CN101384669A - Thermoplastic resin composition and liquid crystal display part or information recording medium part using the composition - Google Patents
Thermoplastic resin composition and liquid crystal display part or information recording medium part using the composition Download PDFInfo
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Abstract
A thermoplastic resin composition suitable for use in thin moldings that exhibits high fluidity, having high dimensional stability, for example, being free from deformation after forming operation, and that excels in rigidity, impact resistance, heat resistance, etc. In particular, there is provided a thermoplastic resin composition comprising 100 parts by weight of resin composition composed of 91 to 99 wt.% of thermoplastic resin with specified melt viscosity (A) and 1 to 9 wt.% of liquid crystal polymer (B) and 0.001 to 2 parts by weight of specified phosphorus oxo acid monoester or diester (C), wherein the liquid crystal polymer (B) is in the state of particle dispersion and wherein the melt viscosity ratio between component (A) and component (B) falls within a specified range. Further, there is provided a liquid crystal display part or information recording medium part.
Description
Technical field
The present invention relates to a kind of by the thermoplastic resin that does not form anisotropy fusion phase with can form the formed thermoplastic resin composition of anisotropy fusion liquid-crystalline polymer mutually.Further, it relates to used information recording medium part in liquid crystal display component used in the display device of these electron-like goods of computer, TV and watch-dog or mobile phone and these electron-like goods of computer.
Background technology
In recent years, the multifunction high performance highly significant of digital devices such as mobile phone, digital camera, portable terminal device.As common structure in these machines, can list and have liquid-crystal display and information recording carrier.
In general, liquid-crystal display (LCD:Liquid Crystal Display) is by glass substrate (glass substrate), transparency electrode (transparentelectrode), liquid crystal (liquid crystal) and the formed LCD faceplate part of colour filter (color filter) and by the reflector (reflector) that is used to provide back light (backlight ling), luminescent lamp (fluorescent lamp), light guiding plate (lightguide panel), diffuser plate (diffusion sheet), this two parts of the formed back light unit of framework backlight (backlight frame) that support integral limit performance reflector function is propped up on prism (prism sheet) and limit constitutes.Aforesaid framework backlight on its function, has the shape that opening portion is set on rectangular-shaped.The ratio of this opening portion is big more, just might obtain the liquid crystal face area big more with respect to the size of liquid-crystal display itself.And rectangular-shaped thickness is thin more, and the slimming of liquid-crystal display itself is just possible more.Therefore, general trend is that the opening portion ratio is bigger, and, rectangular-shaped thickness attenuation.
In addition, as information recording carrier, headed by SD card, CF card (compact flash), the article of SM card (smart media), MS card various patterns such as (memory stick) circulate.These information recording carriers are small-sized, and have the high recording capacity of exceedance MB on memory capacity.
These information recording carriers even now, also can realize small-sized size, but from now on, because the multifunction high performance and the miniaturization of the device of service recorder medium, therefore the reduction of recording medium equipment spatial is necessary, and needs further miniaturization thin-walled property.
Thus, for employed material in liquid crystal display component or the information recording carrier, for thickness but can also effectively realize function, require to have high workability, rigidity and shock-resistance.Thermotolerance, dimensional stability and the flame retardant resistance that also should have in addition, ability heating backlight.As the material with this specific character, up to now, polycarbonate resin is its representative.
In order to realize this purpose, be thickness but the effectively function of implementation framework or recording medium function, use or the information recording carrier material for liquid crystal display component, the back nothing that requires to be shaped is out of shape contour dimensional stability, high workability and rigidity, shock-resistance.Thermotolerance, dimensional stability and the flame retardant resistance that also should have in addition, ability heating backlight.As the material with this specific character, up to now, polycarbonate resin is its representative.
With other resins relatively, polycarbonate resin has good low temperature shock-resistance, self-extinguishing, electrical specification, the transparency, dimensional stability and thermostability, as engineering plastics, is widely used for office automated machine, electric and electronic products etc. always.But because mobile low, polycarbonate resin can not adapt to the framework that carries out thin-walled property or the situation of information recording carrier increases to some extent.In order to remedy this low flow, at high temperature process when being adapted at injection forming or under high speed and high pressure, process, but cause thermolysis or over-drastic residual stress, so it utilizes scope to be restricted owing to heating resin respectively.
On the other hand, as improve mobile method from the material aspect, also in the alloying of studying polycarbonate resin and ABS resin etc.For example, in JP-A 11-293102, disclose with specific ratios and cooperated polycarbonate resin and ABS graft copolymer and have two kinds of vinyl cyanide/styrol copolymers that specified molecular weight distributes, thereby can obtain the good polycarbonate of shaping processability/ABS alloy composite, but its thermotolerance deficiency.
In addition, shown in JP-A 2002-249656, resin combination to polycarbonate resin fluid,matching crystallinity resin has demonstrated good thin molded property, but do not check the words of proportioning, can cause the peeling off etc. of damage, molding top layer of reducing the weld cause by welding strength, therefore can't satisfy function as goods.
Summary of the invention
The invention provides a kind of problem that solves these conventional arts, and mobile high, have high-dimensional stabilities such as the back of shaping is indeformable, rigidity, shock-resistance, thermotolerance etc. are good, and thickness but can also effectively realize thermoplastic resin composition as the function of liquid crystal display component or information recording medium part.Further, provide a kind of rectangular-shaped ratio of opening portion big, and thickness but the effective liquid crystal display component material of implementation framework function.In addition, also provide a kind of thickness but can also effectively realize the information recording carrier material of recording medium function.
The inventor in order to achieve the above object, the flow material of high rigidity and high heat resistance of height is tried to explore repeatedly and studied, found that by cooperating the specified quantitative liquid-crystalline polymer showing particular melt viscosity and do not form in the thermoplastic resin of anisotropy fusion phase, cooperate specific phosphorus oxygen acid monoesters or diester in addition, and the melt viscosity ratio of thermoplastic resin and liquid-crystalline polymer is controlled in the specified range, thereby can adapt to the requirement of thin-walled property, finish the present invention thus.
In addition, also find to pass through with the material of above-mentioned composite resin composition as liquid crystal display component or information recording medium part, the problem such as peel off that does not then have damage, the molding top layer of the described weld of JP-A 2002-249656, and can adapt to the requirement of thin-walled property, finish the present invention thus.
The present invention is a kind of thermoplastic resin composition, it is characterized in that, this thermoplastic resin composition by with respect to 100 weight parts by (A) of 91～99 weight % use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under the melt viscosity measured by the capillary type mobilometer be that (B) of 100～300Pas and thermoplastic resin that does not form anisotropy fusion phase and 1～9 weight % can form the formed resin combination of anisotropy fusion liquid-crystalline polymer mutually, cooperate 0.001～2 weight part (C) to be selected from represented phosphorus oxygen acid monoesters of following general formula (I), (II) and in the diester one or more, wherein (B) liquid-crystalline polymer is a particles dispersed
(A) composition and (B) composition, use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under melt viscosity ratio (A η)/(the B η) that measured by the capillary type mobilometer be 3.2～4.0.
(X)
nP(＝O)(OR)
3-n (I)
(X)
nP(OR)
3-n (II)
[in the formula, n is 1 or 2, and X is hydrogen atom, hydroxyl or any monovalent organic radical group, can be identical or different when being a plurality of at it.R is monovalence or divalent organic group, can be identical or different when being a plurality of at it.]
The invention provides a kind of liquid crystal display component, it is characterized in that, by with above-mentioned thermoplastic resin composition, that is, and use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under ratio (A η)/(the B η) of the melt viscosity measured by the capillary type mobilometer be that thermoplastic resin composition's injection forming of 3.2～4.0 obtains, and on rectangular-shaped, be provided with desirable opening portion, the ratio of opening portion is 30～95% of rectangular-shaped the total area, and rectangular-shaped thickness is 0.3～3mm.
The invention provides a kind of information recording medium part, it is characterized in that, by with above-mentioned thermoplastic resin composition, that is, and use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under ratio (A η)/(the B η) of the melt viscosity measured by the capillary type mobilometer be that thermoplastic resin composition's injection forming of 3.2～4.0 obtains, and rectangular-shaped minor face/length limit ratio is 0.3～1.0, and rectangular-shaped thickness is 0.3～3mm.
Embodiment
Below, the present invention is elaborated.The used thermoplastic resin that does not form anisotropy fusion phase (A) among the present invention must be can be at the thermoplastic resin of 300 ℃ of following melt-processed.What is called can be 300 ℃ of following melt-processed, particularly, be meant use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under the melt viscosity measured by the capillary type mobilometer satisfy the scope of 100～300Pas, and when not causing its character modification to unallowed degree, also can process because of deterioration.
As this thermoplastic resin (A), can enumerate, for example polyester based resins such as polyolefins such as polyethylene, polypropylene, poly(4-methyl-1-pentene) (being total to) polymkeric substance, pet resin, polybutylene terephthalate resin, polycarbonate resin, polyamide-based resin, ABS resin, polyarylene sulfide resin, polyacrylic ester and based on resin of these resins etc.Polyester based resins such as wherein preferred pet resin, polybutylene terephthalate resin, polycarbonate resin, and preferred especially shaping shrinkage rate and the lower polycarbonate resin of linear expansivity.
Among the present invention, be preferably used as the polycarbonate resin of thermoplastic resin (A), can enumerate and have the carbonic ether structure, and aromatic series homopolymerization or Copolycarbonate by aromatic dicarboxylic phenol system compound and reactions such as carbonyl chloride or carbonic diester are obtained.Herein, as the aromatic dicarboxylic phenol system compound, can use 2,2-two (4-hydroxy phenyl) propane, 2,2-two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane, two (4-hydroxy phenyl) butane, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) butane, 2,2-two (4-hydroxyl-3, the 5-phenylbenzene) butane, 2,2-two (4-hydroxyl-3,5-diethyl phenyl) propane, 1,1-two (4-hydroxy phenyl) hexanaphthene, 1-phenyl-1,1-two (4-hydroxy phenyl) ethane etc., and they can use separately, also can be used as mixture and use.In the above-mentioned substance, preferred 2,2-two (4-hydroxy phenyl) propane.
The liquid-crystalline polymer that uses among the present invention (B) is meant the melt processable polymkeric substance with the character that can form optical anisotropy fusion phase, and has by be subjected to the character that shear-stress is arranged in parallel the polymer molecular chain formation rule under molten state.This polymer molecule generally is elongated, flats, and very high along the molecular long axis rigidity, normally has a base polymer of a plurality of chain lengthening keys that have any coaxial or parallel relation.The character of anisotropy fusion phase can be confirmed by the polarisation test procedure commonly used of utilizing crossed polarizers.More specifically, can be by using the Leitz polarizing microscope, carrying out the affirmation of anisotropy fusion phase observing the method that is carried in the fusion sample on the hot platform of Leitz with 40 times multiplying power under the nitrogen atmosphere.When checking applicable to liquid-crystalline polymer of the present invention between crossed nicols, even be in the fusion stationary state, polarized light is also transmissive usually, and demonstrates optical anisotropy.
As aforementioned such liquid-crystalline polymer (B), be not particularly limited, but be preferably aromatic polyester or aromatic polyester acid amides, part comprises the polyester of aromatic polyester or aromatic polyester acid amides also in this scope in same molecular chain.And in the time of can using under 60 ℃ concentration with 0.1 weight % to be dissolved in it in Pentafluorophenol, preferably have at least about 2.0dl/g, more preferably the material of the logarithm viscosity (I.V.) of 2.0～10.0dl/g.
As aromatic polyester or aromatic polyester acid amides, especially preferably have at least a above compound that is selected from aromatic hydroxy-carboxylic, aromatic hydroxyl amine, the aromatic diamine aromatic polyester, aromatic polyester acid amides as constituent applicable to liquid-crystalline polymer of the present invention (B).
More specifically, can enumerate:
(1) mainly by one or more aromatic hydroxy-carboxylics and the formed polyester of derivative thereof;
(2) mainly by (a) one or more aromatic hydroxy-carboxylics and derivative thereof, (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acid and derivative thereof and (c) at least a or two above aromatic diols, alicyclic dibasic alcohol, aliphatic dihydroxy alcohol and the formed polyester of derivative thereof;
(3) mainly by (a) one or more aromatic hydroxy-carboxylics and derivative thereof, (b) one or more aromatic hydroxyl amine, aromatic diamine and derivative thereof and (c) the formed polyesteramide of one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acid and derivative thereof;
(4) mainly by (a) one or more aromatic hydroxy-carboxylics and derivative thereof, (b) one or more aromatic hydroxyl amine, aromatic diamine and derivative thereof, (c) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acid and derivative thereof and (d) at least a or two above aromatic diols, alicyclic dibasic alcohol, aliphatic dihydroxy alcohol and the formed polyesteramide of derivative thereof etc.In addition, can also in above-mentioned constituent and with molecular weight, adjust agent as required.
As the preferred example that constitutes applicable to the particular compound of foregoing liquid crystal polymkeric substance of the present invention (B), can enumerate P-hydroxybenzoic acid, 6-hydroxyl-aromatic hydroxy-carboxylics, 2 such as 2-naphthoic acid, 6-dihydroxy naphthlene, 1,4-dihydroxy naphthlene, 4,4 '-dihydroxybiphenyl, Resorcinol, Resorcinol, by following logical formula V and the represented aromatic diols such as compound of general formula (VI); Terephthalic acid, m-phthalic acid, 4,4 '-diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acids and by the represented aromatic dicarboxylic acids such as compound of following general formula (VII); Aromatic amine such as p-aminophenol, Ursol D.
(wherein, X: be selected from alkylene (C
1～C
4), alkylidene group ,-O-,-SO-,-SO
2-,-S-,-group among the CO-, Y: be selected from-(CH
2)
n-(n=1～4) ,-O (CH
2)
nThe group of O-(n=1～4))
As being applicable to particularly preferred liquid-crystalline polymer of the present invention (B), be to be the aromatic polyester of main composition unit composition with P-hydroxybenzoic acid and 6-hydroxyl-2-naphthoic acid.
Be dispersed in the molding of thermoplastic resin (A) matrix in mutually for liquid-crystalline polymer (B) with fibrous or needle-like differential, by using conventional extrusion device that both are mixing, with liquid-crystalline polymer (B) particles dispersed at the thermoplastic resin composition extrusion molding of thermoplastic resin (A) matrix in mutually, then the shearing force by at this moment obtains above-mentioned molding, but when the ratio thermoplastic resin (A) of liquid-crystalline polymer (B) for a long time, the matrix phase reversion, even it is and mutually nonreversible at matrix, if the amount of liquid-crystalline polymer (B) is many, then because the increase of the amount of the existing liquid-crystalline polymer in molding weld, thereby cause the decline of welding strength, therefore not preferred.In addition, above-mentioned liquid-crystalline polymer (B) is dispersed in the thermoplastic resin (A) with fibrous, and this enhancing purpose for thermoplastic resin (A) is very important, but liquid-crystalline polymer (B) is when having formed filamentary structure near the molding top layer, cause the top layer to be peeled off, therefore not preferred.
In order to address this problem, liquid-crystalline polymer (B) is necessary for, and has granular dispersion state near the molding top layer, and demonstrates fibrous dispersion state in molding inside.Thus, in order to satisfy whole requirements that peel off on the mobile rigidity welding strength of thin-walled top layer, must extremely strictly control the melt viscosity of thermoplastic resin (A) and the addition of liquid-crystalline polymer (B).Therefore, in the present invention, the melt viscosity of thermoplastic resin (A), use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under the capillary type mobilometer measure, be necessary for 100～300Pas, and be preferably 160～180Pas, and the use level of liquid-crystalline polymer (B) must be that the thermoplastic resin (A) with respect to 91～99 weight % is 1～9 weight %.When the melt viscosity of thermoplastic resin (A) during less than 100Pas, welding strength is poor, and when it surpasses 300Pas, has the situation that peel off on the top layer that produces.In addition,, can't obtain thin-walled flowability, and when it surpasses 9 weight %, have problems aspect peeling off on welding strength, top layer as purpose when the use level of liquid-crystalline polymer (B) during less than 1 weight %.
In liquid crystal display component of the present invention or information recording medium part, also use composition same as described above.
When thermoplastic resin (A) was polycarbonate resin, its preferred viscosity-average molecular weight was 17500～18900.
In addition, (A) composition and (B) the melt viscosity ratio of composition is also very important, its use respectively internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under melt viscosity ratio (A η)/(the B η) of melt viscosity (A η) and (B) melt viscosity of composition (B η) of (A) composition of being measured by the capillary type mobilometer in 3.2～4.0 scope the time, can take into account thin-walled mobile and welding strength, top layer and peel off.
In addition, in the present invention,, must add phosphorus compound in order when being shaped, to make liquid-crystalline polymer (B) fibrosis as mentioned above.Particularly, when being polycarbonate resin, liquid-crystalline polymer and polycarbonate resin are not island and disperse at the thermoplastic resin that does not form anisotropy fusion phase (A), even injection forming also has not Fibrotic situation, this effect is remarkable.As this phosphorus compound, be phosphorus oxygen acid monoesters and diester (C), and be by following general formula (I), (II) represented this material.
(X)
nP(＝O)(OR)
3-n (I)
(X)
nP(OR)
3-n (II)
[in the formula, n is 1 or 2, and X is hydrogen atom, hydroxyl or any monovalent organic radical group, can be identical or different when being a plurality of at it.R is monovalence or divalent organic group, can be identical or different when being a plurality of at it.]
Generally speaking, phosphonic acid ester (phosphonate) compound, phosphinate (phosphinate) compound, phosphinate (phosphonite) compound, phosphinous acid ester (phosphinite) compound and be fit at the organo phosphorous compounds that intramolecularly contains these textural elements.
Object lesson as phosphonate compound; can enumerate, for example the dimethyl phosphine acid esters; diethyl phosphonate; the dibutyl phosphonic acid ester; two (ethylhexyl) phosphonic acid ester; the didecyl phosphonic acid ester; two palmityl phosphonic acid esters; the distearyl phosphonic acid ester; the dilauryl phosphonic acid ester; the diphenylphosphine acid esters; the dibenzyl phosphonic acid ester; dimethylbenzene acyl group phosphonic acid ester; two (nonyl phenyl) phosphonic acid ester; two oleyl phosphonic esters; the dimethyl methyl phosphonate acid esters; the diethylmethyl phosphonic acid ester; two (ethylhexyl) methylphosphonate; two palmityl methylphosphonates; the distearyl methylphosphonate; the dilauryl methylphosphonate; the diphenyl methyl phosphonic acid ester; the 3,5-dimethylphenyl phosphonic acid ester; diethyl phenyl phosphonic acid ester; two (ethylhexyl) Phenylphosphine acid esters; two palmityl Phenylphosphine acid esters; distearyl Phenylphosphine acid esters; dilauryl Phenylphosphine acid esters; phenylbenzene phenyl phosphonic acid ester; dibenzyl Phenylphosphine acid esters etc.
Object lesson as phosphinate compounds; can enumerate, for example the methyl phosphinate; the ethyl phosphinate; the butyl phosphinate; the ethylhexyl phosphinate; the palmityl phosphinate; the stearyl phosphinate; the lauryl phosphinate; the phenyl phosphinic acid ester; the benzyl phosphinate; the toluyl phosphinate; nonyl phenyl phosphinate; the oil base phosphinate; the ethyl-methyl phosphinate; ethyl dimethyl phosphinate; (ethylhexyl) methyl phosphinate; (ethylhexyl) dimethyl phosphinate; palmityl methyl phosphinate; palmityl dimethyl phosphinate; stearyl methyl phosphinate; stearyl dimethyl phosphinate; the lauryl methyl phosphinate; the lauryl dimethyl phosphinate; the phenyl methyl phosphinate; the ethylphenyl phosphinate; (ethylhexyl) phenyl phosphinic acid ester; palmityl phenyl phosphinic acid ester; stearyl phenyl phosphinic acid ester; stearyl diphenyl phosphonic acid ester; lauryl phenyl phosphinic acid ester; lauryl diphenyl phosphonic acid ester; the phenyl phosphinate; benzyl phenyl phosphinate etc.
Object lesson as phosphinate compound, can enumerate, for example the dimethyl phosphinate, the diethyl phosphinate, the dibutyl phosphinate, two (ethylhexyl) phosphinate, the didecyl phosphinate, two palmityl phosphinates, the distearyl phosphinate, the dilauryl phosphinate, the phenylbenzene phosphinate, the dibenzyl phosphinate, the xylyl phosphinate, two (nonyl phenyl) phosphinate, two oil base phosphinates, dimethyl methyl phosphinate, the diethylmethyl phosphinate, two (ethylhexyl) methyl phosphinate, two palmityl methyl phosphinates, distearyl methyl phosphinate, dilauryl methyl phosphinate, the diphenyl methyl phosphinate, the 3,5-dimethylphenyl phosphinate, diethyl phenyl phosphinate, two (ethylhexyl) phenyl-phosphonite ester, two palmityl phenyl-phosphonite esters, distearyl phenyl-phosphonite ester, dilauryl phenyl-phosphonite ester, phenylbenzene phenyl phosphinate, dibenzyl phenyl-phosphonite ester etc.
Object lesson as the phosphinous acid ester cpds; can enumerate, for example methyl phosphinous acid ester; ethyl phosphinous acid ester; butyl phosphinous acid ester; ethylhexyl phosphinous acid ester; palmityl phosphinous acid ester; stearyl phosphinous acid ester; lauryl phosphinous acid ester; phenyl phosphinous acid ester; benzyl phosphinous acid ester; toluyl phosphinous acid ester; nonyl phenyl phosphinous acid ester; oil base phosphinous acid ester; ethyl-methyl phosphinous acid ester; ethyl dimethyl phosphinous acid ester; (ethylhexyl) methyl phosphinous acid ester; (ethylhexyl) dimethyl phosphinous acid ester; palmityl methyl phosphinous acid ester; palmityl dimethyl phosphinous acid ester; stearyl methyl phosphinous acid ester; stearyl dimethyl phosphinous acid ester; lauryl methyl phosphinous acid ester; lauryl dimethyl phosphinous acid ester; phenyl methyl phosphinous acid ester; ethylphenyl phosphinous acid ester; (ethylhexyl) phenyl phosphinous acid ester; palmityl phenyl phosphinous acid ester; stearyl phenyl phosphinous acid ester; stearyl phenylbenzene phosphinous acid ester; lauryl phenyl phosphinous acid ester; lauryl phenylbenzene phosphinous acid ester; phenyl phosphinous acid ester; benzyl phenyl phosphinous acid ester etc.Wherein, especially preferably use by the represented phosphonic acid ester of general formula (III).
H(OH)
mP(＝O)(OR’)
2-m (III)
[in the formula, m is 0 or 1, and R ' is an any monovalent organic radical group.]
In addition, as the phosphorus compound of (C), can also use the organo phosphorous compounds that comprises above-mentioned phosphonic acid ester, phosphinate, phosphinate, phosphinous acid ester structure key element at intramolecularly.As its object lesson, can enumerate following compound.
The use level of this specific phosphorus compound (C), with respect to 100 weight parts by (A) thermoplastic resin of 91～99 weight % and the formed resin combination of (B) liquid-crystalline polymer of 1～9 weight %, be 0.001～2 weight part, and be preferably 0.01～0.5 weight part especially.If use level less than 0.001 weight part makes the Fibrotic effect of liquid-crystalline polymer little in then being shaped, and if it surpasses 2 weight parts, material property is reduced.
In addition, for the thermoplastic resin composition, by adding additives such as pigment, oxidation inhibitor, stablizer, softening agent, lubricant, releasing agent and fire retardant such as nucleator, carbon black, and the composition of having given desirable characteristic is also included among the thermoplastic resin composition of the present invention.
When making this thermoplastic resin composition, as long as cooperate various compositions and carry out mixing in the aforementioned component ratio.Be generally, mixing with forcing machine, extrude to granular, and be used for injection forming etc., but be not limited to extruding of this use forcing machine.Information recording medium part of the present invention, by above-mentioned composite resin composition by conventional manufacturing process injection molding method and easily being shaped for example.
Liquid crystal display component of the present invention or information recording medium part, by above-mentioned thermoplastic resin composition by conventional manufacturing process injection molding method and easily being shaped for example.
Like this molding that obtains, being (B) liquid-crystalline polymer is dispersed in molding in (A) thermoplastic resin with island, particularly, is below the 30 μ m from molding surface 50 μ m with the average major diameter of (B) liquid-crystalline polymer particulate of interior top layer part, even and thin-walled, also has the flowability that fully to fill mould, has high elastic coefficient in addition, therefore, even molding as thin as a wafer, can not cause that the lip-deep resin cortex of molding peels off yet, can be shaped without a doubt, and can not cause torsional deformation etc.In addition, owing to kept this good plasticity, and compare with goods in the past and can reduce cast gate (gate) and count, so can reduce the weight of cross gate (runner), can be described as very economical.
Owing to have high shape (size) stability, therefore even have thickness and be 3mm ratio following and opening portion and be 30～95% such liquid crystal display components of rectangular-shaped the total area, can not cause that also the lip-deep resin cortex of molding peels off and be shaped, and demonstrated good welding strength, can not cause torsional deformation etc.In addition, owing to kept this good plasticity, and compare with goods in the past and can reduce cast gate and count, so can reduce the weight of cross gate, can be described as very economical.
Owing to have high shape (size) stability, even so molding as thin as a wafer, particularly rectangular-shaped minor face/length limit ratio is 0.3～1.0, rectangular-shaped thickness is the such information recording medium part of 0.3～3mm, can not cause that also the lip-deep resin cortex of molding peels off and be shaped, and demonstrated good welding strength, and can not cause torsional deformation etc.In addition, owing to kept this good plasticity, and compare with goods in the past and can reduce cast gate and count, so can reduce the weight of cross gate, can be described as very economical.
Therefore, be suitable as most in recent years the more and more material of the liquid crystal display component of thin-walled property or information recording medium part, and with headed by the watch-dog, is useful to for example portable information terminals such as digital camera, camera integrated VTR, mobile telephone, PDA, notebook computer etc. with TV.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these.
Embodiment 1～5
At first, (Supreme Being people changes into (strain) manufacturing, PANLITEL1225L with 2 kinds of polycarbonate resins; 300 ℃, 1000sec
-1Shearing rate under melt viscosity be 225Pas, viscosity-average molecular weight is 19700 and PANLITE CM1000; 300 ℃, 1000sec
-1Shearing rate under melt viscosity be 90Pas, viscosity-average molecular weight is 16000) the particle blend, preparation has the polycarbonate resin of the melt viscosity of table 1 record.In this polycarbonate resin, add liquid-crystalline polymer (Polyplastics Co., Ltd.'s manufacturing of the amount shown in the table 1, A950) and distearyl phosphorous acid hydrogen ester (north of the city chemical industry (strain) is made, JP218SS), and biaxial extruder melting mixing under 300 ℃ resin temperature of use 30mm, granulation obtains the resin combination of target.
In extruding operation, add to note in extruding not entrained air in mixing thing and form oxidizing condition, and by decompression operation volatile component be removed from venting port on one side, Yi Bian prepare the resin combination of target.
Then, use the resin combination of gained, the as follows evaluation.
(melt viscosity)
Use and have internal diameter as 1mm, length capillary type mobilometer, at 300 ℃, 1000sec as the 20mm nozzle
-1Shearing rate under measure.
(stripping test)
The use resin temperature is 300 ℃ a injection machine, is that thickness is the test film of 0.8mm by above-mentioned shaping particles.Then, adhesive tape joining on the test film surface, is torn again, carry out stripping test.After the stripping test, (NIRECO CORPORATION makes, and LUZEX-FS), measures the area of released part, calculates (area of the area/test film of released part) to use picture processing to measure machine.This value is more little, and then the area of released part is more little, can think that peel property is good more.
(welding strength)
The use resin temperature is 300 ℃ a injection machine, is that thickness is the bonding pad of 0.8mm by above-mentioned shaping particles, and according to ISO178, carries out crooked welding strength and measure.
(excellent length of flow)
At resin temperature is that 300 ℃, injection pressure are that to be configured as width under the 200MPa be that 5mm, thickness are the excellent flow model of 0.3mm, measures length of flow.
(bending elastic modulus)
The use resin temperature is 300 ℃ a injection machine, is that thickness is the test film of 0.8mm by above-mentioned shaping particles, and measures bending elastic modulus according to ISO178 D 790.
(particle diameter of liquid-crystalline polymer)
By thickness is the test film that has welding of 0.8mm, cuts out the thin slice that thickness is 0.5 μ m on flow direction, uses polarizing microscope observation liquid-crystalline polymer particle.(NIRECO CORPORATION makes, and LUZEX-FS), measures average major diameter to use picture processing to measure machine to particle diameter.
Comparative example 1～5
As shown in table 1, (comparative example 2,3,5 (in addition to invent situation about stipulating for the addition of liquid-crystalline polymer above the discontented unabridged version of the melt viscosity ratio of situation (comparative example 1), polycarbonate resin and the liquid-crystalline polymer of the present invention's regulation, employed polycarbonate resin is the Lexan 141 that General Electric company used among the TOHKEMY 2002-249656 communique embodiment makes in the comparative example 5)), the situation (comparative example 4) of not adding liquid-crystalline polymer, the preparation resin combination is estimated.
Embodiment 6～10
Use the resin combination of embodiment 1～5, the as follows evaluation.
(melt viscosity)
Similarly measure with embodiment 1.
(shaping peak pressure)
(Sumitomo heavy-duty machine tool is made using injection machine, SE30D), at resin temperature is 300 ℃, die temperature is 80 ℃, injection speed is to be configured as under the 200mm/sec when rectangular-shaped the middle body of long 65mm, wide 45mm, thick 0.3mm has the molding (1 aciculiform cast gate) of the rectangular-shaped opening portion of being similarly of long 61mm, wide 41mm, measures the shaping peak pressure of this moment.This shaping peak pressure is low more, can think that then plasticity is good more.
(welding stretching split test)
Use above-mentioned molding, weld the stretching split test with rectangular aperture part.Use a fixedly minor face of molding of anchor clamps, and with the minor face of hook stretching opposite side, the weld of estimating then when stretching with 5mm/min speed has or not damage (breaking).As estimating machine, use ORIENTEC Co., the omnipotent puller system UTA-KN that LTD makes.
(stripping test)
Above-mentioned molding with rectangular aperture part is put into 200ml distilled water, use the ultrasonic washer W-115 of this polyelectrons manufacturing, under the condition of 45kHz, 300W, carry out 1 minute ultrasonic washing.After the washing, observation has or not because of peeling off the fluffing that forms in the top layer of molding.
(bending elastic modulus)
Measure similarly to Example 1.
Comparative example 6～11
According to the ratio shown in the table 2, the resin combination of the gained of the resin combination of manufacturing objective, and use is similarly to Example 1 made molding similarly to Example 6, and is estimated.
These the results are shown in table 2.
Embodiment 11～20
Use the resin combination of embodiment 1～5, make 2 kinds of molding shown below, and form peak pressure, welding stretching split test, stripping test.
Molding A (embodiment 11～15, table 3)
(FANUC makes using injection machine, ROBOSHOTS-2000i30A), be 300 ℃ at resin temperature, die temperature is 80 ℃, when injection speed is the rectangle molding (side gate) of 1 long 40mm of shaping, wide 25mm, thick 0.18mm under the 400mm/sec, measure the shaping peak pressure of this moment.This shaping peak pressure is low more, can think that then plasticity is good more.
Molding B (embodiment 16～20, table 4)
(Sumitomo heavy-duty machine tool is made using injection machine, SE130D-HP-C360M), be 300 ℃ at resin temperature, die temperature is 80 ℃, when injection speed is the rectangle molding (side gate) of 8 long 21mm of shaping, wide 18mm, thick 0.15mm under the 600mm/sec, measure the shaping peak pressure of this moment.
(melt viscosity)
Measure similarly to Example 1.
(welding stretching split test)
Use above-mentioned molding, weld the stretching split test with rectangular aperture part.Use a fixedly minor face of molding of anchor clamps, and with the minor face of hook stretching opposite side, estimate then when stretching with 5mm/min speed, the weld has or not damage (breaking).As estimating machine, use ORIENTEC Co., the omnipotent puller system UTA-KN that LTD makes.
(stripping test)
Adhesive tape joining on the surface of above-mentioned rectangle molding, is torn then, carry out stripping test.After the stripping test, (NIRECOCORPORATION makes, and LUZEX-FS), measures the area of released part, calculates (area of the area/test film of released part) to use picture processing to measure machine.This value is more little, and then the area of released part is more little, can think that peel property is good more.
(bending elastic modulus)
Measure similarly to Example 1.
Comparative example 12～17
According to the ratio shown in the table 3, manufacturing purpose resin combination similarly to Example 1 then uses the resin combination of gained, makes molding A similarly to Example 11, and estimates.
Comparative example 18～23
Use prepared resin combination in the comparative example 12～17, make molding B similarly to Example 16, and it is estimated.
These the results are shown in table 3～4.
Claims (10)
1. a thermoplastic resin composition is characterized in that, this thermoplastic resin composition by with respect to 100 weight parts by (A) of 91～99 weight % use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under the melt viscosity measured by the capillary type mobilometer be that (B) of 100～300Pas and thermoplastic resin that does not form anisotropy fusion phase and 1～9 weight % can form the formed resin combination of anisotropy fusion liquid-crystalline polymer mutually, cooperate 0.001～2 weight part (C) to be selected from represented phosphorus oxygen acid monoesters of following general formula (I), (II) and in the diester one or more, wherein (B) liquid-crystalline polymer is a particles dispersed
(A) composition and (B) composition, use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under melt viscosity ratio (A η)/(the B η) that measured by the capillary type mobilometer be 3.2～4.0.
(X)
nP(＝O)(OR)
3-n (I)
(X)
nP(OR)
3-n (II)
[in the formula, n is 1 or 2, and X is hydrogen atom, hydroxyl or any monovalent organic radical group, can be identical or different when being a plurality of at it.R is monovalence or divalent organic group, can be identical or different when being a plurality of at it.]
2. thermoplastic resin composition according to claim 1, wherein (A) not form the thermoplastic resin of anisotropy fusion phase be polycarbonate resin.
3. thermoplastic resin composition according to claim 2, wherein the viscosity-average molecular weight of (A) polycarbonate resin is 17500～18900.
4. according to each described thermoplastic resin composition of claim 1～3, wherein (C) phosphorus oxygen acid monoesters and diester are by the represented phosphonic acid ester of following general formula (III).
H(OH)
mP(＝O)(OR’)
2-m (III)
[in the formula, m is 0 or 1, and R ' is an any monovalent organic radical group.]
5. according to each described thermoplastic resin composition of claim 1～4, wherein (C) phosphorus oxygen acid monoesters and diester are by the represented phosphonic acid ester of following general formula (IV).
[in the formula, Y is the α of divalence, ω-dioxy base organic group.]
6. molding, described molding obtains by each described thermoplastic resin composition of claim 1～5 is shaped, and (B) liquid-crystalline polymer is dispersed in (A) thermoplastic resin with island, and, be below the 30 μ m with the average major diameter of (B) liquid-crystalline polymer particulate of interior top layer part from molding surface 50 μ m.
7. a liquid crystal display component is characterized in that, it is by with each described thermoplastic resin composition of claim 1 to 5, that is, (A) composition and (B) composition, use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under melt viscosity ratio (A η)/(the B η) that measured by the capillary type mobilometer be that thermoplastic resin composition's injection forming of 3.2～4.0 obtains, and on rectangular-shaped, be provided with desirable opening portion, the ratio of opening portion is 30～95% of rectangular-shaped the total area, and rectangular-shaped thickness is 0.3～3mm.
8. liquid crystal display component according to claim 7, to be (B) liquid-crystalline polymer be dispersed in molding in (A) thermoplastic resin with island for it, and be below the 30 μ m from molding surface 50 μ m with the average major diameter of (B) liquid-crystalline polymer particulate of interior top layer part.
9. an information recording medium part is characterized in that, it is by requiring profit 1 to 5 each described thermoplastic resin composition, that is, (A) composition and (B) composition, use internal diameter as 1mm, length as the nozzle of 20mm, at 300 ℃, 1000sec
-1Shearing rate under melt viscosity ratio (A η)/(the B η) that measured by the capillary type mobilometer be that thermoplastic resin composition's injection forming of 3.2～4.0 obtains, and rectangular-shaped minor face/length limit ratio is 0.3～1.0, and rectangular-shaped thickness is 0.3～3mm.
10. information recording medium part according to claim 9, to be (B) liquid-crystalline polymer be dispersed in molding in (A) thermoplastic resin with island for it, and be below the 30 μ m from molding surface 50 μ m with the average major diameter of (B) liquid-crystalline polymer of interior top layer part.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP035376/2006 | 2006-02-13 | ||
| JP2006035376A JP5063901B2 (en) | 2006-02-13 | 2006-02-13 | Thermoplastic resin composition |
| JP042206/2006 | 2006-02-20 | ||
| JP042207/2006 | 2006-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101384669A true CN101384669A (en) | 2009-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2007800053933A Pending CN101384669A (en) | 2006-02-13 | 2007-02-08 | Thermoplastic resin composition and liquid crystal display part or information recording medium part using the composition |
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| JP (1) | JP5063901B2 (en) |
| CN (1) | CN101384669A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662139A (en) * | 2020-12-09 | 2021-04-16 | 上海普利特化工新材料有限公司 | High-melt-strength liquid crystal polyester resin composition for film and preparation method thereof |
| CN113906093A (en) * | 2019-05-08 | 2022-01-07 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7353288B2 (en) | 2018-02-20 | 2023-09-29 | ティコナ・エルエルシー | thermally conductive polymer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3759180B2 (en) * | 1993-11-11 | 2006-03-22 | ポリプラスチックス株式会社 | Synthetic resin composition molded body |
| JP2000119415A (en) * | 1998-10-14 | 2000-04-25 | Toray Ind Inc | Polyester film |
| JP4395900B2 (en) * | 1998-11-30 | 2010-01-13 | 東レ株式会社 | Thermoplastic resin composition and molded article |
| JP3664915B2 (en) * | 1999-07-16 | 2005-06-29 | ポリプラスチックス株式会社 | Thermoplastic resin composition and molded article thereof |
| JP2001089581A (en) * | 1999-09-22 | 2001-04-03 | Toray Ind Inc | Sheet and its production |
| JP2002249656A (en) * | 2000-12-19 | 2002-09-06 | Toray Ind Inc | Resin composition for component of thin information recording medium and molding |
-
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113906093A (en) * | 2019-05-08 | 2022-01-07 | 三菱工程塑料株式会社 | Polycarbonate resin composition |
| CN112662139A (en) * | 2020-12-09 | 2021-04-16 | 上海普利特化工新材料有限公司 | High-melt-strength liquid crystal polyester resin composition for film and preparation method thereof |
| CN112662139B (en) * | 2020-12-09 | 2022-09-20 | 上海普利特化工新材料有限公司 | High-melt-strength liquid crystal polyester resin composition for film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5063901B2 (en) | 2012-10-31 |
| JP2007211211A (en) | 2007-08-23 |
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