invention, can also use fire retardant in the resin combination of the present invention.As fire retardant, for example can enumerate metal salts of organic acids beyond the brominated epoxy resin, brominated Polystyrene, brominated polycarbonate, bromination polyacrylic ester, phosplate compound, phosphoric acid ester oligomer compounds, phosphonate oligomers compound, phosphonitrile oligomer compounds, phosphonic acid amide compound, sulfonate and silicon based flame retardant etc., these can use more than one.This fire retardant can cooperate the known use level with respect to polycarbonate resin respectively.

In resin combination of the present invention, in the scope of not damaging purpose of the present invention, can also use a spot of B composition other resins or elastomerics in addition, though this resin is had no particular limits, but, consider the transparency after polycarbonate resin cooperates, can preferably enumerate polyethylene terephthalate, polybutylene terephthalate, PEN, the polyethylene terephthalate with cyclohexanedimethanol (CHDM) copolymerization, polyarylester, polysulfones, polyphenylene ether, Resins, epoxy, reach phenoxy resin etc.These other resins are 0.5～15 weight part with respect to the A composition of 100 weight parts, are preferably 1～10 weight part.

And then, in resin combination of the present invention, can also cooperate various inorganic filling materials, flow ability modifying agent (material beyond the B composition), antiseptic-germicide, photochemical catalysis class stain control agent, light diffusing agent, light height to reflect with white pigment and photochromic agent etc.

(haze value)

In the resin combination of the present invention, flat runner to the thickness 2mm of the arithmetic average roughness (Ra) that constitutes and have 0.03 μ m by this resin combination, the haze value of measuring with JIS K7105 is 0.3～20%, is preferably 0.3～5%, more preferably 0.3～3%.Haze value is to measure by turbidometer.This level and smooth flat board obtains by the following method, after being about to particle and being carried out in accordance with regulations drying, and injection molding in the chamber that the die surface by the arithmetic average roughness (Ra) of 0.03 μ m constitutes and obtaining.The arithmetic average roughness of die surface (Ra) can use the surfaceness meter to measure.

(about the manufacture method of resin combination)

When making resin combination of the present invention, its manufacture method is had no particular limits.But, poly carbonate resin composition of the present invention preferably by to various compositions in addition melting mixing make.

As the concrete grammar of above-mentioned melting mixing, can enumerate Banbury, mixing roller, forcing machine etc.Wherein, consider preferred forcing machine, the more preferably multiple screw extruder of biaxial extruder etc. from the melting efficiency aspect.Preferred embodiment is as described below in this biaxial extruder.That is, the screw rod shape can adopt screw-type screw rod (the ネ ジ ス Network リ of single thread, double thread and triple thread _ユ-), preferably especially use the transporting power of molten resin or shear all wide double thread 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 by kneading disk part (perhaps suitable with it the mixing part) formation 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, the zone before forcing machine mould portion is provided with and is used to remove the filtering net of sneaking into extruding impurities in raw materials etc., also impurity can be removed from resin combination thus.As this filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.

And, to with B composition and other additive (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 polycarbonate resin being supplied with independently forcing machine respectively; (ii) adopt the mixing machine of super mixing machine etc., in advance additive and polycarbonate resin powder are carried out pre-mixing after, resupply the method for forcing machine.In addition, in any method, the polycarbonate of the A1 composition in the polycarbonate resin-poly organo alkyl copolymer and other polycarbonate both can be the compounds that becomes one, and also can be independently solids of difference.

Aforesaid method one of (ii), for needed starting material all being carried out resupply after the pre-mixing method of forcing machine.Other method is the host (マ ス -drug) that is combined with additive with making high density earlier, this host is further carried out pre-mixing individually or with remaining polycarbonate resin after, resupply the method for forcing machine.In addition, this host can be selected Powdered and this powder is compressed the arbitrary shape that granulation etc. obtains.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-blend approach, but the mixing tank of the high-speed stirring type of preferred super mixing tank etc.Further, as other pre-blend approach, for example can enumerate polycarbonate resin and additive are dispersed in solvent and behind the obtain solution, remove the method for this solvent.In addition,, can enumerate (iii) and in advance additive and polycarbonate resin be carried out melting mixing, make the method for host grain (マ ス -ペ レ Star ト) as the third method

By the resin that biaxial extruder 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.In addition, resultant particle shape can be the general shape of cylindrical, corner post shape and sphere etc., but 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.

(about the moulding product that form by resin combination of the present invention)

The resin combination of the present invention that obtains as mentioned above, the particle that will make as mentioned above carries out injection molding and produces various one-tenth products usually.In this injection molding, not only can adopt common forming method, can also be according to purpose, suitably adopt injection compression molding, injection pressure moulding, air-auxiliary injection forming, foaming (comprising the moulding of injecting), insert moulding by supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection moulding of heating cooling mould molding, dual-color forming, interlayer moulding and ultra-high speed injection molding 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.

In addition, resin combination of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet and 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 extension operation, also can be shaped to heat-shrinkable tube or exhibiting optical function film.In addition, also can poly carbonate resin composition of the present invention be manufactured the moulding product by rotoforming or blow molding etc.

The moulding product that formed by resin combination of thin-walled shape with the good transparency and weather resistance can be provided thus.And, to the moulding product that form by resin combination of the present invention, can carry out various surface treatments.In this said surface treatment, be meant that the top layer at synthetic resin of evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (plating, plated by electroless plating, fusion plating etc.), application, coating, printing etc. forms the processing of new coating, can use the method that is generally used in the 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, metallic coating (evaporation) etc. particularly.Wherein, hard coat is preferred especially and is necessary surface treatment.

The inventor etc. think the embodiments of the present invention of present the best, are the embodiments that has compiled the preferable range of above-mentioned each important document, for example, have put down in writing its typical example in the following embodiments.Certainly the present invention is not subjected to the restriction of these embodiments.

Embodiment

The present invention is described by the following examples.But the present invention is not limited to this.In addition, the mensuration of various characteristics is to carry out according to following method among the embodiment; Raw material uses the raw material of the following stated.

(1) evaluation of poly carbonate resin composition

(i) transparency of moulding product: it is the metal die of the cavity face of 0.03 μ m that use has arithmetic average roughness (Ra), by injection moulding machine (SG-150U, Sumitomo heavy-duty machine tool industry (strain) system), under the condition of 290 ℃ of center housing temperatures, 80 ℃ of metal die temperature, be that 50mm, length are that 90mm, thickness are from watering the three-segment type plate that oral-lateral is respectively 3mm (length 20mm), 2mm (length 45mm), 1mm (length 25mm) with 50 seconds shaping cycle forming width.Be total light transmittance and the Haze in the profiled sheeting of 2.0mm portion with the thickness of this three-segment type plate, measure according to the standard of ASTM D1003.Haze represents the mist degree of moulding product, and its numerical value low haze more is more little.

(ii) mobile: the SG-150U shaper that uses Sumitomo heavy-duty machine tool industry (strain) to make, estimate length of flow by Archimedes (archimedes) type helicoidal flow metal die (stream thickness 2mm, flow path width 8mm).Condition is: 290 ℃ of center housing temperatures, 70 ℃ of metal die temperature, injection pressure 100MPa.

(iii) fatigue characteristic: use so-called "＜" shape test piece shown in Figure 1, observe each test piece in fatigue test until the difference that reaches the disruptive number of times (said breaking is meant the state that test piece can not the bearing test load, and do not mean that test piece is cut off into two parts).With the mean value of three test pieces as the number of times that breaks.Test is to implement under the condition of the sine wave of 23 ℃ of temperature, relative humidity 50%, vibration number 1Hz, overall loading 6.86N (7kgf).Testing apparatus then uses protracted test machine (Tianjin, island サ-ボ パ Le サ-EHF-FDI-10LA type, (strain) Shimadzu Seisakusho Ltd. makes).Test piece is by injection moulding machine (SG-150U, Sumitomo heavy-duty machine tool industry (strain) make), under 80 ℃ of 290 ℃ of center housing temperatures, metal die temperature with in addition moulding of shaping cycle 50 seconds.

Embodiment 1～5 and comparative example 1～3

With the resin combination of following method manufacturing by the described cooperation composition of proportions of table 1.In addition, explanation is to carry out according to the symbol in the following table.The described composition full dose of table 1 is taken by weighing to the bag of polyethylene system, by shaking the uniform premixture of mixing manufacture.This premixture is supplied to the aftermost the 1st of the exhaust biaxial extruder that screw diameter is 30mm (TEX-30XSST, (strain) JSW makes) to be added in the inlet.Extrude is to carry out under following condition: use vacuum pump, and under the vacuum of 3kPa, center housing temperature is that 230～280 ℃ of (evenly rising between the barrel～mould of screw rod root), screw speed 180rpm and extrusion capacities hourly are 15kg.After the strand of extruding cooled off in water-bath, cut off with tablets press, thereby make its granulating.Resulting granules is respectively made the test piece of above-mentioned test usefulness in drying under 120 ℃ after 6 hours with the heated air circulation type drying machine.

The use starting material that table 1 is put down in writing are as follows.

(A composition)

(A1 composition)

PC-PDMS-1: the viscosity-average molecular weight made from following manufacture method 20,300, the polydimethylsiloxane amount of mean polymerisation degree 25 are that the extraction ratio of 4 weight %, normal hexane is that 1.2 weight %, molecular weight distribution (Mw/Mn) are polycarbonate-poly organo alkyl copolymers of 2.4.

PC-PDMS-2: the viscosity-average molecular weight made from following manufacture method 20,000, the polydimethylsiloxane amount of mean polymerisation degree 38 are that the extraction ratio of 4 weight %, normal hexane is that 1.7 weight %, molecular weight distribution (Mw/Mn) are polycarbonate-poly organo alkyl copolymers of 2.4.

PC-PDMS-3: the viscosity-average molecular weight made from following manufacture method 16,000, the polydimethylsiloxane amount of mean polymerisation degree 25 are that the extraction ratio of 4 weight %, normal hexane is that 1.3 weight %, molecular weight distribution (Mw/Mn) are polycarbonate-poly organo alkyl copolymers of 2.4.

PC-PDMS-4 (relatively using): the viscosity-average molecular weight made from following manufacture method 20,000, the polydimethylsiloxane amount of mean polymerisation degree 67 are that the extraction ratio of 3.9 weight %, normal hexane is that 2.2 weight %, molecular weight distribution (Mw/Mn) are polycarbonate-poly organo alkyl copolymers of 2.4.

Use the manufacturing of A1 composition to carry out in accordance with the following methods in above-mentioned.In addition, " part " expression weight part in this explanation.

(manufacture method of PC-PDMS-1): take into account in the reactor of stirrer and to add ion exchanged water 3 having temperature, 650 parts of the aqueous sodium hydroxide solutions of 310 parts and 48.5 weight %, make 1.2 parts of its dissolving hydrosulphite, then dissolve 596 parts of dihydroxyphenyl propanes, then, add methylene dichloride 2,230 parts, fierce on one side stirring, at 20 ℃ down with about 40 minute be blown into phosgene 312 part on one side, make and react.After being blown into the phosgene end, the temperature of reaction solution is raised to 28 ℃, add 173 parts of the aqueous sodium hydroxide solutions of 16 parts of p-tert-butylphenols, 48.5 weight % and seal two ends with o-allyl phenol, two ends contain the polydimethylsiloxane (X-22-1875 of the mean polymerisation degree 25 of phenol hydroxyl, SHIN-ETSU HANTOTAI's chemical industry (strain) is made) 31 parts, make behind the emulsified state high degree of agitation once more.This stirs down, and reaction solution adds 0.9 part of triethylamine and continues down for 26～31 ℃ to stir in temperature and finished in 1 hour to react under 26 ℃ of states.After reaction finishes, separate organic phase, dilute with methylene dichloride, make hydrochloric acid acidity after the washing and wash, when the electric conductivity of water is almost identical with ion exchanged water, join in the kneader that is full of warm water, evaporate methylene dichloride while stirring, obtain the powder of multipolymer.The viscosity-average molecular weight of this multipolymer is 20,300, and the polydimethylsiloxane component content is 3.95 weight %.This content can basis ¹The mensuration of H-NMR is calculated.The multipolymer that obtains is carried out Suo Gelite extraction 3 hours with normal hexane (superfine with the pure medicine of light (strain) system) with 20 times/hour cycles, calculate the n-hexane extraction ratio.This ratio is 1.2 weight % among the polydimethylsiloxane 100 weight % that contain in multipolymer.In addition, measuring the molecular weight distribution of calculating (Mw/Mn) by GPC is 2.4.

(manufacture method of PC-PDMS-2): in the manufacture method of above-mentioned PC-1, as polydimethylsiloxane, add and seal two ends with o-chavicol, polydimethylsiloxane (the X-22-1821 that contains the mean polymerisation degree 38 of phenol hydroxyl at two ends, SHIN-ETSU HANTOTAI's chemical industry (strain) system) outside 31 parts, other can obtain the powder of multipolymer in the same manner with the manufacture method of PC-1.The viscosity-average molecular weight of this multipolymer is 20,000, and the polydimethylsiloxane component content is 4 weight %, and the n-hexane extraction ratio is that 1.7 weight % and molecular weight distribution (Mw/Mn) are 2.4.

(manufacture method of PC-PDMS-3): except adding 24 parts of p-tert.-butyl phenols, obtain the powder of multipolymer in the same manner with the manufacture method of PC-1.The viscosity-average molecular weight of this multipolymer is 16,000, and the polydimethylsiloxane component content is 4 weight %, and the n-hexane extraction ratio is that 1.3 weight % and molecular weight distribution (Mw/Mn) are 2.4.

(manufacture method of PC-PDMS-4): in the manufacture method of above-mentioned PC-1, as polydimethylsiloxane, add and seal two ends with o-chavicol, polydimethylsiloxane (the X-22-1822 that contains the mean polymerisation degree 67 of phenol hydroxyl at two ends, SHIN-ETSU HANTOTAI's chemical industry (strain) system) outside 31 parts, other can obtain the powder of multipolymer in the same manner with the manufacture method of PC-1.The viscosity-average molecular weight of this multipolymer is 20,000, and the polydimethylsiloxane component content is 3.9 weight %, and the n-hexane extraction ratio is that 2.2 weight % and molecular weight distribution (Mw/Mn) are 2.4.

(polycarbonate beyond the A1 composition)

PC-1: viscosity-average molecular weight is 19,700 straight chain shape aromatic polycarbonate resin powder (パ Application ラ イ ト L-1225WX, Supreme Being people change into (strain) system)

PC-2: viscosity-average molecular weight is 16,000 straight chain shape aromatic polycarbonate resin powder (パ Application ラ イ ト CM-1000, Supreme Being people change into (strain) system)

(B composition)

B-1: the mean polymerisation degree by following manufacture method manufacturing is about 7, number-average molecular weight is 2,400 polycarbonate oligomer.

The manufacturing of B-1 composition is to carry out according to following method.In addition, " part " in this explanation is the expression weight part.

(manufacture method of B-1): take into account in the reactor of stirrer and drop into 3 being provided with temperature, the aqueous sodium hydroxide solution of 48.5 weight % of 310 parts ion exchanged water and 650 parts, make 1.2 parts of its dissolving hydrosulphite, then dissolve 596 parts of dihydroxyphenyl propanes, then, add methylene dichloride 2,230 parts, fierce on one side stirring, at 17 ℃ down with about 40 minute be blown into phosgene 325 part on one side, make and react.After being blown into phosgene and finishing, the temperature of reaction solution is raised to 28 ℃, adds 173 parts of the aqueous sodium hydroxide solutions of 48.5 weight % and be dissolved in 118 parts of p-tert-butylphenols in 955 parts of the methylene dichloride, make behind the emulsified state high degree of agitation once more.This stirs down, and reaction solution adds 1.8 parts of triethylamines under 26 ℃ of states, continues stirring down 26～31 ℃ of temperature and finishes reaction in 1 hour.After reaction finishes, separate organic phase,, make hydrochloric acid acidity after the washing and wash, make the electric conductivity of water almost identical with ion exchanged water with the methylene dichloride dilution.From this dichloromethane solution evaporation methylene dichloride, thereby obtain the polycarbonate oligomer.Terminal group analysis by NMR knows that number-average molecular weight is 2,400.

(C composition; Releasing agent)

C-1: the sodium metal content is the Zerol (reason is ground VITAMIN (strain) system) of 0.2ppm

C-2: the sodium metal content is the Zerol (reason is ground VITAMIN (strain) system) of 9.8ppm

In addition, above-mentioned sodium metal content can be measured with the method for WO2006/025587 brochure record.In addition, this stearic acid is the expression principal constituent, is to be the mixture of raw material with the vegetative grease.

(other composition)

ST-P1: phosphinate is thermo-stabilizer (サ Application De ス Block P-EPQ (trade(brand)name), a Network ラ リ ア Application ト society system)

ST-P2: phosphorous acid ester is thermo-stabilizer (Irgafos168 (trade(brand)name), a チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ society system)

ST-H1: phenol is antioxidant (Irganox1076 (trade(brand)name), チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ society system)

UVA:2.2 '-p-phenylene two (3,1-benzoxazine-4-ketone) (CEI-P, bamboo wood oil fat (strain) system)

BLM: the blueing agent masterbatch makes blueing agent reach 0.1 weight % and makes by super mixing machine uniform mixing blueing agent (マ Network ロ レ Star Network ス バ イ オ レ Star ト B, バ イ エ Le society system) and above-mentioned PC-2.

The embodiment from table 1 and the comparison of comparative example, the transparency of resin combination of the present invention, mobile reaching with fatigue characteristic are the excellent in te pins of durability of representative as can be seen.

And then, the particle that obtains in the foregoing description 1～4 is made SG260M-HP with Sumitomo heavy-duty machine tool industry (strain), under 320 ℃ of center housing temperatures, 80 ℃ of metal die temperature, injection speed 50mm/sec and 70 seconds condition of shaping cycle, the test piece that the UL94 combustion test of molding thickness 0.4mm is used.All can not injected short circuit, the demoulding is bad and the transparent moulding product of residual strain.Haze value is 0.3～0.4.

Resin combination of the present invention, owing to have flowability, the transparency and the weather resistance of improvement, so can utilize these characteristics launching purposes on the untapped parts in the past.Wherein, be particularly useful for the thin-walled injection-molded article, particularly be applicable to the purposes aspect of accepting external force repeatedly that requires the transparency.As the object lesson of thin-walled injection-molded article, the various outer casing forming product, lens barrel, storage card, speaking trumpet, tape cassete, planar luminous body, micromachine that can enumerate battery case etc. are with parts, the moulding product of band hinge or moulding product, printing opacity and/or light-conducting type button class, the touch screen parts etc. that hinge is used.Therefore, played industrial effect especially.

Industrial applicibility

Resin combination of the present invention, owing to have the good transparency and mobile, so in above-mentioned usefulness Beyond the way, also can utilize widely small-sized lens and lens unit, light-card substrate, display screen cover, Require various framework classes, game device and circuit protective cover, sender unit cap class and the Medical treatment device of visual effect Tool etc. In addition, for above-mentioned button products formed, also applicable to from before behind sprue cutting The structure of bonding plate-shaped member is to the button moulding with plate-shaped member and the integrated injection molding structure of button Product. In this case, the thickness of plate-shaped member approximately is 50～200 μ m, and is extremely thin applicable to having The injection-molded article of wall part.

Claims (11)

1. resin combination contains as the polycarbonate resin of A composition and as the polycarbonate oligomer of B composition, and wherein, with respect to the A composition of 100 weight parts, the content of B composition is 0.1～20 weight part; The A composition is made up of the polycarbonate-poly organo alkyl copolymer of the polyorganosiloxane units of representing as following general formula of containing of A1 composition (α 1), or form by the polycarbonate beyond this A1 composition and the A1 composition, in 100 weight %A compositions, the content of polyorganosiloxane units is 0.1～20 weight %; The mean polymerisation degree of B composition is 3～15,

In the general formula (α 1), R ₁, R ₂, R ₃And R ₄The alkyl or phenyl of expression carbonatoms 1～6 is same to each other or different to each other; R ₅Expression is from organic residue of the divalence of aliphatics or aromatics; N represents the unitary repeat number in the parantheses, and the mean value of this repeat number is 10～60, and the structural unit in the parantheses is two or more mixing or single structure.

2. resin combination according to claim 1, wherein, as the polycarbonate-poly organo alkyl copolymer of above-mentioned A1 composition, it has as the structural unit of the following general formula of general formula (α 1) (α 2) and has the structural unit of representing with following general formula (i)

In the general formula (α 2), R ₁, R ₂, R ₃And R ₄And n is identical with the definition of above-mentioned general formula (α 1); R ₁₁And R ₁₂The alkylidene group of expression carbonatoms 2～6 is same to each other or different to each other; Y is illustrated in the R that combines with phenyl ring ₁₁, R ₁₂And the hydrogen atom or the alkoxyl group that replace on the different positions of Sauerstoffatom (O),

In the general formula (i), A represents organic residue, the singly-bound of at least a kind divalence selecting or the key of selecting arbitrarily from following formula (i-4) from the group of being made up of following formula (i-1)～(i-3) and (i-5); S and t are respectively 0 or 1～4 integer independently; R ₁₃And R ₁₄Organic residue of selecting in the group of representing halogen atom respectively independently or forming by the aralkoxy of the aryloxy of the aralkyl of the aryl of the cycloalkyloxy of the cycloalkyl of the alkoxyl group of the alkyl of carbonatoms 1～10, carbonatoms 1～10, carbonatoms 6～20, carbonatoms 6～20, carbonatoms 6～10, carbonatoms 7～20, carbonatoms 6～10 and carbonatoms 7～20

In the formula (i-1), R ₁₅, R ₁₆, R ₁₇And R ₁₈The alkyl of representing hydrogen atom, halogen atom or carbonatoms 1～3 respectively independently,

In the formula (i-2), R ₁₉And R ₂₀The alkyl of representing hydrogen atom, halogen atom or carbonatoms 1～3 respectively independently,

In the formula (i-3), u represents 4～11 integer, the R that these are a plurality of ₂₁And R ₂₂Represent the group from alkyl, selected respectively independently by hydrogen atom, halogen atom and carbonatoms 1～3,

In the formula (i-5), R ₂₃And R ₂₄Represent the group from alkyl, selected respectively independently by hydrogen atom, halogen atom and carbonatoms 1～10.

3. resin combination according to claim 1 and 2, wherein, the viscosity-average molecular weight of above-mentioned A composition is 16,000～25,000.

4. resin combination according to claim 3, wherein, the viscosity-average molecular weight of above-mentioned A1 composition is 16,000～25,000.

5. according to any described resin combination in the claim 1～4, wherein, in the above-mentioned A composition, the polyorganosiloxane units content that contains in 100 weight %A1 compositions is 1～20 weight %, and the polyorganosiloxane units content in 100 weight %A compositions is 0.5～5 weight %.

6. according to any described resin combination in the claim 1～5, wherein, the n in the above-mentioned general formula (α 1) is 16～50.

7. according to any described resin combination in the claim 1～6, wherein, above-mentioned B composition is the oligomer that the structural unit by following general formula (β 1) forms,

In the general formula (β 1), A, s, t, R ₁₃And R ₁₄All expressions and same group, atom or the numerical value of above-mentioned formula (i).

8. resin combination according to claim 7, wherein, above-mentioned B composition is the oligomer of following general formula (β 2) expression,

In the general formula (β 2), A, s, t, R ₁₃And R ₁₄All expressions and same group, atom or the numerical value of above-mentioned formula (i); Z represent carbonatoms that the part of hydrogen atom, hydrogen atom is replaced by fluorine atom or do not replaced by fluorine atom be 1～9 straight chain or branched-chain alkyl or phenyl substituted alkyl, carbonatoms be 10～50 chain alkyl, Siliciumatom number be 4～40 organopolysiloxane chain or-X-C _mH _2m+1, wherein, X is-R-O-,-R-CO-O-or-R-O-CO-, this R represents that singly-bound or carbonatoms are the aliphatic alkyl of 1～10 divalence, and m represents 10～50 integer, and r represents 1～5 integer, and p represents 3～15 integer.

9. according to any described resin combination in the claim 1～8, wherein, the mist value of the 2mm thickness of measuring with JIS K7105 is 0.3～20%.

10. transparent resin moulding product are with the resin combination injection molding of claim 9 and obtain.

11. transparent resin moulding product according to claim 10, wherein, the wall thickness of above-mentioned injection-molded article mainly is that the part by 0.05～0.5mm constitutes.

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