CN101381510A - Thermoplastic resin compositions - Google Patents

Abstract

The invention provides a thermoplastic resin composition, wherein the transmittance at a wavelength lambda of 808 nanometers is less than 65 percent, and the transmittance at a wavelength lambda of 850 nanometers is more than 70 percent as measured by a test piece with the thickness of 1 millimeter; preferably provides a thermoplastic resin composition, wherein the transmittance at the wavelength lambda of 808 nanometers is less than 36 percent, and the transmittance at the wavelength lambda of 850 nanometers is more than 84 percent as measured by the test piece with the thickness of 1 millimeter; and more preferably provides a thermoplastic resin composition which also contains a thermal stabilizer. The invention provides a formed product which contains the composition, and in particular relates to a sheet component and a laminated body, wherein the laminated body is obtained through laser welding of the formed product and a formed product of the thermoplastic resin, wherein the transmittance at the wavelength lambda of 808 nanometers of the thermoplastic resin is more than 75 percent as measured by the test piece with the thickness of 1 millimeter. The invention also provides a thermoplastic resin composition which has superior permeability within adequate specific wavelength as an optical sensor component, can perform laser welding with other materials and has superior absorbency within laser welding wavelength, a formed product and a sheet component which contain the thermoplastic resin composition, and a laminated body which uses the thermoplastic resin composition.

Description

The thermoplastic resin composition

Technical field

The multilayer body and the touch panel sensor (touch panel sensor) that the present invention relates to the thermoplastic resin composition and comprise its moulding product, sheet component and comprise it are used multilayer body, and wherein said thermoplastic resin composition has feature aspect the transmittance at wavelength X=808nm and 850nm place.In more detail, the multilayer body and the touch panel sensor multilayer body that the present invention relates to the thermoplastic resin composition and comprise its moulding product, sheet component and comprise it, wherein, described thermoplastic resin composition is characterised in that: its transmittance at wavelength X=808nm place is low, transmittance height at wavelength X=850nm place, in addition, the transmittance at each wavelength place of wavelength X=380nm～670nm is below 1%.

Background technology

Thermoplastic resin uses in the multiple use in each field such as automobile, electronics, OA, medical treatment as structure unit or functional component.Application target is various, has by replacing metal to reach lighting, and the purposes such as production efficiency raising, cost reduction, part count minimizing of the easy forming process of utilizing it are arranged in addition.In recent years, though the resinifying of parts has the trend of more and more quickening, according to the difference of parts, the end resinifying is arranged also, the trend of higher functionization, miniaturization.That is, in the past functional to be arranged not only, also to pass through further additional function, improve design freedom or parts integrated, reach additional effect such as reduce cost, otherwise will be difficult to be accepted by market, this is real place.Wherein, compare, big quantity research is carried out in the multifunction of the thermoplastic resin of excellent in workability with thermosetting resin.

As research to multifunction, strainer resin combination through near infrared light is for example arranged, its for add copper phthalocyanine compounds and azo class or diazonium class dyestuff in the synthetic resins that has the transparency near infrared region at wavelength 700nm～1600nm, the anthraquinone kind solvent is green, absorb greatly at wavelength 860nm, 950nm transmitance height, wavelength place below 750nm, be applicable to that physics and chemistry learns machine with optical filter (for example referring to Patent Document 1,2).As same research example the strainer resin combination is arranged, it forms (for example referring to Patent Document 3) for the metallo phthalocyanine beyond interpolation metal-free phthalocyanine compounds or the copper removal in the synthetic resins that has the transparency to the near infrared region at wavelength 700nm～1600nm.

But along with the raising of led technology, therefore the luminous possibility that becomes of the LED of the various wavelength that Wavelength distribution is narrower, needs efficiently to see through the strainer resin combination of new generation of the higher function of specific wavelength in recent years.When the wavelength region may of photodiode is in the visible region, mainly be pilot lamp or indicating meter as electrical equipment.If when being in region of ultra-red, be used for information transmission between machinery and the machinery with element or optical sensor etc.The wavelength of photodiode is determined according to semiconductor material, as the representative wavelength of the LED that is used for optical sensor, can be enumerated for example 830nm, 850nm, 880nm, 940nm etc.Especially be fit to use the LED of wavelength 850nm,, need its perviousness excellence at wavelength 850nm place as the light-filter material.Though transmittance is high more good more, generally speaking is limited to more than 60% down, is preferably more than 70%, more preferably more than 80%.

On the other hand, thermoplastic resin is aspect its characteristic, and is more by the moulding product of melt moldings such as injection moulding, compressing tablet, and shape is also comparatively complicated.And it is the be bonded with each other operation of making product of these each moulding product is a lot.As method of joining, utilize the joint of tackiness agent, mechanical engagement etc. by bolt etc. in use always, still, there is the problem of adhesion strength in the tackiness agent, the problem that the mechanical engagement by bolt etc. exists expense, fixed hour, weight to increase.Though also in the application of forming processing technology such as research double-shot moulding, insert moulding, its essential mould structure complexity, maybe must prepare special shaper, the example that cost increases is more, therefore, still can not reach the fully level of practicability.

To this, the welding of heat of friction such as indirect heating welding, Vibration Welding, ultrasonic welding such as laser welding (レ-ザ-molten), hot plate welding can engage at short notice, do not use tackiness agent, metal parts in addition, do not need the specially-shaped machine yet, thereby problems such as described cost, weight increase, environmental pollution can not appear, therefore, the research that engages by these methods increases (for example referring to Patent Document 4,5,6,7).

Especially, as the laser welding of one of indirect heating welding, be to superimposed resin molded body irradiating laser light, make its side who sees through irradiation, absorb the technology of carrying out fusion, welding the opposing party then.This technology has and can three-dimensional engage, noncontact processing, do not produce advantage such as overlap, is adopted (reference example such as patent documentation 8) by a lot of fields.

As the laser that uses in the laser welding, can enumerate carbon dioxide laser (wavelength about 10,600nm), Nd:YAG laser (wavelength about 1,064nm), Nd:YVO4 laser (wavelength about 1,064nm) with as the green laser (the about 532nm of wavelength) of the second harmonic of Nd:YAG laser, Nd:YVO4 laser, diode laser (about 780nm of wavelength～980nm) etc., the preferably diode laser of excellence aspect oscillation frequency.Optical maser wavelength is used 808nm, 840nm, 940nm more, but wherein preferably uses the situation of 808nm wavelength more.

For satisfying this weldability, thermoplastic resin must the fusion by the optical maser wavelength that absorbs irradiation.According to patent documentation 9,, use carbon black as tinting material at the composition of the laser absorption material that is used for laser welding.In addition, according to patent documentation 10,, using ABS resin (the サ イ コ ラ Star Network EX18A of black at the composition of the laser absorption material that is used for laser welding; UMG ABS (strain) makes).Give under the situation of laser absorption as black colorants such as this use carbon blacks, because carbon black all shows excellent absorption under all wavelengths, so easy laser welding.But owing to also absorb the light of wavelength beyond the laser, be used for when the such requirement of above-mentioned optical filter parts sees through the article of performance of particular wavelength region, because of the former of photoabsorption thereby take place that transmitter is bad, noise, mishandle, therefore be difficult to use.In addition, also there is the drawback to be adjusted into desirable shades of colour etc.

(patent documentation 1) spy opens clear 59-010909 communique

(patent documentation 2) spy opens clear 59-023307 communique

(patent documentation 3) spy opens clear 60-139757 communique

(patent documentation 4) spy opens clear 62-049850 communique

(patent documentation 5) spy opens the 2000-218698 communique

(patent documentation 6) spy opens the 2001-071384 communique

(patent documentation 7) spy opens the 2005-166359 communique

(patent documentation 8) spy opens the 2004-188802 communique

(patent documentation 9) spy opens the 2004-168997 communique

(patent documentation 10) spy opens the 2005-029657 communique

Summary of the invention

The object of the present invention is to provide the specific wavelength perviousness excellence that is suiting with parts as optical sensor; And can with the other materials laser welding at laser welding wavelength absorption thermoplastic resin excellent composition and comprise its moulding product, sheet component and the multilayer body that comprises it.

The inventor furthers investigate for achieving the above object, found that the thermoplastic resin composition who has feature on the transmittance of wavelength X=808nm and 850nm is the resin combination that meets above-mentioned purpose, and further further investigation, finished the present invention.

According to the present invention, (1) thermoplastic resin composition is provided, it is characterized in that the transmittance of measuring with the test film of thickness 1mm at wavelength X=808nm place is below 65%, and the transmittance at wavelength X=850nm place is more than 70%.According to this characteristic (1), can obtain a kind of resin combination, it is using the laser of wavelength X=808nm to carry out the laser welding excellence of laser welding with other materials, and as the light sensor component of the laser that detects wavelength X=850nm, sensitivity excellence.In this scope, preferably the transmittance at wavelength X=808nm place is below 50%, and the transmittance at wavelength X=850nm place is the resin combination more than 75%; More preferably the transmittance at wavelength X=808nm place is below 40%, and the transmittance at wavelength X=850nm place is the resin combination more than 80%; Most preferably the transmittance at wavelength X=808nm place is below 36%, and the transmittance at wavelength X=850nm place is the resin combination more than 84%.

Described have most preferably that the resin combination of characteristic is a kind of thermoplastic resin composition, it is excellent more aspect the laser welding of the laser that uses wavelength X=808nm, and owing to the transmitance of the light beyond wavelength X=850nm significantly descends, mishandle due to the noise perception reduces, so as the optical sensor of the laser that detects wavelength X=850nm, sensitivity is excellent more.

Further,, the invention provides the thermoplastic resin composition that (2) have above-mentioned characteristic (1) as preferred scheme, its transmittance at wavelength X=380nm～each wavelength of 670nm of measuring with the test film of thickness 1mm is below 1%.According to this characteristic (2), the thermoplastic resin composition who is fit to high function light-filter can be provided, it uses the laser of wavelength X=808nm to carry out the laser welding excellence of laser welding, and remove (cut) on a large scale visible light, optionally to see through wavelength be the light of 850nm.

As one of preferred version of the present invention is the thermoplastic resin composition of (3) above-mentioned (1) or (2), and it contains thermoplastic resin (A composition) and dyes pigment ((dying the face material), dyestuff and/or pigment) (B composition).Compare with other title complexs, owing to add dying pigment transmittance being altered a great deal of minute quantity, so in general its use level is set fewly.According to this scheme (3), following thermoplastic resin composition can be provided, it is easy to the character that keeps thermoplastic resin original, particularly thermostability decline is few, the sensitivity excellence of the light sensor component of the laser of the laser welding of the laser of use wavelength X=808nm and conduct detection wavelength X=850nm.As one of preferred version of the present invention, the thermoplastic resin composition of (4) above-mentioned (1)～(3) is characterized in that, contains more than 2 kinds and dyes pigment.

As one of preferred version of the present invention, (5) thermoplastic resin composition of above-mentioned (1)～(4), wherein, thermoplastic resin (A composition) is for being selected from least a kind in polycarbonate resin, vibrin, polyarylester (polyarylate) resin, acrylic resin and the styrene resin.According to this scheme (5), the thermoplastic resin composition can be provided, and it is for utilizing general easy obtaining and the laser welding of laser general engineering plastic, that use wavelength X=808nm of appearance excellence and as the sensitivity excellence of the light sensor component of the laser that detects wavelength X=850nm.

As one of preferred scheme of the present invention, the thermoplastic resin composition of (6) above-mentioned (1)～(5) is characterized in that, contains thermo-stabilizer (C composition).In recent years, it is the thinning trend of purpose that thermoplastic resin molded article has with the weight reduction, and purposes also increases in many-side.Processing technology, commercialization technology are also improving, but the demand molten resin is than higher temperature scope stabilization in the past, improve in the thermostability that can stand the continuous use under the hot conditions.According to this scheme (6), a kind of thermoplastic resin composition is provided, the light sensor component excellence that the laser welding of the laser of its use wavelength X=808nm and conduct detect the laser of wavelength X=850nm, and thermostability improves.

As one of preferred scheme of the present invention, (7) moulding product, it comprises the thermoplastic resin composition of above-mentioned (1)～(6).According to this scheme (7), a kind of thermoplastic resin molded article can be provided, its use wavelength X=808nm laser laser welding and as the practicality excellence of the light sensor component of the perviousness excellence of the laser of wavelength X=850nm.

As one of preferred scheme of the present invention, the described moulding product in (8) above-mentioned (7), wherein the moulding product are sheet component.According to this scheme (8), a kind of moulding product can be provided, it is applicable to the various sheet components of perviousness of laser of laser welding, the λ=850nm of the laser that need to use λ=808nm.

As one of preferred scheme of the present invention, (9) multilayer body, it is to be that the moulding product of the thermoplastic resin composition more than 75% form by laser welding with the moulding product of above-mentioned (7) or (8), with comprising the transmittance of measuring with the test film of thickness 1mm at wavelength X=808nm place.According to this scheme (9), a kind of multilayer body that is applicable to light sensor component can be provided, be that the moulding product of the thermoplastic resin composition more than 75% are stacked wherein by moulding product (7) or (8) and the transmittance that is included in wavelength X=808nm place, can prevent adhering to or scratching of chemical reagent, water, so in addition since also reduced dust adhere to can stable for extended periods of time sensitivity, and the state of the moulding product of (7) or (8) can be by visual frequent affirmation.This multilayer body especially is suitable for as the touch panel sensor parts.The general optical sensor that comprises infrared LED and phototransistor that uses of touch panel sensor, if adhere to dust, water droplet etc. on the infrared rays light path, then light can not arrive phototransistor, causes transmitter bad, so must dustproof, anti-water droplet.In addition, also must the demonstration LCD of touch panel sensor being protected, waterproof and dustproof, as its countermeasure, is to engage transparent protection panel on sensor element mostly.Based on this reason, the moulding product that comprise thermoplastic resin composition of the present invention are suitable for the panel (bezel) of making the touch panel sensor parts, and these moulding product and thermoplastic resin are suitable for as the touch panel sensor parts through the multilayer body that laser welding forms.

Below further the present invention is described in detail.

Embodiment

Thermoplastic resin composition of the present invention be that various additives headed by the pigment, packing material etc. obtain by in thermoplastic resin, cooperating to dye, the thermoplastic resin composition who has feature aspect the transmittance of specific wavelength, above-mentioned thermoplastic resin, title complex are not particularly limited.

Thermoplastic resin (A composition) as constituting thermoplastic resin composition of the present invention is not particularly limited, and can enumerate known in the past various thermoplastic resins.As this thermoplastic resin, can enumerate for example polycarbonate resin, pet resin, the PEN resin, vibrin such as polybutylene terephthalate resin, polyarylate resin, polyamide resin, polyimide resin, polyetherimide resin, urethane resin, silicone resin, polyphenylene oxide resin, polyphenylene sulfide, polysulfone resin, polyethylene, polyolefin resines such as polypropylene, polystyrene resin, vinyl cyanide/styrol copolymer (AS resin), styrene-maleic anhydride copolymer, acrylonitrile/butadiene/styrene multipolymer (ABS resin), polymethacrylate resin, plexiglass, resol, Resins, epoxy, phenoxy resin, cyclic polyolefin resin etc.In addition, as elastomerics, can enumerate for example iso-butylene/synthetic polyisoprene, styrene/butadiene rubbers, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide-based elastomerics and hud typed elastomerics MBS (methyl methacrylate/phenylethylene/butadiene) rubber and MAS (methyl methacrylate/vinyl cyanide/vinylbenzene) rubber etc.

Wherein, because the shape of the appearance of the moulding product that melt molding obtains, dimensional stability, complexity is through forming process, from this aspect of good forming process (flow characteristics during injection moulding etc.), preferred amorphism (amorphism) transparent thermoplastic resin.This amorphism transparent thermoplastic resin also comprises the crystalline thermoplastic resin that crystallization velocity is slow, as the typical example of this crystalline thermoplastic resin, polyethylene terephthalate and PEN is arranged.This transparent thermoplastic resin can be homopolymer, also can be multipolymer, in addition, can be independent polymkeric substance, also can be mixture of polymers more than 2 kinds.As the preferably transparent thermoplastic resin that constitutes thermoplastic resin of the present invention, can enumerate for example polycarbonate resin, pet resin, the PEN resin, polyarylate resin, styrene resin (comprising the HIPS resin), vinyl cyanide/styrol copolymer (AS resin), phenylethylene/maleic anhydride copolymer, acrylonitrile/butadiene/styrene multipolymer (so-called transparent ABS resin), plexiglass, methyl methacrylate/styrol copolymer (MS resin), cyclic polyolefin resin, polyphenylene oxide resin and phenoxy resin etc.More preferably, general easy obtain and the formability excellence, as the polycarbonate resin (A-1 composition), vibrin (A-2 composition), polyarylate resin (A-3 composition), styrene resin (A-4 composition), the acrylic resin (A-5 composition) that are extensive use of engineering plastics.

Below the preferred polycarbonate resin (A-1 composition) that uses is in the present invention described.

＜A-1 composition: polycarbonate resin 〉

The polycarbonate resin (following abbreviate as sometimes " polycarbonate ") that is suitable among the present invention is obtained by dihydric phenol and carbonate precursor reaction, as reaction method, can enumerate for example the solid phase ester-interchange method of interface polycondensation, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

Object lesson as above-mentioned dihydric phenol, can enumerate Resorcinol, Resorcinol, 4,4 '-xenol (PVC Off エ ノ-Le), 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane of 2-(common name " dihydroxyphenyl propane "), 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to the phenylene diisopropylidene) xenol (diphenol), 4,4 '-(metaphenylene diisopropylidene) xenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane, two (3,5-two bromo-4-hydroxy phenyls) sulfone, two (4-hydroxy-3-methyl phenyl) thioether, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc., two (4-hydroxy phenyl) alkane wherein commonly used, especially dihydroxyphenyl propane (following abbreviate as sometimes " BPA ").

Among the present invention, except polycarbonate, can also use and adopt special polycarbonate that other dihydric phenols make as the A-1 composition as the dihydroxyphenyl propane class of polycarbonate commonly used.

For example, as part or all of dihydric phenol composition, use 4,4 '-(metaphenylene diisopropylidene) xenol (following be called for short sometimes " BPM "), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane (following be called for short sometimes " Bis-TMC "), 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (4-hydroxy-3-methyl phenyl) fluorenes of 9-(following be called for short sometimes " BCF ") are fit to the dimensional change due to the suction, in the strict especially purposes of the requirement of morphological stability.The consumption of the dihydric phenol beyond these BPA is preferably overall 5 moles of the dihydric phenol composition that constitutes this polycarbonate more than the %, is preferably 10 moles especially more than the %.

Especially, requiring high rigidity and requiring to constitute the copolymerization polycarbonate of the A-1 composition especially preferably following (1)～(3) of resin combination under the situation of better hydrolytic resistance.

(1) copolymerization polycarbonate, wherein, in constituting 100 moles of % of dihydric phenol composition of this polycarbonate, BPM is 20～80 moles of % (preferred 40～75 moles of %, more preferably 45～65 moles of %), and BCF is 20～80 moles of % (preferred 25～60 moles of %, more preferably 35～55 moles of %).

(2) copolymerization polycarbonate, wherein, in constituting 100 moles of % of dihydric phenol composition of this polycarbonate, BPA is 10～95 moles of % (preferred 50～90 moles of %, more preferably 60～85 moles of %), and BCF is 5～90 moles of % (preferred 10～50 moles of %, more preferably 15～40 moles of %).

(3) copolymerization polycarbonate, wherein, in the 100 moles of % of dihydric phenol composition that constitute this polycarbonate, BPM is 20～80 moles of % (preferred 40～75 moles of %, more preferably 45～65 moles of %), and Bis-TMC is 20～80 moles of % (preferred 25～60 moles of %, more preferably 35～55 moles of %).

These special polycarbonate can use separately, also can use suitably mixing more than 2 kinds.In addition, also they can be mixed use with widely used bisphenol A polycarbonate.

About the method for making and the characteristic of these special polycarbonate, for example, open the spy that flat 6-172508 communique, spy are opened flat 8-27370 communique, the spy opens in 2001-55435 communique and the Te Kai 2002-117580 communique etc. and is documented.

In addition, in above-mentioned various polycarbonate, by adjusting copolymerization composition etc., make the hydrolytic resistance of polymkeric substance self of water-intake rate and Tg (second-order transition temperature) polycarbonate in following ranges good, and the low warpage properties after the moulding is very excellent, is particularly suitable for requiring the field of morphological stability.

(i) water-intake rate is 0.05～0.15%, and is preferred 0.06～0.13%, and Tg be 120～180 ℃ polycarbonate or

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

At this, the water-intake rate of polycarbonate is the discoideus test film that adopts diameter 45mm, thickness 3.0mm, in 23 ℃ water, flood 24 hours according to ISO62-1980 after, the moisture rate value of mensuration.In addition, Tg (second-order transition temperature) measures the numerical value of trying to achieve according to JIS K7121 by differential scanning calorimeter (DSC).

On the other hand, as carbonate precursor, (Ha ロ ホ Le メ-ト) etc. specifically can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc. can to use carboxylic acid halides, carbonic ether or haloformate.

When preparing polycarbonate by interfacial polymerization, as required, also can use catalyzer, end to stop agent, be used to antioxidant that prevents the dihydric phenol oxidation etc. by such dihydric phenol and carbonate precursor.In addition, polycarbonate also can be branching polycarbonate (the difference Port リ カ-ボ ネ-ト) of the multi-functional aromatics that copolymerization 3 officials can be above.Can above multi-functional aromatics as 3 officials used herein, for example can enumerate 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane etc.

Under the situation that contains the multi-functional compounds who generates branching polycarbonate, its amount is 0.001～1 mole of % in the polycarbonate total amount, is preferably 0.005～0.9 mole of %, is preferably 0.01～0.8 mole of % especially.In addition, especially under the situation of melt transesterification process, generate branched structure sometimes, about the amount of this branched structure as side reaction, for 0.001～1 mole of % of polycarbonate total amount, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially.In addition, the ratio of this branched structure can be passed through ¹H-NMR measures and calculates.

In addition, in thermoplastic resin composition of the present invention, can the copolymerization polycarbonate and the polyestercarbonate of this 2 functionality carboxylic acid of copolymerization and 2 functionality alcohol simultaneously of polyestercarbonate, the copolymerization 2 functionality alcohol (comprising alicyclic) of 2 functionality carboxylic acids of copolymerization aromatic series or aliphatics (comprising alicyclic) as the aromatic polycarbonate resin of A-1 composition.In addition, also can be to mix the mixture obtain more than 2 kinds by the gained polycarbonate.

Here the used preferred alpha, omega-dicarboxylic acid of aliphatics 2 functionality carboxylic acids.As aliphatics 2 functionality carboxylic acids, for example preferably enumerate alicyclic dicarboxylic acids such as straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid and cyclohexane dicarboxylic acid.As 2 functionality alcohol, more preferably alicyclic diol, for example cyclohexanedimethanol, cyclohexanediol, tristane dimethanol etc.

Further, in the present invention, as the A-1 composition, the polycarbonate of the polyorganosiloxane units-poly organo alkyl copolymer that also can use copolymerization.

As the aromatic polycarbonate resin of A-1 composition can be mixing more than 2 kinds of the different polycarbonate of above-mentioned dihydric phenol, the polycarbonate that contains the branching composition, polyestercarbonate, polycarbonate-various polycarbonate such as poly organo alkyl copolymer.And also polycarbonate that can the preparation method is different, end stop to use mixing more than 2 kinds of the different polycarbonate of agent etc.

Reaction formation as the preparation method's of polycarbonate resin of the present invention interfacial polymerization, melt transesterification process, the solid phase ester-interchange method of carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc. is the currently known methods of records such as various documents and patent gazette.

Unqualified to viscosity-average molecular weight as the polycarbonate resin of A-1 composition.But since viscosity-average molecular weight less than 10,000 o'clock, reductions such as intensity, and above 50,000 o'clock, the forming process reduction, thus preferred 10,000～50,000 scope, more preferably 12,000～30,000 scope, further preferred 13,000～25,000 scope.In this case, in keeping the scope of formability etc., also can mix the polycarbonate of viscosity-average molecular weight beyond above-mentioned scope.For example, can cooperate viscosity-average molecular weight to surpass 50,000 high-molecular-weight polycarbonate composition.

Viscosity-average molecular weight described in the present invention is at first calculated specific viscosity (η by following formula _SP).Under 20 ℃, aromatic copolycarbonate 0.7g is dissolved among the methylene dichloride 100ml, measures with ostwald's viscometer, and then try to achieve specific viscosity by gained solution.

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

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

By the specific viscosity (η that tries to achieve _SP) calculate viscosity-average molecular weight M according to following mathematical expression.

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

[η]＝1.23×10 ^-4M ^0.83

c＝0.7

Below the preferred vibrin (A-2 composition) that uses is in the present invention described.

＜A-2 composition: vibrin 〉

The vibrin (following abbreviate as sometimes " polyester ") that preferably uses is polymkeric substance or the multipolymer that obtains by the condensation reaction of carrying out as principal constituent with dicarboxylic acid or its reactive derivatives and dibasic alcohol or its ester derivative in the present invention.

As dicarboxylic acid described here, the preferred terephthalic acid that uses, m-phthalic acid, phthalic acid (acid of オ Le ト Off Le), 1, the 5-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl ether dicarboxylic acid, 4,4 '-biphenyl methane dicarboxylic acid, 4,4 '-biphenyl sulfone dicarboxylic acid, 4,4 '-biphenyl isopropylidene dicarboxylic acid, 1, two (phenoxy group) ethane-4 of 2-, 4 '-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 '-right-terphenyl dicarboxylic acid (4,4-p--Off エ ニ レ Application ジ カ Le ボ Application acid), 2, fragrant same clan dicarboxylic acid such as 5-pyridine dicarboxylic acid can especially preferably use terephthalic acid, 2, the 6-naphthalene dicarboxylic acids.

Dicarboxylic acid also can be use mixing two or more.In addition, if a spot of words, this dicarboxylic acid also can mix use with more than one of alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids such as adipic acid, nonane diacid, sebacic acid, dodecanedioic acid, cyclohexane dicarboxylic acid etc.

In addition, as the glycol of polyester composition of the present invention, can enumerate for example ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol, 2-methyl isophthalic acid, aliphatic diols such as ammediol, glycol ether, triglycol; Alicyclic diols such as 1,4 cyclohexane dimethanol etc.; 2, two (beta-hydroxy ethoxyl phenenyl) propane etc. of 2-contain the glycol of aromatic ring etc.; And their mixture etc.And if a spot of words, but also the copolymerization molecular weight is 400～6,000 long chain diol, i.e. polyoxyethylene glycol, poly--1, ammediol, poly--1, more than one of 4-butyleneglycol etc.

In addition, polyester of the present invention can carry out branching by importing a spot of branching agent.Kind to branching agent is unqualified, can enumerate for example trimesic acid, trihemellitic acid, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane etc.

As concrete vibrin, can enumerate polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN (PEN), PBN (PBN), polyethylene-1, two (phenoxy group) ethane-4 of 2-, 4 '-dicarboxylic esters etc. can be enumerated poly-m-phthalic acid/ethylene glycol terephthalate, poly terephthalic acid/copolyester or polyarylesters such as m-phthalic acid butanediol ester in addition.Wherein, polyethylene terephthalate, PEN, polyarylester and their mixture that can preferably use the transparency, mechanical properties etc. to keep in balance.

Further specify the preferred in the present invention polyethylene terephthalate (PET) that uses.Polyethylene terephthalate is for being the polymkeric substance that dominant shape becomes as the terephthalic acid of dicarboxylic acid composition with ethylene glycol as diol component; In forming the dicarboxylic acid composition and diol component of polyethylene terephthalate, 70 moles of % among 100 moles of % of dicarboxylic acid composition are above, preferred 90 moles of % are above, most preferably 99 moles of % are above is the polyester of aromatic dicarboxylic acid.

Polyethylene terephthalate also can be to comprise the polyethylene terephthalate of terephthalic acid dicarboxylic acid in addition as copolymer composition.As described other the example of dicarboxylic acid composition, can enumerate for example m-phthalic acid, 2-chlorine terephthalic acid, 2,5-dichloroterephthalicacid acid, 2-methyl terephthalic acid, 4,4-Stilbene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, two phenylformic acid, two (to carboxyl phenyl) methane, anthracene dicarboxylic acid, 4,4-phenyl ether dicarboxylic acid, 4,4-biphenoxyl ethane dicarboxylic acid, 5-sulfoisophthalic acid sodium, ethylidene-two-para Toluic Acid etc.These dicarboxylic acid can use separately, perhaps use mixing more than 2 kinds.When being 100 moles of % with the dicarboxylic acid total amount, the dicarboxylic acid composition beyond the terephthalic acid be preferably 30 moles of % following, more preferably 20 moles below the %.

Further, polyethylene terephthalate, except above-mentioned aromatic dicarboxylic acid, all right copolymerization is less than the aliphatic dicarboxylic acid composition of 30 moles of %.As its object lesson, can enumerate hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid etc.

In addition, polyethylene terephthalate also can be to comprise the polyethylene terephthalate of ethylene glycol diol component in addition as copolymer composition.As other diol components, can enumerate for example ethylene glycol, glycol ether, 1,2-propylene glycol, 1, ammediol, 2, trans-or-2,2,4,4-tetramethyl--1,3-cyclobutanediol, 1,4-butyleneglycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene-glycol, cyclohexanediol, terephthalyl alcohol, dihydroxyphenyl propane, tetrabromo-bisphenol, tetrabromo-bisphenol-two (2-hydroxyethyl ether) etc.These can use separately, perhaps use mixing more than 2 kinds.

Further, also can use as the diol component copolymerization polyethylene terephthalate of micro-polyoxyethylene glycol.As the molecular weight of polyoxyethylene glycol, preferred 150～6,000 scope.

As the proportion of composing of polyoxyethylene glycol composition, in diol component 100 weight %, be preferably 5 weight % following, more preferably 3 weight % following, more preferably below the 2 weight %.On the other hand, as lower limit, more than the preferred 0.5 weight %, more preferably more than the 1 weight %.

Further, in the polyethylene terephthalate, side reaction product during as common polymerization contains the 0.5 mole of glycol ether composition more than the % of having an appointment in 100 moles of % of diol component, this glycol ether composition be preferably 6 moles of % following, more preferably 5 moles below the %.

In polyethylene terephthalate of the present invention, for the part of terephthalic acid composition change the m-phthalic acid composition into and poly terephthalic acid/ethylene isophthalate multipolymer of obtaining (below, sometimes abbreviate the TA/IA multipolymer as), constitute the terephthalic acid of dicarboxylic acid composition of this multipolymer and the ratio of m-phthalic acid, when being 100 moles of % with total dicarboxylic acid composition, terephthalic acid is 70～99.9 moles of %, preferred 75～99 moles of %, more preferably 80～99 moles of %; M-phthalic acid is 0.1～30 mole of %, preferred 1～25 mole of %, more preferably 1～20 mole of %.

Further, in this TA/IA multipolymer, except terephthalic acid and m-phthalic acid, following, preferred 5 moles below the % of can the copolymerization naphthalene dicarboxylic acids etc. above-mentioned 10 moles of % of aromatic dicarboxylic acid; In addition, following, preferred 3 moles below the % of can the copolymerization hexanodioic acid etc. above-mentioned 5 moles of % of aliphatic dicarboxylic acid, but the TA/IA multipolymer that only constitutes of dicarboxylic acid composition most preferably by terephthalic acid and m-phthalic acid.In addition,, most preferably make spent glycol separately as the diol component in the TA/IA multipolymer, but also can copolymerization ethylene glycol diol component in addition.

In polyethylene terephthalate of the present invention, become the neopentyl glycol composition and polyethylene terephthalate/neopentyl glycol ester copolymer (the following EG/NPG multipolymer that abbreviates as sometimes) of obtaining for a part with glycol component, constitute the ethylene glycol of diol component of this multipolymer and the ratio of neopentyl glycol, when being 100 moles of % with the total diol composition, ethylene glycol is 90～99 moles of %, preferred 95～99 moles of %, more preferably 97～99 moles of %; Neopentyl glycol is 1～10 mole of %, preferred 1～8 mole of %, more preferably 1～5 mole of %.In addition, also can copolymerization ethylene glycol and neopentyl glycol diol component in addition.

In this EG/NPG multipolymer, following, preferred 5 moles below the % of above-mentioned 10 moles of % of aromatic dicarboxylic acid such as the m-phthalic acid beyond can the copolymerization terephthalic acid, naphthalene dicarboxylic acids; Or following, preferred 3 moles below the % of above-mentioned 5 moles of % of aliphatic dicarboxylic acid such as hexanodioic acid, but most preferably the dicarboxylic acid composition only is the EG/NPG multipolymer of terephthalic acid.In addition, also can the copolymerization aliphatic dicarboxylic acid.

Preparation method about the polyethylene terephthalate that uses among the present invention, can be by usual method, under the condition that the polycondensation catalyst that contains titanium, germanium, antimony etc. exists, make dicarboxylic acid composition and above-mentioned diol component polymerization while heating, and with outside water byproduct or the lower alcohol discharge system.As germanium class polymerizing catalyst, oxide compound, oxyhydroxide, halogenide, alkoxide, phenates of germanium etc. are for example arranged; More specifically, for example can enumerate germanium dioxide, hydroxide germanium, germanium tetrachloride, tetramethoxy germanium etc.In addition, insoluble catalyzer such as ANTIMONY TRIOXIDE SB 203 99.8 PCT for example.

In addition, in the present invention, can and use compounds such as manganese known, that in the transesterification reaction of polycondensation last stage, use, zinc, calcium, magnesium in the past; And also can be after transesterification reaction finish, the compound by phosphoric acid or phosphorous acid etc. makes this catalyst deactivation carry out polycondensation.The preparation method of polyethylene terephthalate can be any method in batch-type, the successive polymerization formula.

In addition, as the polyethylene terephthalate that uses among the present invention, also can be the regeneration polyethylene terephthalate that forms by various pet resin goods regeneration.As described resin, for example can enumerate mainly that container, film, sheet material, fiber etc. are main, but more preferably container, be the PET bottle.Its advantage is, goods between the usage period short situation quality many, regenerating resin stable easily and than being easier to avoid sneaking into foreign matter.

As the technical scheme of described regeneration pet resin, for example specifically can enumerate with PET bottle (1) pulverize, (2) washing, (3) dehydrate, (4) heat fusing, form particulate state.Can certainly use the pulverizing of only having carried out (1) material, proceed to (2) washing material or proceed to the exsiccant material of (3).And, also can after washing, pulverize.In addition, if consider the thermostability this point of gained resin combination, then preferably under regeneration contains the state of moisture in the pet resin, do not carry out melt-processed, but preferably to through the resin of washing procedure at least will with carry out drying treatment before aromatic copolycarbonate mixes.In addition, as the regeneration pet resin, also can use the unacceptable product of goods, from annotating pulverizing product that road or runner etc. obtain or with the particle that obtains after their fusions etc.

As the regeneration polyethylene terephthalate,, also widely know with the used pet resin depolymerization of recovery, in the technology of making polyethylene terephthalate near the stage of raw material once again.But, under the situation of this polyethylene terephthalate, have the characteristic that approaches new raw material usually.Therefore, as more suitable polyethylene terephthalate, can enumerate the pet resin that used pet resin is regenerated and obtained without the depolymerization operation in the present invention.Further, also the pet resin and the regeneration pet resin of new raw material can be mixed use.

Molecular weight to pet resin is not particularly limited, but is being solvent with the ortho chloro phenol, is being 0.6～1.5, is preferably 0.65～1.2, more preferably 0.7～1.15 35 ℃ of limiting viscosities of measuring down.

Further specify the preferred PEN (PEN) that uses among the present invention.

PEN (following claim sometimes " PEN ") is with 2, and the 6-naphthalene dicarboxylic acids is main sour composition, is the vibrin of main diol component with ethylene glycol.That is can copolymerization a small amount of other sour composition, diol component and the oxygen acid composition of PEN of the present invention.

About PEN, become among 100 moles of % of component at the total dicarboxylic acid that constitutes this polyester, 2,6-naphthalene dicarboxylic acids composition is 85～97 moles of %, and becomes among 100 moles of % of component at total diol, glycol component is 85～100 moles of %.2, the combination of 6-naphthalene dicarboxylic acids composition and other sour compositions can appropriateness suppress its crystallinity, realizes moulding processibility and stretch orientation simultaneously.In the present invention, 2,6-naphthalene dicarboxylic acids composition is meant from 2, and the repeating unit of 6-naphthalene dicarboxylic acids can be by 2, and 6-naphthalene dicarboxylic acids and ester thereof formation property derivative imports among the PEN.In addition, other sour composition also can import among the PEN by this acid itself or its ester formation property derivative.As ester formation property derivative here, can enumerate for example lower alkyl esters, phenylester and acid anhydrides etc.

About preferred PEN in the present invention, become among 100 moles of % of component at the total dicarboxylic acid that constitutes this polyester, comprise 2,85～97 moles of % of 6-naphthalene dicarboxylic acids composition and be selected from m-phthalic acid and the terephthalic acid composition in 3～15 moles of % of at least a kind of dicarboxylic acid composition.By m-phthalic acid and/or the terephthalic acid that contains this specified quantitative, can realize simultaneously that crystallinity reduces and stretch orientation, can obtain fully and the intensity and the good moulding product of shock-resistance of uniformly extension.The ratio of m-phthalic acid and/or terephthalic acid is the scope of 5～12 moles of % more preferably.These acid preferably are included in the PEN resin as copolymer composition, wherein preferred especially terephthalic acid.

On the other hand, as the sour composition that can contain among the PEN beyond m-phthalic acid and the terephthalic acid, for example can enumerate 2, aromatic dicarboxylic acids such as 7-naphthalene dicarboxylic acids, tert.-butylbenzene dioctyl phthalate, biphenoxyl ethane dicarboxylic acid, diphenyldicarboxylic acid, biphenoxyl ethane dicarboxylic acid, sulfobenzide dicarboxylic acid, phenyl ether dicarboxylic acid, phenylmethane dicarboxylic acid, benzophenone dicarboxylic acid and diphenyl sulfide dicarboxylic acid; Aliphatic dicarboxylic acids such as oxalic acid, succsinic acid, hexanodioic acid, sebacic acid and dodecanedioic acid; Alicyclic dicarboxylic acids such as six hydrogen terephthalic acids, perhydronaphthalene dicarboxylic acid and tetraline dicarboxylic acid etc. (as mentioned above, comprising these sour esters formation property derivative).

As diol component that can contain, except that ethylene glycol among the PEN, can enumerate for example propylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, 1,5-pentanediol, 1, aliphatic diols such as 6-hexylene glycol, neopentyl glycol and glycol ether; Alicyclic diols such as cyclohexanedimethanol and tristane dimethanol; Dihydric phenols such as dihydroxyphenyl propane, Resorcinol, Resorcinol and dihydroxybiphenyl; The oxyalkylene affixture of dihydroxyphenyl propane aromatic diols such as (ア Le キ レ Application オ キ サ イ De are paid and added thing); Polyoxyethylene glycol and poly-1, polyvalent alcohols such as 4-butyleneglycol; And fluorenes such as two hydroxyl-oxethyl phenyl fluorenes, or the like.

In addition, as the oxygen acid composition that can contain among the PEN, can enumerate hydroxy-benzoic acid and hydroxy diphenyl carboxylic acid etc.

Further, in the scope of harmless the object of the invention, PEN of the present invention can contain 3 officials can above sour composition or diol component.As the above sour composition of 3 officials energy, trihemellitic acid etc. is for example arranged, as the above diol component of 3 officials energy, glycerine, trimethyl propane and tetramethylolmethane etc. are for example arranged.The above components in proportions of 3 officials energy in 100 moles of % of each constituent, is preferably used below 2 moles of %, is more preferably used 1 mole below the %.

During polymerization PEN, can be suitable for known in the past various polymerization processs.As an example wherein, as, making ethylene glycol, 2, the dimethyl esters of 6-naphthalene dicarboxylic acids and copolymer composition (terephthalic acid dimethyl esters etc.) carry out transesterify, the method for under reduced pressure carrying out polycondensation then in distillation for removing methanol.In the present invention, in order further to improve limiting viscosity, especially preferably carry out solid state polymerization.As transesterification catalyst, preferably enumerate calcium acetate, magnesium acetate etc.As transesterification catalyst, can also enumerate acetate, monocarboxylate, alkoxide and the oxide compound etc. of magnesium, manganese, calcium and zinc etc. in addition in addition.In addition, for making this transesterification catalyst inactivation, preferably after transesterification reaction, add phosphorus compounds such as trimethyl phosphite 99.In addition,, can use germanium compound, titanium compound and antimony compounds etc., for example the alkoxide of germanium dioxide, hydroxide germanium, germanium, four titanium butoxide, tetraisopropoxy titanium and titanous oxalate etc. as polymerisation catalysts.

Molecular weight to PEN is not particularly limited, but the limiting viscosity that records in 25 ℃ ortho chloro phenol solvent is preferably more than the 0.55dl/g, more preferably more than the 0.6dl/g, more preferably more than the 0.65dl/g.If limiting viscosity is more than the 0.55dl/g, crystallization time lengthening then, the condition and range during forming process broadens, and favourable situation is many.On the other hand, this limiting viscosity is preferably below the 1.3dl/g, more preferably below the 1.2dl/g.Under the too high situation of limiting viscosity, the moulding product are easy to generate distortion or space, and are therefore not preferred.

The preferred in the present invention polyarylate resin of using (A-3 composition) below is described.

＜A-3 composition: polyarylate resin 〉

Polyarylate resin is obtained by aromatic dicarboxylic acid or derivatives thereof and dihydric phenol or derivatives thereof.As the aromatic dicarboxylic acid that is used to prepare polyarylester, if can provide satisfied polymkeric substance with dihydric phenol reaction, then can be for arbitrarily, can use a kind or will mix more than 2 kinds and use.

As preferred aromatic dicarboxylic acid composition.Can enumerate for example terephthalic acid, m-phthalic acid.In addition, also can be their mixture.

Object lesson as the dihydric phenol composition, can enumerate 2, two (4-hydroxy phenyl) propane of 2-, 2, two (the 4-hydroxyls-3 of 2-, the 5-dibromo phenyl) propane, 2, two (4-hydroxyl-3, the 5-dichlorophenyl) propane of 2-, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxy benzophenone, 4,4 '-dihydroxyl ditan, 2,2 '-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 4,4 '-dihydroxybiphenyl, Resorcinol etc.These dihydric phenol compositions are the para-orientation body, but also can use other isomer, further, and also can be with ethylene glycol, propylene glycol, neopentyl glycol etc. and dihydric phenol composition and usefulness.

As preferred polyarylate resin in above-mentioned, the aromatic dicarboxylic acid composition be can enumerate and terephthalic acid and m-phthalic acid comprised, comprise 2 as the dihydric phenol composition, the polyarylate resin of two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-.The ratio of terephthalic acid and m-phthalic acid, preferred terephthalic acid/isophthalic acid=9/1～1/9 (mol ratio) considers preferred especially 7/3～3/7 from melt processable, balancing performance aspect.

As other representational polyarylate resin, can enumerate the aromatic dicarboxylic acid composition and comprise terephthalic acid, the dihydric phenol composition comprises the polyarylate resin of dihydroxyphenyl propane and Resorcinol.For the ratio of this dihydroxyphenyl propane and Resorcinol, preferred dihydroxyphenyl propane/Resorcinol=50/50～70/30 (mol ratio), further preferred 55/45～70/30, more preferably 60/40～70/30.

From rerum natura and extrude the processibility aspect and consider that polyarylate resin viscosity-average molecular weight of the present invention preferably is about 7,000～100,000 scope.In addition, polyarylate resin can be selected any polymerization process in interface polycondensation and the transesterification reaction method.

Preferred in the present invention styrene resin (A-4 composition) and the acrylic resin (A-5 composition) that uses below is described.

＜A-4 composition: styrene resin 〉

Styrene resin also can be enumerated o-methyl styrene, a vinyl toluene, p-methylstyrene, 2 except that vinylbenzene, 4-dimethyl styrene, ethyl styrene, to nuclear alkyl-substituted styrenes such as t-butyl styrene; The polymkeric substance of alpha-alkyl such as alpha-methyl styrene, Alpha-Methyl-p-methylstyrene substituted phenylethylene etc.; And the above and other multipolymer of vinyl compound more than at least a kind of their a kind; Their two or more multipolymer.

As above-mentioned vinyl compound that can copolymerization, for example can enumerate unsaturated nitrile compound classes such as vinyl cyanide, methacrylonitrile; Acid anhydrides such as maleic anhydride etc., particularly preferred polymkeric substance is polystyrene (comprising syndiotactic polystyrene), styrene/acrylonitrile copolymer (AS resin) in these polymkeric substance.

＜A-5 composition: acrylic resin 〉

Acrylic resin, except that methyl acrylate, also can enumerate alkyl acrylates such as ethyl propenoate, propyl acrylate, isopropyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate, 2-EHA, cyclohexyl acrylate, dodecylacrylate, vinylformic acid stearyl, phenyl acrylate, benzyl acrylate; The perhaps polymkeric substance of alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, Octyl methacrylate, methacrylic acid 2-ethylhexyl, cyclohexyl methacrylate, lauryl methacrylate, methacrylic acid stearyl, phenyl methacrylate, benzyl methacrylate etc.; And their multipolymer more than 2 kinds.In these polymkeric substance, particularly preferred polymkeric substance is a polymethylmethacrylate.

Thermoplastic resin composition of the present invention is characterised in that and cooperates additive, packing material that in above-mentioned thermoplastic resin it has feature on the transmittance of certain wave strong point.As this title complex, can make thermoplastic resin composition's wavelength curve change, keep original characteristic, mechanical properties or the flowability of thermoplastic resin to be easy to aspect considerations such as prediction from a small amount of interpolation, preferably dye pigment, below this is dyed pigment be elaborated.

＜dye pigment 〉

That be fit to use among the present invention dyes pigment (B composition), and to measure the transmittance of its 200mg/1L chloroformic solution at wavelength X=808nm place be below 65% and the transmittance at wavelength X=850nm place is more than 70% with the Xiao Chi of thickness 1mm.Further, in addition, more preferably with the Xiao Chi of thickness 1mm measure its 200mg/1L chloroformic solution at the transmittance of each wavelength of wavelength X=380nm～670nm at the pigment that dyes below 1%.In addition, use under the situation of the mixture that dyes pigment more than 2 kinds, with the light absorption ratio of the 200mg/1L chloroformic solution that respectively dyes pigment measured with the Xiao Chi of thickness 1mm at wavelength X=808nm place be Ai808 (%), light absorption ratio at wavelength X=850nm place be Ai850 (%), respectively dye pigment with respect to the ratio of dying the pigment composition total amount be Ri (weight %) (wherein, i is for dying the pigment numbering) time, dye pigment composition and preferably satisfy following formula.

$\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Ai}808\×\mathrm{Ri}>35$

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}\mathrm{Ai}850\&times;\mathrm{Ri}<30$

As this pigment that dyes, for example can be listed as dyestuffs such as lifting perylene class dyestuff, coumarins dyestuff, thioindigo class dyestuff, anthraquinone dyes, cyanine class dyestuff, thioxanthene ketone dyestuff, Prussian blue etc. yellow prussiate, perynone (ペ リ ノ Application) class dyestuff, quinoline dyestuff, quinacridine ketone dyestuff, dioxazines dyestuff, isoindoline ketone dyestuff, phthalocyanines dye or on various plate-like fillers, have the metallic pigment of metal tunicle or metal oxide coating.Be easy to the angle consideration from the transmitance control of wavelength 808nm and 850nm, the anthraquinone dyes in the preferred coloring agent, cyanine class dyestuff, but be not confined to these dyestuffs especially.As the representation example of this dyestuff, for example can enumerate SDA7257, SDA7950, SDA7257, SDA6533, the SDA9393 of IR-750, CY-2, CY-4, CY-9 and the ト ス コ company of Japanese chemical drug society, SIR-114 of Mitsui Chemicals society etc.

As the above-mentioned pigment that dyes that dyes beyond the pigment, can enumerate bluing agent, fluorescence dye (comprising white dyes) etc.Bluing agent is meant by absorbing the pigment that dyes that orange or xanchromatic light is blueness or purple, special preferred coloring agent.As the representation example of bluing agent, the マ Network ロ レ Star Network ス バ イ オ レ Star ト B of バ イ エ Le company and the Port リ シ Application ス レ Application Block Le-RLS of マ Network ロ レ Star Network ス Block Le-RR and Network ラ リ ア Application ト company etc. are for example arranged.As fluorescence dye, can enumerate coumarins fluorescence dye, chromene fluorochrome, perylene fluorochrome, anthraquinone fluorochrome, thioindigo fluorochrome, xanthene fluorochrome, xanthone fluorochrome, thioxanthene fluorochrome, thioxanthone fluorochrome, thiazides fluorescence dye and diamino Stilbene fluorochrome etc.Wherein preferred thermotolerance is good, few coumarins fluorescence dye, chromene fluorochrome and the perylene fluorochrome of deterioration during forming process.

The above-mentioned pigment that dyes can use a kind or with mix using more than 2 kinds, is benchmark with 100 parts by weight of thermoplastic resin, and its content is preferably 0.00001～1 weight part, more preferably 0.00002～0.5 weight part, 0.0001～0.3 weight part most preferably.

Thermoplastic resin composition of the present invention not influencing in the scope in the characteristic of certain wave strong point of claim defined, is preferably contained thermo-stabilizer (C composition) except dying pigment (B composition).As the feature of thermoplastic resin, can enumerate easy processing forming, require the raising by the goods design freedom in addition or parts are integrated reduces cost or find novel designability etc.Processing technology or goods development of technology are remarkable, still, for reaching above-mentioned requirements, must adopting the higher in the past processing temperature case of ratio more, therefore wish the molten resin thermostabilization.In addition, the purposes of thermoplastic resin has diversified tendency, think in the past the article that can not use resinifying also under study for action, be desirably in the long-term reliability under the hot environment.Below, describe in detail be used to improve the thermostability of molten resin, for making the thermally-stabilised thermo-stabilizer that uses (C composition) under hot environment.

As the thermo-stabilizer (C composition) that is fit among the present invention use, can enumerate Phosphorus stablizer (C-1 composition), Hinered phenols stablizer (C-2 composition), other stablizers (C-3 composition) etc., this stablizer can be used for molecular weight or the form and aspect of stabilising thermoplastic resin combination when machine-shaping, prevents the deterioration of moulding product when life-time service.

＜C-1 composition: Phosphorus stablizer 〉

As Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.

Particularly, as phosphorous acid ester, can enumerate for example triphenyl phosphorous acid ester, 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, three (diethyl phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester, distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, and the dicyclohexyl pentaerythritol diphosphites etc.

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

As phosphate compound, can enumerate for example tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl tolyl phosphate, the adjacent xenyl phenyl ester (diphenyl monoorthoxenylphosphate) of di(2-ethylhexyl)phosphate phenyl list, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound, for example as, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc., wherein, preferred four (di-tert-butyl-phenyl)-biphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite esters.This phosphinate compound preferably can and be used with the bi-ester of phosphite with the aryl that has replaced 2 above alkyl.

As phosphonate compound, can enumerate for example phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.

As tertiary phosphine, can enumerate for example triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three p-methylphenyl phosphines, three naphthyl phosphines and phenylbenzene benzyl phosphine etc.Particularly preferred tertiary phosphine is a triphenylphosphine.

Above-mentioned Phosphorus stablizer not only can use a kind, also can use mixing more than 2 kinds.In the above-mentioned Phosphorus stablizer, the phosphorous acid ester of preferred phosphinate compound or following general formula (1) expression.

(in the formula (1), R and R ' expression carbonatoms is that 6～30 alkyl or carbonatoms are 6～30 aryl, each other can be identical, and perhaps also can be different.)

As mentioned above, as phosphinate compound, preferred four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, with this phosphinate is the stablizer of principal constituent, can use among commercially available Sandostab P-EPQ (trade mark, Clariant company make) and the Irgafos P-EPQ (trade mark, CIBA SPECIALTY CHEMICALS company makes) any.

In addition, preferred bi-ester of phosphite is a distearyl pentaerythrityl diphosphite, two (2 in above-mentioned formula (1), the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites.

Distearyl pentaerythrityl diphosphite can use any among commercially available ア デ カ ス Block PEP-8 (trade mark, rising sun electrochemical industry (strain) company makes), the JPP681S (trade mark, north of the city chemical industry (strain) company makes).Two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites can use commercially available ア デ カ ス Block PEP-24G (trade mark, the manufacturing of rising sun electrochemical industry (strain) company), Alkanox P-24 (trade mark, the manufacturing of Great Lakes company), Ultranox P626 (trade mark, the manufacturing of GE Specialty Chemicals company), Doverphos S-9432 (trade mark, Dover Chemical company makes) and any of Irgaofos126 and 126FF (trade mark, CIBASPECIALTY CHEMICALS company makes) etc.Two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites can easily use commercially available ア デ カ ス Block PEP-36 (trade mark, rising sun electrochemical industry (strain) is made).In addition, two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites can use any among commercially available ア デ カ ス Block PEP-45 (trade mark, rising sun electrochemical industry (strain) is made), the Doverphos S-9228 (trade mark, Dover Chemical company makes).

A composition with 100 weight parts is a benchmark, the use level of Phosphorus stablizer be preferably 0.0005～2 weight part, more preferably 0.001～1.5 weight part, most preferably be 0.003～1 weight part.

＜C-2 composition: Hinered phenols stablizer 〉

As hindered phenol compound, can use all cpds that in thermoplastic resin, cooperates usually.As described hindered phenol compound; can enumerate for example alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester 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-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-DI-tert-butylphenol compounds); 4; 4 '-butylidene two (3-methyl-6-DI-tert-butylphenol compounds); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [2-tertiary butyl-4-hydroxy-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) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-di ethylene bis-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2,4-pair-(n-octyl sulfo-)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1; 3; the 5-triazine; N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2,4,6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1,3,5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; four [methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester; 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl group }-1, the 1-dimethyl ethyl]-2; 4; 8,10-four oxaspiros [5,5] undecane; four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1; 3; 5-trimethylammonium-2,4,6-three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene; and three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) isocyanuric acid ester etc.

In the present invention, preferred four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, the octadecyl-3-(3 that uses in the above-claimed cpd, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, and 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.Preferred especially 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned hindered phenol anti-oxidants can use separately, perhaps uses mixing more than 2 kinds.

A composition with 100 weight parts is a benchmark, the use level of hindered phenol anti-oxidants be preferably 0.001～2 weight part, more preferably 0.005～1.5 weight part, most preferably be 0.01～1 weight part.

In addition, preferably cooperate in Phosphorus stablizer (C-1 composition) and the hindered phenol anti-oxidants (C-2 composition) any, more preferably with them and use.And under the situation of usefulness, A composition with 100 weight parts is a benchmark, more preferably cooperates 0.01～0.3 weight part, preferred 0.02～0.25 weight part, the more preferably Phosphorus stablizer of 0.03～0.2 weight part and 0.01～0.3 weight part, preferred 0.02～0.25 weight part, the more preferably hindered phenol anti-oxidants of 0.03～0.2 weight part.

＜C-3 composition: other stablizers 〉

Other thermo-stabilizers preferably with above-mentioned Phosphorus stablizer, hindered phenol anti-oxidants in any and usefulness, more preferably with both and use.As described other thermo-stabilizers, for example preferred, with 3-hydroxyl-5, the resultant of 7-di-t-butyl-furans-2-ketone and o-Xylol is the lactone stablizer of representative (detailed content of this stablizer is documented in the spy and opens in the flat 7-233160 communique).Described compound just has an Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS company makes) commercially available, can use this compound.And the stablizer that this compound and various bi-ester of phosphite and hindered phenol compound mix is just in city's mid-sales.For example, the Irganox HP-2921 of preferred above-mentioned company manufacturing.Also can use premixed stablizer in the present invention.A composition with 100 weight parts is a benchmark, and the use level of lactone stablizer is preferably 0.0005～0.05 weight part, 0.001～0.03 weight part more preferably.

In addition, as other stablizer, can enumerate tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-dodecyl thiopropionate), reach glycerol-sulphur-containing stabilizers such as 3-stearyl thiopropionate.Under the situation that resin combination is applied to the rotational moulding shaping, described stablizer is effective especially.A composition with 100 weight parts is a benchmark, and the use level of this sulphur-containing stabilizer is preferably 0.001～0.1 weight part, 0.01～0.08 weight part more preferably.

＜about other title complexs 〉

In the present invention, being matched with composition in the above-mentioned A composition thermoplastic resin is not limited in and dyes pigment (B composition), thermo-stabilizer (C composition), not influencing in the scope in the characteristic of specific wavelength of claims defined, also can use the various title complexs that in thermoplastic resin, use usually.Below these title complexs are described.

(i) packing material

In thermoplastic resin composition of the present invention, the material as the transmittance that helps to be apparent in specific wavelength can cooperate known in the past various packing materials.As packing material, preferred silicate minerals class filler or category of glass filler.As described silicate minerals class filler, preferably enumerate talcum, white mica, synthetic fluorine mica, terre verte and wollastonite, as described category of glass filler, glass fibre, sheet glass and glass milled fiber etc. are for example arranged.Silicate minerals class filler and category of glass filler also can use its surface through metal oxide coated fillers such as titanium peroxide, zinc oxide, cerium oxide and silicon oxide.

Above-mentioned packing material also can carry out surface treatment with various surface treatment agents in advance.As described surface treatment agent, can carry out surface treatment by various surface treatment agents such as silane coupling agent (comprising alkylalkoxy silane, poly-hydrogen organo-siloxane (Port リ オ Le ガ ノ Ha イ De ロ ジ エ Application シ ロ キ サ Application) etc.), high-grade aliphatic ester, acid compound (as phosphorous acid, phosphoric acid, carboxylic acid and carboxylic acid anhydride etc.) and waxes.Further, also can make particulate state with collecting agent granulations such as various resins, high-grade aliphatic ester and waxes.

A composition with 100 weight parts is a benchmark, and packing material can be that the upper limit cooperates with 100 weight parts.This upper limit is preferably 25 weight parts, 20 weight parts more preferably.Under the too much situation of packing material use level, bad order takes place easily, thermostability reduces.

(ii) fire retardant

Can cooperate known in the past various fire retardants among the thermoplastic resin composition of the present invention.By cooperating the compound that uses as fire retardant, not only improved flame retardant resistance, and, can also improve as static electricity resistance, flowability, rigidity and thermostability according to the character of each compound.

As this fire retardant, can enumerate (ii-1) organic metal salt based flame retardant (organic sulfonic acid alkali (soil) metal-salt for example, borate metal salt based flame retardant and stannic acid metallic salt fire retardant etc.), (ii-2) organic phosphates fire retardant (phosplate compound for example, the phosphoric acid ester oligomer compounds, the phosphonate oligomers compound, phosphazene compound and phosphonic amide etc.), (ii-3) comprise the type siloxane fire retardant of silicone compounds, and (ii-4) halogen fire retardant (brominated epoxy resin for example, brominated Polystyrene, brominated polycarbonate (comprising oligopolymer), bromination polyacrylic ester and chlorinatedpolyethylene etc.) etc.

(ii-1) organic metal salt based flame retardant

The organic metal salt based flame retardant not only can be kept thermotolerance substantially, also brings static electricity resistance simultaneously at least, is favourable in this.The organic metal salt based flame retardant that the most advantageously uses is fluorine-containing organometalate compound in the present invention.Fluorine-containing organometalate compound of the present invention is meant a kind of metal salt compound, and it comprises: the organic acid anionic component and the cation constituent that comprises metal ion that comprise the alkyl with fluorine replacement.As preferred object lesson, can enumerate the metal-salt of fluoro organic sulfonic acid, the metal-salt of fluoro organo-sulfate and the metal-salt of fluoro organophosphate.Fluorine-containing organometalate compound can use a kind, or uses mixing more than 2 kinds.The metal-salt of wherein preferred fluoro organic sulfonic acid, especially preferably has a metal organic sulfonate of perfluoroalkyl.Here the scope of the carbonatoms of perfluoroalkyl preferred 1～18, more preferably 1～10 scope, further preferred 1～8 scope.

The metal that constitutes the metal ion of organic metallic salt fire retardant is basic metal or alkaline-earth metal, as basic metal, can enumerate lithium, sodium, potassium, rubidium and caesium, as alkaline-earth metal, can enumerate beryllium, magnesium, calcium, strontium and barium.More preferably basic metal.Therefore preferred organic metal salt based flame retardant is the perfluoro alkyl sulfonic acid an alkali metal salt.In this basic metal, preferred rubidium and caesium under the situation that the transparency is had relatively high expectations, still, because it is not general and purifying is also very difficult, the result is unfavorable sometimes aspect cost.On the other hand, favourable lithium and sodium are unfavorable aspect transparent on the contrary aspect cost, flame retardant resistance.Consider these, the basic metal in the perfluoro alkyl sulfonic acid an alkali metal salt can be selected to use (making い divide the け Ru), but be best suited at the balanced excellent perfluoro alkyl sulfonic acid sylvite of either side characteristic.This sylvite can and be used with the perfluoro alkyl sulfonic acid an alkali metal salt that is made of other alkali metal.

As this perfluoro alkyl sulfonic acid an alkali metal salt, can enumerate trifluoromethanesulfonic acid potassium, perfluor fourth potassium sulfonate, the own potassium sulfonate of perfluor, perfluorooctane sulfonate potassium, five fluorine ethyl sulfonic acid sodium, perfluor fourth sodium sulfonate, perfluorooctane sulfonate sodium, trifluoromethanesulfonic acid lithium, perfluor fourth sulfonic acid lithium, perfluor sulfonic acid in heptan lithium, trifluoromethanesulfonic acid caesium, perfluor fourth sulfonic acid caesium, perfluorooctane sulfonate caesium, the own sulfonic acid caesium of perfluor, perfluor fourth sulfonic acid rubidium and the own sulfonic acid rubidium of perfluor etc., these can use a kind, or will also use more than 2 kinds.Wherein preferred especially perfluor fourth potassium sulfonate.

Above-mentioned fluorine-containing organic metal salt is preferably below the 50ppm by the content of the fluorion (not changing thing イ オ Application) of ion-chromatographic determination, more preferably 20ppm following, more preferably below the 10ppm.The content of fluorion is low more, and flame retardant resistance, photostabilization are good more.In fact the lower limit of content of fluoride ion can be 0, but take all factors into consideration from purification procedures number and effect aspect, in practicality about preferred 0.2ppm.The perfluoro alkyl sulfonic acid an alkali metal salt of this content of fluoride ion for example can following purifying.The perfluoro alkyl sulfonic acid an alkali metal salt is joined in the ion exchanged water of 2～10 times of weight of this metal-salt, it is dissolved at 40～90 ℃ (more preferably 60～85 ℃).This perfluoro alkyl sulfonic acid an alkali metal salt, by with in alkaline carbonate or the oxyhydroxide and the method for perfluoro alkyl sulfonic acid, or with in alkaline carbonate or the oxyhydroxide and the method for perfluoroalkyl sulfonic acid fluoride (the preferred latter's method) generate.In addition, the preferred especially resistance value of described ion exchanged water is the above water of 18M Ω cm.The solution that has dissolved metal-salt was stirred 0.1～3 hour more preferably 0.5～2.5 hour under said temperature.Cool off this solution to 0～40 ℃ then, preferably be cooled to 10～35 ℃.Separate out crystallization by cooling.Take out the crystallization of separating out by filtering.The perfluoro alkyl sulfonic acid an alkali metal salt for preparing the purifying that is more suitable for thus.

A composition with 100 weight parts is a benchmark, and the use level of fluorine-containing organometalate compound is preferably 0.005～0.6 weight part, more preferably 0.005～0.2 weight part, 0.008～0.13 weight part more preferably.By cooperating the fluorine-containing organic metal salt of above-mentioned preferable range degree, in performance expectation effect (for example flame retardant resistance, static electricity resistance etc.), also reduced sunproof detrimentally affect to poly carbonate resin composition.

In addition, as the organic metal salt based flame retardant beyond the above-mentioned fluorine-containing organometalate compound, the preferred not metal-salt of the organic sulfonic acid of contain fluorine atoms.As this metal-salt, can enumerate an alkali metal salt of aliphatic sulfonic, the alkaline earth salt of aliphatic sulfonic, an alkali metal salt of aromatic sulphonic acid and the alkaline earth salt of aromatic sulphonic acid etc. (all not contain fluorine atoms).

As the preferred example of aliphatic sulfonic metal-salt, can enumerate alkyl sulfonate alkali (soil) metal-salt, these can use a kind, or will also use (statement of alkali (soil) metal-salt is meant the meaning that an alkali metal salt, alkaline earth salt include) more than 2 kinds here.Preferred example as the alkylsulphonic acid that uses in abovementioned alkyl azochlorosulfonate acid alkali (soil) metal-salt, can enumerate methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, methyl fourth sulfonic acid, own sulfonic acid, heptan sulfonic acid, hot sulfonic acid etc., these can use a kind, or will also use more than 2 kinds.

As the aromatic sulphonic acid that uses in aromatic sulphonic acid alkali (soil) metal-salt, can enumerate the sulfonic acid of the aromatic thioether that is selected from monomer shape or polymkeric substance shape, the sulfonic acid of aromatic carboxylic acid and ester, the sulfonic acid of the aromatic ether of monomer shape or polymkeric substance shape, the sulfonic acid of aromatic sulfonic acid ester, the aromatic sulphonic acid of monomer shape or polymkeric substance shape, the aromatic series sulfone sulfonic acid of monomer shape or polymkeric substance shape, the sulfonic acid of aromatic ketone, hetero ring type sulfonic acid, the sulfonic acid of aromatic series sulfoxide, at least a kind of acid in the condenses that methylene fundamental mode key by aromatic sulphonic acid forms, these can use a kind, or will also use more than 2 kinds.

Concrete example as aromatic sulphonic acid alkali (soil) metal-salt, can enumerate for example diphenyl sulfide-4,4 '-disulfonic acid disodium, diphenyl sulfide-4,4 '-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalic acid (Port リ エ チ レ Application テ レ Off Le acid Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), 1-methoxynaphthalene-4-calcium sulphonate, 4-dodecylphenyl ether disulfonic acid disodium, poly-(2,6-dimethyl phenylate (phenyleneoxide)) the many sodium of many sulfonic acid, poly-(1, the 3-phenylate) the many sodium of many sulfonic acid, poly-(1, the 4-phenylate) the many sodium of many sulfonic acid, poly-(2,6-phenylbenzene phenylate) the many potassium of many sulfonic acid, poly-(2-fluoro-6-butyl phenylate) poly-sulfonic acid lithium, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, the Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to the benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, the thionaphthene sodium sulfonate, thionyl benzene-4-potassium sulfonate, the formalin condenses of sodium naphthalene sulfonate and the formalin condenses of anthracene sulfonic acid sodium etc.

On the other hand, alkali (soil) metal-salt as sulfuric ester, can enumerate alkali (soil) metal-salt of the sulfuric ester of monobasic and/or polyalcohols especially, as the sulfuric ester of this monobasic and/or polyalcohols, can enumerate single, two, three, four sulfuric esters of sulfuric ester, the tetramethylolmethane of methyl sulfate, sulfovinic acid, sulfuric acid dodecyl ester, sulfuric acid cetyl ester, polyoxyethylene alkyl phenyl ether, the sulfuric ester of glyceryl monolaurate, the sulfuric ester of monopalmitin and sulfuric ester of glyceryl monostearate etc.As alkali (soil) metal-salt of these sulfuric esters, alkali (soil) metal-salt that can the preferably sulfuric acid dodecyl ester.

In addition; as other alkali (soil) metal-salt; alkali (soil) metal-salt of aromatic sulfonamide can be enumerated, for example asccharin can be enumerated; N-(p-methylphenyl alkylsulfonyl)-to toluene sulfo group imide (N-(p-ト リ Le ス Le ホ ニ Le-p-ト Le エ Application ス Le ホ イ ミ De); alkali (soil) metal-salt of N-(N '-benzylamino carbonyl) sulfanilyl-imines (N-(N '-ベ Application ジ Le ア ミ ノ カ Le ボ ニ Le) ス Le Off ア ニ Le イ ミ De) and N-(phenyl carboxyl) sulfanilyl-imines (N-(Off エ ニ Le カ Le ボ キ シ Le) ス Le Off ア ニ Le イ ミ De) etc.

The preferred not metal-salt of the organic sulfonic acid of contain fluorine atoms is aromatic sulphonic acid alkali (soil) metal-salt in above-mentioned, preferred especially sylvite.When cooperating this aromatic sulphonic acid alkali (soil) metal-salt, be benchmark with the A composition of 100 weight parts, its content is 0.001～1 weight part, be preferably 0.005～0.5 weight part, more preferably 0.01～0.1 weight part.

(ii-2) organic phosphates fire retardant

As the organic phosphates fire retardant, the preferred aryl groups phosphate compound.This aryl phosphoric acids ester cpds has the effect that improves flame retardant resistance, and because phosphate compound has the plasticization effect, though reduced thermotolerance, from this point of forming process that improves resin combination of the present invention, is favourable.This phosphate compound can use in the past as the known various phosphate compounds of fire retardant, but more preferably uses the phosphate compound more than a kind or 2 kinds of following general formula (2) expression.

(wherein, the X in the following formula represents by dihydric phenol deutero-divalent organic group, R ¹¹, R ¹², R ¹³And R ¹⁴Represent that respectively n represents 0～5 integer by monohydric phenol deutero-any monovalent organic radical group.)

The phosphate compound of following formula also can be the mixture of compound with different n numbers, and under the situation of this mixture, average n number is preferably 0.5～1.5, more preferably 0.8～1.2, more preferably 0.95～1.15, be preferably 1～1.14 especially.

Preferred object lesson as the dihydric phenol of the above-mentioned X that derives, Resorcinol, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxybiphenyl (dihydroxydiphenyl), dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) thioether are for example arranged, wherein preferred Resorcinol, dihydroxyphenyl propane and dihydroxybiphenyl.

As the above-mentioned R that derives ¹¹, R ¹², R ¹³And R ¹⁴The preferred object lesson of monohydric phenol, phenol, cresols, xylenol, isopropyl-phenol, butylphenol are for example arranged and to cumyl phenol, wherein preferred phenol and 2,6-xylenol.

In addition, this monohydric phenol also can be replaced by halogen atom, as the object lesson that has by the phosphate compound of this monohydric phenol deutero-group, can enumerate three (2,4,6-tribromo phenyl) phosphoric acid ester and three (2, the 4-dibromo phenyl) phosphoric acid ester, three (4-bromophenyl) phosphoric acid ester etc.

On the other hand, object lesson as the phosphate compound that does not replace halogen atom, preferred triphenyl and three (2,6-xylyl (xylyl)) phosplate compound such as phosphoric acid ester, and with Resorcinol two two (2, the 6-xylyl) phosphoric acid ester) is the phosphoric acid ester oligopolymer of main body, with 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) is the phosphoric acid ester oligopolymer of main body, (main body represents to contain on a small quantity other different compositions of the polymerization degree here, preferably contains more than the composition 80 weight % of the n=1 in the above-mentioned formula (2) based on the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphoesters), more preferably more than the 85 weight %, further more than the preferred 90 weight %).A composition with 100 weight parts is a benchmark, and the use level of organic phosphates fire retardant is preferably 0.1～30 weight part, more preferably 1～25 weight part, 5～20 weight parts more preferably.

(ii-3) type siloxane fire retardant

Chemical reaction when the siloxane compound that uses as the type siloxane fire retardant can pass through burning in the present invention improves flame retardant resistance.As this compound, all cpds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Think that silicone compounds forms structure in when burning by self bonding or with composition bonding from resin, or the reduction reaction when forming by this structure, give the polycarbonate resin flame retardant effect.Therefore, preferably contain in above-mentioned reaction active high group, more specifically, preferably contain at least a group in alkoxyl group and the hydrogen (being Si-H) of being selected from of specified amount.Proportional as containing of described group (alkoxyl group, Si-H yl), preferred 0.1～1.2mol/100g, more preferably 0.12～1mol/100g, further preferred 0.15～0.6mol/100g.This ratio is to try to achieve according to caustic leaching process, the hydrogen of silicone compound deposits yields by analytical unit weight or the amount of alcohol.In addition, the preferred carbonatoms of alkoxyl group is 1～4 alkoxyl group, preferred especially methoxyl group.

Usually, the structure of silicone compounds is made of 4 kinds of siloxane unit arbitrary combination as follows.That is,

M unit: (CH ₃) ₃SiO _1/2, H (CH ₃) ₂SiO _1/2, H ₂(CH ₃) SiO _1/2, (CH ₃) ₂(CH ₂=CH) SiO _1/2, (CH ₃) ₂(C ₆H ₅) SiO _1/2, (CH ₃) (C ₆H ₅) (CH ₂=CH) SiO _1/2Deng 1 functionality siloxane unit;

D unit: (CH ₃) ₂SiO, H (CH ₃) SiO, H ₂SiO, H (C ₆H ₅) SiO, (CH ₃) (CH ₂=CH) SiO, (C ₆H ₅) ₂2 functionality siloxane units such as SiO;

T unit: (CH ₃) SiO _3/2, (C ₃H ₇) SiO _3/2, HSiO _3/2, (CH ₂=CH) SiO _3/2, (C ₆H ₅) SiO _3/2Deng 3 functionality siloxane units;

Q unit: SiO ₂4 functionality siloxane units of expression.

The structure of the silicone compounds that uses in the type siloxane fire retardant particularly, as rational formula, can be enumerated D _n, T _p, M _mD _n, M _mT _p, M _mQ _q, M _mD _nT _p, M _mD _nQ _q, M _mT _pQ _q, M _mD _nT _pQ _q, D _nT _p, D _nQ _q, D _nT _pQ _qWherein the structure of preferred silicone compounds is M _mD _n, M _mT _p, M _mD _nT _p, M _mD _nQ _q, preferred structure is M _mD _nOr M _mD _nT _p

Here, the Coefficient m in the above-mentioned rational formula, n, p, q are the integer more than 1 of the polymerization degree of each siloxane unit of expression, and the summation of coefficient is the mean polymerisation degree of silicone compounds in each rational formula.The scope of this mean polymerisation degree preferred 3～150, more preferably 3～80 scope, further preferred 3～60 scope, preferred especially 4～40 scope.In this preferred range, excellent more aspect flame retardant resistance.Further, as hereinafter described, the silicone compounds that contains the specified amount aromatic group is also excellent aspect the transparency, form and aspect.

In addition, when among m, n, p, the q any was numerical value more than 2, the siloxane unit that has this coefficient can be institute's bonded hydrogen atom, the different siloxane unit more than 2 kinds of organic residue.

Silicone compounds can be the straight chain shape, also can have branched structure.In addition, organic residue of bonding is that carbonatoms is organic residue of 1～30, more preferably 1～20 on the Siliciumatom.As this organic residue, can enumerate alkyl such as methyl, ethyl, propyl group, butyl, hexyl and decyl particularly; Cycloalkyl such as cyclohexyl; Aryl such as phenyl; And aralkyl such as tolyl.More preferably carbonatoms is 1～8 alkyl, thiazolinyl or aryl.As alkyl, carbonatomss such as special preferable methyl, ethyl and propyl group are 1～4 alkyl.

Further, the silicone compounds that uses as the type siloxane fire retardant preferably contains aryl.Contain proportional (the aromatic group amount) of the aromatic group of more preferably following general formula (3) expression is 10～70 weight % (more preferably 15～60 weight %).

(in the formula (3), X represents that independently of one another OH base, carbonatoms are 1～20 the organic residue of monovalence.N represents 0～5 integer.And, in formula (3) when n be 2 when above, can get different types of separately X.)

Silicone compounds as the type siloxane fire retardant uses except above-mentioned Si-H base and alkoxyl group, also can contain reactive group, as this reactive group, can enumerate for example amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and metacryloxy etc.

As silicone compounds, preferably enumerate the unitary at least a above silicone compounds of the formation that contains following general formula (4) and (5) expression with Si-H base.

(in formula (4) and the formula (5), Z ¹～Z ³Represent that independently of one another hydrogen atom, carbonatoms are the compound of 1～20 organic residue of monovalence or following formula (6) expression.α ¹～α ³Represent 0 or 1 independently of one another.M1 represents the integer more than 0 or 1.And in formula (5), when m1 is 2 when above, repeating unit can be mutually different a plurality of repeating units.)

(in the formula (6), Z ⁴～Z ⁸Represent that independently of one another hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence.α ⁴～α ⁸Represent 0 or 1 independently of one another.M2 represents the integer more than 0 or 1.And in formula (6), when m2 is 2 when above, repeating unit can be mutually different a plurality of repeating units.)

As in the siloxane compound of type siloxane fire retardant,, can enumerate at least a kind of compound in the compound that for example is selected from general formula (7) and general formula (8) expression as silicone compounds with alkoxyl group.

(in the formula (7), β ¹Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl and carbonatoms are 6～12 aryl and aralkyl.γ ¹, γ ², γ ³, γ ⁴, γ ⁵And γ ⁶The expression carbonatoms is that 1～6 alkyl and cycloalkyl and carbonatoms are 6～12 aryl and aralkyl, and at least 1 group is an aryl or aralkyl.δ ¹, δ ²And δ ³The expression carbonatoms is 1～4 alkoxyl group.)

(in the formula (8), β ²And β ³Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl and carbonatoms are 6～12 aryl and aralkyl.γ ⁷, γ ⁸, γ ⁹, γ ¹⁰, γ ¹¹, γ ¹², γ ¹³And γ ¹⁴The expression carbonatoms is that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl and carbonatoms are 6～12 aryl and aralkyl, and at least 1 group is an aryl or aralkyl.δ ⁴, δ ⁵, δ ⁶And δ ⁷The expression carbonatoms is 1～4 alkoxyl group.)

A composition with 100 weight parts is a benchmark, and the use level of type siloxane fire retardant is preferably 0.01～10 weight part, further preferred 0.1～8 weight part, more preferably 1～5 weight part.

(ii-4) halogen fire retardant

As halogen fire retardant of the present invention, preferred especially brominated polycarbonate (comprising oligopolymer).The brominated polycarbonate excellent heat resistance, and can significantly improve flame retardant resistance.The brominated polycarbonate that uses among the present invention serve as the brominated polycarbonates that all constitute unitary at least 60 moles of %, preferred 80 moles of % for the formation unit with following general formula (9) expression, especially preferably in fact by the brominated polycarbonate of the formation unit formation of following general formula (9) expression.

(in the formula (9), X is a bromine atoms, R be carbonatoms be 1～4 alkylidene group (ア Le キ レ Application base), carbonatoms be 1～4 alkylidene (ア Le キ リ デ Application base) or-SO ₂-.)

In addition, in this formula (9), preferred R represent methylene radical, ethylidene, isopropylidene (イ ソ プ ロ ピ リ デ Application base) ,-SO ₂-Bie preferred isopropylidene.

The chloroformic acid ester group that brominated polycarbonate is preferred remaining is terminal few, and terminal chlorine dose is below the 0.3ppm, more preferably below the 0.2ppm.End chlorine dose is following tries to achieve for this: sample dissolution in methylene dichloride, is added 4-(to nitrobenzyl) pyridine then, with terminal chlorine (terminal chloro-formic ester) reaction, adopt ultraviolet-visible pectrophotometer (U-3200 of Hitachi) to measure.Terminal chlorine dose is 0.3ppm when following, and the thermostability of poly carbonate resin composition is better, and can high-temperature molding, and the result may be provided in the more excellent poly carbonate resin composition of type processibility.

In addition, the C-terminal that brominated polycarbonate is preferred remaining is few.More specifically, with respect to 1 mole of the formation unit of brominated polycarbonate, the terminal hydroxyl amount is preferably below 0.0005 mole, more preferably below 0.0003 mole.The terminal hydroxyl amount can be passed through sample dissolution to adopt in deuterochloroform ¹The H-NMR method is measured and is tried to achieve.If above-mentioned terminal hydroxyl amount can further improve the thermostability of poly carbonate resin composition.

The scope of the specific viscosity of brominated polycarbonate preferred 0.015～0.1, more preferably 0.015～0.08 scope.The formula of the above-mentioned specific viscosity that the specific viscosity of brominated polycarbonate is adopted in the time of can be according to the viscosity-average molecular weight of above-mentioned calculating polycarbonate resin of the present invention calculates.

A composition with 100 weight parts is a benchmark, and the use level of halogen fire retardant is preferably 0.1～30 weight part, more preferably 1～25 weight part, further preferred 5～15 weight parts.

(iii) Antidrip agent (drip and prevent agent)

In thermoplastic resin composition of the present invention, can cooperate Antidrip agent.By with this Antidrip agent and above-mentioned fire retardant and usefulness, can obtain better flame retardant resistance.As this Antidrip agent, can enumerate and have the fluoropolymer that protofibril forms ability, as this polymkeric substance, can enumerate tetrafluoroethylene, tetrafluoroethylene copolymer (for example tetrafluoroethylene/hexafluoropropylene copolymer etc.), by No. 4379910 described partially fluorinated polymkeric substance of communique of United States Patent (USP), fluoridize the polycarbonate resin of diphenol preparation etc., preferably polytetrafluoroethylene (below be sometimes referred to as PTFE).

Have the tetrafluoroethylene (fibrillation PTFE) that protofibril forms ability and have high molecular weight, at bonding between the PTFE under the external actions such as shearing force, having becomes fibrous trend.Its number-average molecular weight is 1,500,000～tens million of scope, its lower limit more preferably 3,000,000.This number-average molecular weight such as spy open disclosed method in the flat 6-145520 communique, calculate according to the melt viscosity at 380 ℃ tetrafluoroethylene.That is, fibrillation PTFE is 10 by the melt viscosity at 380 ℃ of the mensuration of the method described in the above-mentioned communique ⁷～10 ¹³The scope of poise, preferred 10 ⁸～10 ¹²The scope of poise.

Above-mentioned PTFE except use solid shape, can also use the aqueous liquid dispersion form.In addition, for improve this have PTFE that protofibril forms ability in resin dispersiveness and obtain excellent flame-retardant performance and mechanical characteristics, can use PTFE mixture with other mixed with resin forms.In addition, also can preferably use to have and open in the flat 6-145520 communique disclosedly as the spy, be core, be the goods of the structure of shell with low-molecular-weight tetrafluoroethylene with described fibrillation PTFE.

As the commercially available product of fibrillation PTFE, can enumerate for example テ Off ロ Application (registered trademark) 6J, Port リ Off ロ Application MPA FA500, the F-201L etc. of ダ イ キ Application chemical industry (strain) of Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain).The commercially available product of the aqueous liquid dispersion of fibrillation PTFE can be enumerated Off Le オ Application AD-1, the AD-936 of rising sun ア イ シ-ア イ Off ロ ロ Port リ マ-ズ (strain) manufacturing, Off Le オ Application D-1, the D-2 that ダ イ キ Application industry (strain) is made, the conduct representatives such as テ Off ロ Application (registered trademark) 30J that Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain) is made.

Fibrillation PTFE as mixed style, can use the goods that obtain by following method: (1) mixes the aqueous liquid dispersion of fibrillation PTFE and the aqueous liquid dispersion or the solution of organic polymer, carry out co-precipitation, obtain the method (spy opens clear 60-258263 communique, the spy opens the method for records such as clear 63-154744 communique) of common cohesion mixture; (2) with aqueous liquid dispersion and the exsiccant organic polymer particle blended method (spy opens the method for putting down in writing in the flat 4-272957 communique) of fibrillation PTFE; (3) aqueous liquid dispersion and the organic polymer particle solution with fibrillation PTFE mixes, and removes the method (spy opens flat 06-220210 communique, the spy opens the method for records such as flat 08-188653 communique) of all kinds of SOLVENTS then from this mixture simultaneously; (4) will in the aqueous liquid dispersion of fibrillation PTFE, be formed with the method (spy opens the method for putting down in writing in the flat 9-95583 communique) of the monomer polymerization of organic polymer; And after (5) mixed the aqueous liquid dispersion of PTFE and organic polymer dispersion liquid, further polymerising ethylene class monomer in this mixed dispersion liquid obtained the method (spy opens the method for records such as flat 11-29679 communique) of mixture then.As the commercially available product of the fibrillation PTFE of these mixed styles, can enumerate " BLENDEX B449 " (trade(brand)name) that " メ Block レ Application A3800 " (trade(brand)name) and GE ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ company of Mitsubishi's レ イ ヨ Application (strain) makes etc.

In order more effectively to show thermoplastic resin composition's of the present invention laser welding, preferably differential is diffusing as best one can for above-mentioned fibrillation PTFE.As realizing described microdispersed method, the fibrillation PTFE of above-mentioned mixed style is favourable.In addition, differential is loose also is favourable to the method for the PTFE of aqueous liquid dispersion form directly being supplied with the melting mixing machine.But the PTFE form and aspect that should be noted that the aqueous liquid dispersion form are somewhat poor.As the ratio of the fibrillation PTFE in the mixed style, in this mixture 100 weight %, preferred fibrillation PTFE is 10～80 weight part %, more preferably 15～75 weight part %.When the ratio of fibrillation PTFE during, can reach the good dispersion of fibrillation PTFE in above-mentioned scope.

A composition with 100 weight parts is a benchmark, and the content of fibrillation PTFE in the thermoplastic resin composition is preferably 0.001～1 weight part, 0.1～0.7 weight part more preferably.

(iv) static inhibitor

In thermoplastic resin composition of the present invention, can cooperate static inhibitor.For the moulding product that comprise the thermoplastic resin composition, may have because of dust adheres to and cause bad order or, be particularly suitable for this situation because of static electrification causes the situation of mishandle.As this static inhibitor, for example can enumerate (1) with ten dialkyl benzene sulfonic acid phosphonium salts (ホ ス ホ ニ ウ system salt) be representative fragrant basic sulfonic acid phosphonium salt, and alkane base sulfonic acid phosphonium salt etc. machine sulfonic acid phosphonium salt and as the boric acid microcosmic salt of four fluorine boron acid phosphonium salt are arranged.With the A composition of 100 weight parts is that the content of Gai phosphonium salt of benchmark ， is to be suitable below 5 weight parts, is preferably 0.05～5 weight part, more preferably 1～3.5 weight part, the further scope of preferred 1.5～3 weight parts.

As this static inhibitor, for example can enumerate organic sulfonic acid alkali (soil) metal-salts such as (2) 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 and organic sulfonic acid barium.As previously mentioned, this metal-salt also can be used as the fire retardant use.This metal-salt more specifically can be enumerated the metal-salt of Witco 1298 Soft Acid for example, metal-salt of perfluoro alkyl sulfonic acid etc.A composition with 100 weight parts is a benchmark, and the content of organic sulfonic acid alkali (soil) metal-salt is to be suitable below 0.5 weight part, is preferably 0.001～0.3 weight part, 0.005～0.2 weight part more preferably.An alkali metal salt of special preferred lithium, caesium and rubidium etc.

As this static inhibitor, for example can enumerate organic sulfonic acid ammonium salts such as (3) alkylsulphonic acid ammonium salt and aryl sulfonic acid ammonium salt.A composition with 100 weight parts is a benchmark, and this ammonium salt is to be suitable below 0.05 weight part.As this static inhibitor, for example can enumerate such poly-(oxyalkylene) glycol (Port リ (オ キ シ ア Le キ レ Application) the ゲ リ コ-Le) composition that contains of (4) polyether ester amides and be the polymkeric substance of its constituent.A composition with 100 weight parts is a benchmark, and this polymkeric substance is to be suitable below 5 weight parts.

(the compound that v) has the hot line receptivity

In thermoplastic resin composition of the present invention, can cooperate compound with hot line receptivity.Cooperated the thermoplastic resin composition of this compound can suppress indoor high temperatureization, be particularly suitable in the frame material purposes of vehicle resin window glass or resin window window frame glass (Trees fat Chuang サ Star シ ガ ラ ス).

As this compound, preferably enumerate the various metallic compounds of near infrared absorption ability excellences such as metal boride class near infrared ray absorption such as metal oxide-type near infrared ray absorption, lanthanum boride, cerium boride and tungsten borides such as ATO, ITO, iridium oxide and ruthenium oxide.Metal oxide-type near infrared ray absorption, metal boride class near infrared ray absorption are preferably the scope of 0.1～200ppm (part by weight), the more preferably scope of 0.5～100ppm in thermoplastic resin composition of the present invention.

(vi) light diffusing agent

In thermoplastic resin composition of the present invention, can cooperate light diffusing agent.This light diffusing agent can be enumerated the inorganic fine particles of high molecular particle, low-refraction and their mixture etc.Described high molecular particle is as the known micropartical of the light diffusing agent of polycarbonate resin, polyvinyl resin.Preference as, be the vinylformic acid crosslinked particle of number μ m and poly organic silicon sesquioxyalkane (Port リ オ Le ガ ノ シ Le セ ス キ オ キ サ Application) with the particle diameter for the type siloxane crosslinked particle of representative etc.The shape of light diffusing agent for example has sphere, disc, cylindricality and unsetting etc.Described sphere is nonessential full spherical also, also comprises the situation of distortion; Described cylindricality comprises cubes.Preferred light diffusing agent is spherical, and its particle diameter homogeneous more is good more.A composition with 100 weight parts is a benchmark, and the content of light diffusing agent is preferably 0.005～20 weight part, more preferably 0.01～10 weight part, 0.01～3 weight part more preferably.In addition, can and use light diffusing agent more than 2 kinds.

(vii) UV light absorber

In thermoplastic resin composition of the present invention, can cooperate UV light absorber, variable color when being fit to prevent in light such as sunlight, fluorescence, xenon light or LED light, expose for a long time.As this uv-absorbing agent; can enumerate benzophenone particularly; for example 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base (ス Le ホ キ シ) benzophenone; 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base three hydrogenations (ス Le ホ キ シ ト リ Ha イ De ラ イ De レ イ ト) benzophenone; 2; 2 '-dihydroxyl-4-methoxy benzophenone; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxyl-4,4 '-dimethoxy-5-sodium sulphur oxygen base (ソ ジ ウ system ス Le ホ キ シ) 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.

As this uv-absorbing agent, can enumerate benzotriazole category particularly, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole for example, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone), and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phenyl-diformyl formamino)-the 5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole and can with the multipolymer of the vinyl monomer of this monomer copolymerization, or 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer of the vinyl monomer of this monomer copolymerization etc.

As this uv-absorbing agent, can enumerate the hydroxyphenyltriazinuv class particularly, for example 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propoxy-phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butoxy phenol etc.Can enumerate 2-(4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls)-5-hexyloxy phenol etc. further and change the phenyl of above-mentioned exemplary compounds into 2, the compound that the 4-3,5-dimethylphenyl forms.

As this uv-absorbing agent, can enumerate the cyclic imide esters of gallic acid particularly, for example 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene (ジ Off エ ニ レ Application)) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthalene) two (3,1-benzoxazine-4-ketone) etc.

In addition; as this uv-absorbing agent; can enumerate cyanoacrylate particularly; for example 1,3-is two-[(2 '-cyano group-3 ', 3 '-diphenylprop enoyl-) oxygen base]-2; two [(the 2-cyano group-3 of 2-; 3-diphenylprop enoyl-) oxygen base] methyl) propane and 1,3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene etc.

Further, above-mentioned UV light absorber, it also can be the UV light absorber of polymer-type, it is by adopting the structure of monomeric compound that can radical polymerization, by described ultraviolet-absorbing monomer and/or have the light stability monomer of the structure of hindered amine and the monomer copolymerization of alkyl (methyl) acrylate etc. and obtaining.As above-mentioned ultraviolet-absorbing monomer, preferably in the ester substituting group of (methyl) acrylate, contain the compound of benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide acid esters skeleton and cyanoacrylate skeleton.

In above-mentioned, preferred benzotriazole category and hydroxyphenyltriazinuv class aspect ultraviolet absorption ability, preferred cyclic imide esters of gallic acid and cyanoacrylate aspect thermotolerance.Above-mentioned UV light absorber can be used separately or use with the mixture more than 2 kinds.

A composition with 100 weight parts is a benchmark, and the content of UV light absorber is 0.01～2 weight part, preferred 0.03～2 weight part, more preferably 0.02～1 weight part, further preferred 0.05～0.5 weight part.

(viii) releasing agent

In thermoplastic resin composition of the present invention, can cooperate releasing agent, the distortion that described releasing agent is suitable for improving productivity or reduces the moulding product.As this releasing agent, can use known releasing agent, can enumerate for example polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefins wax (polyethylene wax, 1-olefin polymer etc.Also can use the compound modified of functional group through containing sour modification etc.), silicone compounds, fluorine cpd (with the polyfluoro hydrocarbon ils of poly-fluoroalkyl ether), paraffin, beeswax etc. as representative.A composition with 100 weight parts is a benchmark, and this releasing agent is preferably 0.005～2 weight part.

Wherein, can enumerate fatty acid ester as preferred releasing agent.This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This fatty alcohol can be for 1 yuan of alcohol, also can be the polyvalent alcohol more than 2 yuan.Carbonatoms that in addition should alcohol is 3～32, more preferably 5～30.As described monohydroxy-alcohol, can enumerate for example dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol, eicosanol, Tetracosyl alcohol, 26 alkanol and triacontanol price quote etc.As described polyvalent alcohol, can enumerate tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Polyglycerine (triglycerin～six glycerine), ditrimethylolpropane, Xylitol, Sorbitol Powder and N.F,USP MANNITOL etc.For fatty acid ester of the present invention, more preferably polyvalent alcohol.

On the other hand, the carbonatoms of aliphatic carboxylic acid is preferably 3～32, and preferred especially carbonatoms is 10～22 aliphatic carboxylic acid.As this aliphatic carboxylic acid, can enumerate for example representative examples of saturated aliphatic carboxylic and unsaturated aliphatic carboxylic acids such as Zoomeric acid, oleic acid, linolic acid, linolenic acid, eicosenoic acid, timnodonic acid and cetoleic acid such as capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid (palmitinic acid), margaric acid, octadecanoic acid (stearic acid), nondecylic acid, docosoic, arachic acid and docosoic acid.The preferred carbonatoms of above-mentioned aliphatic carboxylic acid is 14～20 aliphatic carboxylic acid.Wherein, preferred representative examples of saturated aliphatic carboxylic, preferred especially stearic acid and palmitinic acid.

Above-mentioned aliphatic carboxylic acid such as stearic acid, palmitinic acid is because normally by being the animal raw fat of representative with tallow or lard etc. and being that the natural oil lipid manufacturings such as vegetative grease of representative obtain with plam oil or Oleum Helianthi, so these aliphatic carboxylic acids are generally other carboxylic acid compositions' of containing different carbonatomss mixture.Therefore, in the manufacturing of fatty acid ester of the present invention, aliphatic carboxylic acid be can use, stearic acid, palmitinic acid especially preferably used by this natural oil lipid mixture form manufacturing, that contain other carboxylic acid compositions.

Fatty acid ester of the present invention can be any of partial ester or full ester (full ester).But because the common hydroxyl value height of partial ester brings out the resin decomposition easily during high temperature, so more preferably full ester.The acid number of fatty acid ester of the present invention, from the thermostability angle consider to be preferably 20 below, more preferably 4～20 scope, further preferred 4～12 scope.In addition, in fact acid number can be 0.The hydroxyl value of fatty acid ester is 0.1～30 scope more preferably.Iodine number is preferably below 10.In fact iodine number can be 0.These characteristics can be tried to achieve according to the method for regulation among the JIS K 0070.

A composition with 100 weight parts is a benchmark, and the content of this releasing agent is preferably 0.005～2 weight part, more preferably 0.01～1 weight part, 0.05～0.5 weight part more preferably.In this scope, the thermoplastic resin composition has good release property and roll release.Especially, the fatty acid ester of this amount can provide the thermoplastic resin composition with good release property and roll release under the condition of good laser welding.

＜about the preparation method of resin combination 〉

When preparation thermoplastic resin composition of the present invention, its preparation method is not particularly limited.But, for having deviation, precision, the transmittance that makes specific wavelength do not show well, for its moulding product, it is very important that title complex is scattered among the thermoplastic resin composition in heterogeneity, thus thermoplastic resin composition of the present invention preferably by will constitute thermoplastic resin, the title complex melting mixing is prepared.

As the concrete grammar of above-mentioned melting mixing, can enumerate for example Banbury, mixing roller and forcing machine etc., wherein consider preferred forcing machine, more preferably multiple screw extruder such as twin screw extruder from the angle of melting efficiency.In this twin screw extruder, preferred scheme is as described below.The screw rod shape can be used 1,2 and 3 s' screw screw rod (ネ ジ ス Network リ ユ-), especially, can preferably use transmitting capacity at molten resin, shear 2 all wider screw screw rods of the scope of application among both of mixing ability.The ratio (L/D) of screw rod long (L) and diameter (D) is preferably 20～45 in the biaxial extruder, and more preferably 28～42.When L/D is big, reaches homogeneous easily and disperse, but then, under the excessive situation, because thermal degradation when is easy to generate the decomposition of resin.Screw rod need have above mixing district, 1 place, preferably has 1～3 place, and wherein said mixing district is made of the mixing integrated disc portions that is used to improve mixing behavior (or suitable with it mixing part).

Further, as forcing machine, the preferred forcing machine that uses venting hole (vent) with the volatile gases that can slough moisture in the raw material, the generation of melting mixing resin.The preferred disposition vacuum pump is discharged to the forcing machine outside with moisture or the volatile gases that will produce efficiently by venting hole.In addition, sneak into foreign matter of extruding in the raw material etc., can foreign matter be removed from resin combination at the area configurations sieve before the extruder die head in order to remove.As this sieve, can enumerate wire cloth, net-changing device, sintered metal plates (disc filter) etc.

Further, be not particularly limited dying the method that pigment supplies with to forcing machine, but in most cases cooperate in the present invention to dye amount of pigment few, so preferred following method.(i) will dye pigment and thermoplastic resin with Henschel mixer mixing machine pre-mixings such as (comprising high-speed mixer) after, supply with the method for forcing machine.(ii) will dye pigment and thermoplastic resin melting mixing, make female particle (マ ス -ペ レ Star ト

) method.

One of the method for above-mentioned (i), be with after the whole pre-mixings of the starting material of necessity, supply with the method for forcing machine.The method of (2) is in addition, make to be combined with high density and to dye the host of pigment (マ ス -drug), with this host independently or with residual thermoplastic resin etc. further after the pre-mixing, supply with the method for forcing machine.In addition, this host can be selected powder morphology and with any of the form after this powders compression granulation etc.In addition, other pre-blend approach for example has nauta mixer, V-Mixer, Henschel mixer (comprising high-speed mixer), mechanochemistry device and extrudes mixing machine etc., but the mixing machine of high speed stirring-types such as preferred Henschel mixer.Further, as other pre-blend approach, as with thermoplastic resin with dye the pigment homogeneous and be scattered in the solvent and form after the solution method of removing this solvent.

The aforesaid resin of extruding can directly cut off and make particle, perhaps after forming bar, cut off this with tablets press, makes particle.Thermoplastic resin composition of the present invention is owing to the situation that is applied to light sensor component is more, thus the necessary influence that reduces from the dust of outside, therefore preferred purification forcing machine atmosphere on every side.

The gained coating of particles can be general shapes such as cylindrical, square column type and sphere, but pref. cylindrical.Preferred 1～the 5mm of the diameter of this cylinder, more preferably 1.5～4mm, further preferred 2～3.3mm.On the other hand, the preferred 1～30mm of the length of cylinder, more preferably 2～5mm, further preferred 2.5～3.5mm.

＜about comprising thermoplastic resin composition's of the present invention moulding product 〉

Various products are made in the particle injection moulding that the thermoplastic resin composition who obtains as mentioned above will make usually as mentioned above.In this injection moulding, not only can adopt common forming method, can also be according to appropriate purpose, adopt coated and molded, heat insulating mold moulding in compression molding, injection moulding extrusion forming, gas assistant injection molding, foaming (comprising), insert moulding, the mould, injection molding methods such as heating cooling mould molding, dual-color forming, sandwich moulding and ultra-high speed injection moulding obtain the moulding product rapidly by injecting the situation of supercutical fluid.The advantage of these various methods of forming is widely known.In addition, moulding can be selected any of cold runner mode and hot runner mode.

In addition, thermoplastic resin composition of the present invention also can use with forms such as various special-shaped extrusion molding articles, sheet and films by extrusion moulding.In addition, in the moulding of sheet, film, also can use inflation method or rolling process and casting method etc.Further, also can pass through specific stretched operation, be configured as heat-shrinkable tube.In addition, thermoplastic resin composition of the present invention also can make the moulding product by rotational moulding shaping, blow molding etc.

＜about the moulding product that comprise thermoplastic resin composition of the present invention and the thermoplastic resin molded article of laser welding 〉

Below to comprise thermoplastic resin composition's of the present invention moulding product and comprise the transmittance at wavelength X=808nm place that the test film with thickness 1mm as the thermoplastic resin molded article of laser welding records be the moulding product of the thermoplastic resin composition more than 75% in explanation.These moulding product promptly are not particularly limited as long as the transmittance at wavelength X=808nm place that records for the test film that comprises with thickness 1mm is the moulding product of the thermoplastic resin composition more than 75%.As the resin that constitutes synthetic resin, can enumerate vibrin such as polycarbonate resin, polyethylene terephthalate, PEN, polybutylene terephthalate; Polyarylate resin, polyamide resin, polyimide resin, polyetherimide resin, urethane resin, silicone resin, polyphenylene oxide resin, polyphenylens sulfide resin, polysulfone resin, polyethylene, polyolefin resines such as polypropylene, polystyrene resin, vinyl cyanide/styrol copolymer (AS resin), styrene-maleic anhydride copolymer, acrylonitrile/butadiene/styrene multipolymer (ABS resin), polymethacrylate resin, plexiglass, resol, Resins, epoxy, phenoxy resin, cyclic polyolefin resin etc., as elastomerics, can enumerate for example iso-butylene/synthetic polyisoprene, styrene/butadiene rubbers, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide-based elastomerics and hud typed elastomerics MBS (methyl methacrylate/phenylethylene/butadiene) rubber and MAS (methyl methacrylate/vinyl cyanide/vinylbenzene) rubber etc.Wherein, general preferred use is considered to the high thermoplastic resin of transmittance, can enumerate for example polycarbonate resin, pet resin, the PEN resin, polyarylate resin, styrene resin (comprising the HIPS resin), vinyl cyanide/styrol copolymer (AS resin), phenylethylene/maleic anhydride copolymer, acrylonitrile/butadiene/styrene multipolymer (so-called transparent ABS resin), plexiglass, methyl methacrylate/styrol copolymer (MS resin), cyclic polyolefin resin, polyphenylene oxide resin and phenoxy resin etc.The polycarbonate resin that more preferably obtains easily, vibrin, polyarylate resin, styrene resin, acrylic resin etc. as general engineering plastic.Above-mentioned resin can use a kind or will be more than 2 kinds mix and use separately.

In addition and since laser welding be can 3 the welding process of dimension welding, so the shape of the thermoplastic resin molded article of laser welding is not particularly limited.The moulding product that comprise the laser absorption resin combination among this thermoplastic resin molded article and the present invention are paired, and laser welding partly gets final product for the shape that does not have ground, space to engage mutually.

＜about laser welding 〉

Laser welding among the present invention below is described.Method for laser welding is meant under laser permeation member and laser absorption parts state of contact, irradiating laser, making laser see through described laser permeation member is absorbed by described laser absorption parts, make the method for laser permeation member and laser absorption parts welding thus, wherein, to comprise as the test film with thickness 1mm of laser-transmissible resin combination transmittance that record, at wavelength X=808nm place be thermoplastic resin composition more than 75% to described laser permeation member; It is below 65% that described laser absorption parts comprise the transmittance at wavelength X=808nm place that the test film with thickness 1mm as the laser absorption resin combination records and the transmittance at wavelength X=850nm place is thermoplastic resin composition more than 70%.Laser welding is owing to can 3 dimensions welding, so have following feature: increased the degree of freedom that mold shape, goods design; Different with Vibration Welding, do not produce vibration and abrasion powder; Be not easy to produce the degraded appearance that burr etc. make design surface because of face of weld; Deng.

As the laser that uses in the laser welding, can enumerate the second harmonic of carbon dioxide laser (the about 10600nm of wavelength), Nd:YAG laser (the about 1064nm of wavelength), Nd:YVO4 laser (the about 1064nm of wavelength) and Nd:YAG laser or Nd:YVO4 laser green laser (the about 532nm of wavelength), diode laser (the about 780nm of wavelength～980nm) etc., wherein preferred aspect oscillation frequency the diode laser of excellence.Optical maser wavelength is used 808nm, 840nm, 940nm more, still, because resin combination of the present invention has feature on the transmittance at the transmittance at wavelength 808nm place and wavelength 850nm place, so the preferred wavelength that uses is 808nm in laser welding.

For the moulding product and the multilayer body that comprise thermoplastic resin composition of the present invention, can carry out various surface treatments.Here so-called surface treatment, be meant at evaporation (physical vapor deposition, chemical vapor deposition), plating (electroplate, electroless plating applies, fusion plating etc.), be coated with, film, printing etc. forms the surface treatment of new layer on the synthetic resin top layer, can adopt the method that is generally used for aromatic polycarbonate resin.As surface treatment, enumerate specifically that hard coat film (hardcoat), hydrophobic oleophobic are filmed, ultraviolet radiation absorption is filmed, infrared ray absorption is filmed and the various surface treatments of metallic sprayed coating (evaporation etc.) etc.Wherein, hard coat film (hardcoat) is preferred especially and necessary surface treatment.

As moulding product of the present invention, its purposes for example has various vehicles with the sensor applications of the laser machine of the remote control of laser machines (vehicle-mounted lidar, car speed detection laser, traffic congestion detection laser, overall height detection laser etc.), various electrical equipment (TV, video recorder, radio-tape recorder etc.), security protection pick up camera, temperature sensor, touch panel sensor etc. etc.Further, by the multilayer body that the laser welding by these moulding product and thermoplastic resin obtains, can make the outer cover of above-mentioned various transmitters.

Thermoplastic resin composition of the present invention has feature on the transmittance at wavelength X=808nm and 850nm place, can be widely used in vehicle, electric e-machine, security protection machine and other the various fields.Be provided at the remote control of vehicle-mounted lidar, various electrical equipment, the very useful moulding product in purposes aspect of touch panel sensor, therefore, the effect on the industry that the present invention obtains is great.

The inventor thinks that at present best the solution of the present invention is that the preferable range of having summed up above-mentioned each condition forms, and for example, its typical example record in the following embodiments.Certainly, the present invention is not limited in these schemes.

Embodiment

Below enumerate embodiment and further specify the present invention.If no special instructions, the part among the embodiment is weight part, and % is weight %.Evaluation is implemented according to following method.

(I) thermoplastic resin composition's evaluation

(I-I) transmittance: will long 50mm * wide 50mm * thick 1.0mm, surperficial arithmetic average roughness (Ra) be the following level and smooth tabular test film of 0.03 μ m in temperature is that 23 ℃, relative humidity are to preserve in 50% the environment to carry out in 1 day obtaining the transmittance T of test film at wavelength X=808nm place by spectrophotometer (the system U-3210 of (strain) Hitachi type automatic recording spectrophotometer) after state adjusts ₁(%) and the transmittance T at wavelength X=850nm place ₂(%).Also be determined at simultaneously the transmittance at wavelength X=380nm～670nm place, the high transmission rate T that obtains in its scope ₃(%).

(I-II) melting heat stability: after continuously shaped, shaper temporarily stops, and resin is stranded in the barrel.By Visual Confirmation in the outward appearance of being detained the test film that 10 minutes aftershapings obtain.Melt stability is judged by following benchmark.

Zero: do not have silver color (Silver) in the moulding product.

*: in the moulding product silver color is arranged.

(I-III) laser welding: will comprise thermoplastic resin composition of the present invention, long 50mm * wide 50mm * thick 1.0mm, surperficial arithmetic average roughness (Ra) be that the following level and smooth flat test film of 0.03 μ m is as laser absorption moulding product; To comprise transmittance that the test film with thickness 1mm records and be at wavelength X=850nm place thermoplastic resin composition more than 75%, long 50mm * wide 50mm * thick 1.0mm, surperficial arithmetic average roughness (Ra) be that level and smooth tabular test film below the 0.03 μ m is as laser-transmissible moulding product; Keep crimped status with both coincidences and by mechanical clamping device.In laser-beam welding machine (the laser resin welding machine FD-2000 that (strain) Off ア イ Application デ イ バ イ ス makes), above-mentioned coincidence crimping moulding product are set then, make by laser-transmissible moulding product side irradiating laser, the laser that adjustment is come out from laser oscillator, make focus on coincidence face, with live width 2mm optically focused.Then power 20W, sweep velocity 10mm/ second, welding apart from the condition of 20mm under the laser of illumination wavelength lambda=808nm, implement welding.Laser welding is judged by following standard.

◎: laser absorption moulding product and laser-transmissible moulding product are strong to be engaged.

Zero: laser absorption moulding product and laser-transmissible moulding product engage.

*: laser absorption moulding product and laser-transmissible moulding product do not engage.

(I-IV) laser welding portion outward appearance:, estimate the outward appearance of laser welding portion with laser welding.Judge by following benchmark.

Zero: the junction surface outward appearance of laser absorption moulding product and laser-transmissible moulding product does not have damage.

*: when laser absorption moulding product and laser-transmissible moulding product engaged, because from absorptivity moulding product generation cigarette or air, the fusion of the opposite side of the weld part side of absorptivity moulding product, the expansion of bonding area etc. made the appearance damage at junction surface.

(II) preparation of synthetic resin

(II-I) particulate preparation

In 100 parts of thermoplastic resins, dye pigment, thermo-stabilizer and other additive with the use level cooperation of table 1 record, after mixing with mixing machine,, obtain particle with exhaust cellular type twin screw extruder melting mixing.When material resin as polycarbonate when being Powdered, in advance with use level few dye pigment, stablizer respectively with 10～1000 times concentration of use level, make the premixture with the polycarbonate resin powder, all mix by mixing machine then.The TEX30XSST (interlock fully, equidirectional rotation, 2 screw screw rods) that exhaust cellular type twin screw extruder uses (strain) JSW to make.For the type in mixing district, 1 place is arranged near venting hole.Extruding condition is the vacuum tightness 3kPa of discharge-amount 25kg/h, screw speed 150rpm, venting hole.In addition, extrusion temperature partly is certain from the 1st supplying opening to die head, sets respectively according to employed thermoplastic resin.This design temperature, polycarbonate resin and pet resin are that 270 ℃, polyarylate resin are that 310 ℃, styrene resin and acrylic resin are 210 ℃.

(II-II) making of test film

Use the heated air circulation type drying machine after dry 7 hours the gained particle, under the condition of firing rate 20mm/sec, moulding obtains long 50mm * wide 50mm * thick 1.0mm, surperficial arithmetic average roughness (Ra) is the following level and smooth tabular test film of 0.03 μ m with injection moulding machine.The SG260M-HP that injection moulding machine uses Sumitomo heavy-duty machine tool industry (strain) to make.Drying temperature, barrel temperature, die temperature are set respectively according to every kind of thermoplastic resin.When this resin is polycarbonate resin, press 120 ℃ of drying temperatures, 290 ℃ of barrel temperatures, 80 ℃ of enforcements of die temperature.When this resin is pet resin, press 120 ℃ of drying temperatures, 280 ℃ of barrel temperatures, 20 ℃ of enforcements of die temperature.When this resin is polyarylate resin, press 120 ℃ of drying temperatures, 320 ℃ of barrel temperatures, 80 ℃ of enforcements of die temperature.When this resin is styrene resin, press 70 ℃ of drying temperatures, 210 ℃ of barrel temperatures, 40 ℃ of enforcements of die temperature.When this resin is acrylic resin, press 80 ℃ of drying temperatures, 210 ℃ of barrel temperatures, 60 ℃ of enforcements of die temperature.

(II-III) making of laser-transmissible moulding product

Polycarbonate resin laser-transmissible moulding product adopt and above-mentioned (II-I) same method, after mismatching any additives and making particle, adopt and above-mentioned (II-II) same method injection moulding, make test film.Pet resin, polyarylate resin, styrene resin, acrylic resin are particulate state, therefore adopt and above-mentioned (II-II) same method injection moulding, make test film.

Embodiment 1～25 and comparative example 1～26

Preparation comprises the particle of the thermoplastic resin composition of each composition of record in table 1, the table 2, prepares test film and multilayer body according to above-mentioned working method.Evaluation result is shown in table 1, table 2.

Represented each composition of symbol in table 1～table 2 is as follows.

(A composition)

A-1: the viscosity-average molecular weight that is made by interface polycondensation by the dihydroxyphenyl propane photoreactive gas is that (Supreme Being people changes into (strain) system: パ Application ラ イ ト CM-1000) for 16,000 polycarbonate resin powder

A-2: pet resin (Supreme Being people's (strain) system: TR-8580, limiting viscosity 0.8)

A-3: polyarylate resin (ユ ニ チ カ (strain) system: U Port リ マ-U-100)

A-4: polystyrene resin: (Japan's ス チ レ Application (strain) system: ト-ヨ-ス チ ロ-Le G200C)

A-5: plexiglass: (Mitsubishi's レ イ ヨ Application (strain) system: ア Network リ ペ Star ト MD)

(B composition)

B-1: anthraquinone based colorant (Japanese chemical drug (strain) system: IR-750)

B-2: anthraquinone based colorant (Mitsui Chemicals (strain) system: SIR-114)

B-3: cyanine based colorant (Japanese chemical drug (strain) system: CY-4)

The B-4:perynone based colorant (has this chemical industry (strain) to make: R8370)

B-5: the anthraquinone based colorant (has this chemical industry (strain) to make: G5602)

B-6: the quinoline tinting material (has this chemical industry (strain) to make: Y8010)

B-7: carbon black (Mitsubishi Chemical's (strain) system: the カ of Mitsubishi-ボ Application Block ラ Star Network MA-100B)

(C composition)

C-1: with four (2, the 0-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates are principal constituent, contain the stabilizer blend of three (2, the 4-di-tert-butyl-phenyl) the about 10 weight % of phosphorous acid ester (ア Network リ ア Application ト society system: サ Application De ス Block P-EPQ)

C-2: octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (Ciba SpecialtyChemicals K.K. system: Irganox1076)

(other)

WSN: wollastonite (Na イ コ ミ ネ ラ Le ズ society system: NYGLOS4)

SI: methyl phenyl silicone (eastern レ ダ ウ コ-ニ Application ゲ シ リ コ-Application (strain) system: SH-710)

EW: the full ester that forms by tetramethylolmethane and aliphatic carboxylic acid (reason is ground PVC ミ Application (strain) system: リ ケ ス -EW-400)

As seen from the above table, when thermoplastic resin composition of the present invention was 1mm in products thickness, it had feature on the transmittance at wavelength X=808nm and 850nm place.Further, the moulding product that comprise it, comprise that promptly the transmittance at wavelength X=808nm place was the laser welding excellence of the moulding product of the thermoplastic resin more than 75% when thickness was 1mm, be suitable as the sensor element of the remote control of the mechanical, electrical device of laser of various vehicles, security protection pick up camera, temperature sensor, touch panel sensor etc.

Claims (15)

1. the thermoplastic resin composition is characterized in that, be that the transmittance at wavelength=808nm place of the test film mensuration of 1mm is below 65% with thickness, and the transmittance at wavelength X=850nm place is more than 70%.

2. the described thermoplastic resin composition of claim 1 is characterized in that, be that the transmittance at wavelength=808nm place of the test film mensuration of 1mm is below 36% with thickness, and the transmittance at wavelength=850nm place is more than 84%.

3. claim 1 or 2 described thermoplastic resin compositions wherein, are that the transmittance at each wavelength place of wavelength X=380nm～670nm that the test film of 1mm is measured is below 1% with thickness.

4. each described thermoplastic resin composition in the claim 1～3, it contains thermoplastic resin (A composition) and dyes pigment (B composition).

5. the described thermoplastic resin composition of claim 4, wherein, with thickness is the transmittance that the Xiao Chi of 1mm measures the 200mg/1L chloroformic solution dye pigment (B composition), and the transmittance at wavelength=808nm place is below 65% and the transmittance at wavelength X=850nm place is more than 70%.

6. claim 4 or 5 described thermoplastic resin compositions, wherein dying pigment (B composition) is the mixture that dyes pigment more than 2 kinds.

7. the described thermoplastic resin composition of claim 6, wherein, with with thickness be that the light absorption ratio of the 200mg/1L chloroformic solution that respectively dyes pigment at wavelength X=808nm place that the Xiao Chi of 1mm measures is Ai808 (%), light absorption ratio at wavelength X=850nm place is Ai850 (%), respectively dye pigment with respect to the ratio of dying the pigment composition total amount be Ri (weight %) (wherein, i is for dying the pigment numbering) time, dye pigment composition and satisfy following formula:

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}\mathrm{Ai}808\&times;\mathrm{Ri}>35$

$\underset{i=1}{\overset{n}{\mathrm{\&Sigma;}}}\mathrm{Ai}850\&times;\mathrm{Ri}<30.$

8. each described thermoplastic resin composition in the claim 1～7, wherein, thermoplastic resin (A composition) is for being selected from least a kind of thermoplastic resin in polycarbonate resin, vibrin, polyarylate resin, styrene resin and the acrylic resin.

9. the described thermoplastic resin composition of claim 8, wherein, polycarbonate resin is the bisphenol A polycarbonate resin.

10. the described thermoplastic resin composition of claim 8, wherein, vibrin is for being selected from least a kind of vibrin in polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester and the PEN (PEN).

11. each described thermoplastic resin composition in the claim 1～10, it contains thermo-stabilizer (C composition).

12. the moulding product, it comprises each described thermoplastic resin composition in the claim 1～11.

13. the described moulding product of claim 12, wherein, the moulding product are sheet component.

14. multilayer body, it is to be that the transmittance at wavelength X=808nm place that the test film of 1mm is measured is that the moulding product of the thermoplastic resin composition more than 75% obtain by laser welding with claim 12 or 13 described moulding product, with comprising with thickness.

15. the described multilayer body of claim 14, wherein, the described transmittance at wavelength X=808nm place that with thickness is the test film of 1mm is measured is that the thermoplastic resin among the thermoplastic resin composition more than 75% is at least a kind of thermoplastic resin that is selected from polycarbonate resin, vibrin, polyarylate resin, styrene resin and the acrylic resin.