CN101977993B - Resin composition - Google Patents
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- CN101977993B CN101977993B CN200980110355.3A CN200980110355A CN101977993B CN 101977993 B CN101977993 B CN 101977993B CN 200980110355 A CN200980110355 A CN 200980110355A CN 101977993 B CN101977993 B CN 101977993B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
A resin composition including a polyester resin, e.g., PETG, and a polycarbonate resin. The resin composition is suitable for use as, e.g., a card material required to have heat resistance. The resin composition comprises: a polycarbonate resin (A); a polyester resin (B) obtained by condensation-polymerizing a dicarboxylic acid ingredient comprising terephthalic acid as the main component with a glycol ingredient comprising 80-60 mol% ethylene glycol as the main component and 20-40 mol% CHDM (the sum is 100 mol%); and a metal oxide (C). When the resin composition is examined for the dispersion of dynamic viscoelasticity with temperature under the conditions of a strain of 0.1%, frequency of 10 Hz, and heating rate of 3 DEG C/min, there is one main peak with respect to the dispersion of loss modulus and the temperature (Tg) at which the peak appears is in the range of 90-140 DEG C.
Description
Technical field
The present invention relates to can be used as the resin combination that heat-stable material uses, for example, can be used as the resin combination of the raw material use that requires stable on heating plastic cards.
Background technology
Most of plastic cards are to make by the core sheet (core sheet) that will be colored as white and transparent emulsion sheet (over sheet) lamination.As these sheet stock, mainly adopted polyvinyl chloride (PVC), but along with environmental problem etc. comes into one's own more and more, polyester resin becomes main flow gradually now in the past.Wherein, commonly used is approximately 30 % by mole of copolymerized type polyester resins (being called as " PETG ") that are substituted by 1,4 cyclohexane dimethanol and obtain with the glycol component in the pet resin.
, because therefore the poor heat resistance of PETG when making plastic cards take PETG as main raw material, exists following problems: under heat effect, dimensional change or distortion or curling etc. can occur.
Therefore, for the plastic cards take PETG as raw material and resin combination thereof, reported multiple for improving the stable on heating technology of card.
For example, in patent documentation 1～3 grade stable on heating technology that improves card by heat-stable materials such as mixed polycarbonate resinoids in PETG is disclosed.
Patent documentation 1: No. 3045112 communique of Japanese Patent
Patent documentation 2: TOHKEMY 2001-80251 communique
Patent documentation 3: TOHKEMY 2006-35740 communique
Summary of the invention
The problem that invention will solve
Recently, the receiving management that ETC card, digital broadcasting etc. have occurred can load or be placed on card in the car with card etc.Because summer, vehicle interior temperature was high, therefore require these jigs that excellent thermotolerance is arranged.For example, with regard to the ETC card since to make its 90 ℃ of lower dimensional change after placing 6 hours 0.2% with inferior, therefore the stable on heating requirement for this plastic cards improves just day by day.
Based on this, the resin combination that the present invention is directed to polyester resins such as comprising PETG and polycarbonate resin is studied, and a kind of novel resin composition of excellent heat resistance is provided based on the new opinion that obtains in this research.
The method of dealing with problems
In view of the above problems, the invention provides a kind of resin combination, this resin combination comprises polycarbonate resin (A), polyester resin (B) and metal oxide (C), described polyester resin (B) is by dicarboxylic acid composition and diol component polycondensation and obtain, it is principal constituent that described dicarboxylic acid composition comprises terephthalic acid, in described diol component, with respect to the ethylene glycol 80～60 (mol ratio) as principal constituent, contain 20～40 (mol ratios, amount to 100) 1, the 4-cyclohexanedimethanol, wherein, utilization is in strain 0.1%, frequency 10Hz, 3 ℃ of heat-up rates/minute condition under the temperature dispersion of the dynamic viscoelastic that carries out measure and there is a main peak that disperses in the out-of-phase modulus that records, and the temperature (also claiming second-order transition temperature or Tg) that shows this peak value is 90～140 ℃ scopes.
Usually, for polycarbonate resin (being also referred to as " PC resin ") and by diol component (by ethylene glycol and 1,4-cyclohexanedimethanol (being also referred to as " CHDM ") consists of) mixed system of the polyester resin that obtains with dicarboxylic acid composition polycondensation take terephthalic acid as principal constituent, known PC resin and CHDM ratio wherein surpasses between 50 % by mole the polyester resin (being called as " PCTG ") compatiblely, and PC resin and CHDM ratio are incompatible between the polyester resin about 30 % by mole (being called as " PETG ").But, the inventor finds through research, even the mixed system of PC resin and PETG, if to wherein adding specific metal oxide (C), then also may make them compatible, and, at this moment, if its second-order transition temperature (Tg) is adjusted to 90～140 ℃, then can obtain to be particularly suitable for as the desirable resin combination of card with parts.
Description of drawings
Fig. 1 is the mensuration curve of the dynamic viscoelastic of the resin combination that obtains among the embodiment 2.
Fig. 2 is the mensuration curve of the dynamic viscoelastic of the resin combination that obtains in the comparative example 1.
Embodiment
Below, describe for the resin combination (following also be called " this resin combination ") as an example of embodiments of the present invention.Need to prove, scope of the present invention is not subjected to the restriction of the embodiment of following explanation.
This resin combination is the resin combination that comprises polycarbonate resin (A), polyester resin (B) and metal oxide (C).
(polycarbonate resin (A))
The polycarbonate resin (A) that can be used for consisting of this resin combination is made of carbonic acid and glycol or dihydric phenol, is take general formula :-(O-R-O-CO-) resin (R is lipid acid or the aromatic group of divalence) that represents of n-.
For example, can enumerate following resin: use by phenol and the synthetic dihydroxyphenyl propane of acetone, by the resin of the manufacturings such as interfacial polymerization, ester-interchange method, pyridine method; Or by dihydroxyphenyl propane and dicarboxylic acid derivatives, such as to () copolymerization such as phthalyl chloride and the resin that obtains; Perhaps, by the derivative of dihydroxyphenyl propane, such as polymerizations such as tetramethylene dihydroxyphenyl propanes and resin that obtains etc.
Weight-average molecular weight for polycarbonate resin there is no particular restriction.Preference is such as 10,000～100, and 000, especially preferred 20,000～30,000,23,000～28,000 scope particularly preferably wherein.
In addition, the melt flow rate (MFR) for polycarbonate resin does not have particular restriction.For example, being preferably based on melt flow rate (MFR) that JISK7210 measures under 300 ℃, 1.2kg load is 5～20 polycarbonate resin.
It is pointed out that and to use separately a kind of polycarbonate, also the polycarbonate more than 2 kinds can be mixed and use.
(polyester resin (B))
The polyester resin (B) that can be used for consisting of this resin combination is by following dicarboxylic acid composition and following diol component polycondensation and the polyester resin that obtains, i.e. so-called " PETG ", wherein, comprise terephthalic acid as its principal constituent in the described dicarboxylic acid composition; In described diol component, with respect to the ethylene glycol 80～60 (mol ratio) as principal constituent, contain the 1,4 cyclohexane dimethanol (" CHDM ") of 20～40 (mol ratio amounts to 100).
As the dicarboxylic acid composition in the polyester resin (B), as long as contain terephthalic acid as its principal constituent, also can comprise other dicarboxylic acid composition except terephthalic acid.
In addition, as diol component, so long as with respect to the ethylene glycol 80～60 (mol ratio) as principal constituent, contain 20～40 (mol ratios, amount to 100) 1,4 cyclohexane dimethanol (" CHDM ") get final product, also can contain a small amount of other diol components such as Diethylene Glycol.
Wherein, with regard to the CHDM ratio in the polyester resin (B), can commercial obtain except the CHDM ratio is PETG below 40 % by mole, also have the CHDM ratio to surpass 50 % by mole PCTG.It is known that the two is compatible with each other in PCTG and PC resin blend system, but for PCTG and PC resin blend system, because relatively poor aspect the discolouration that causes in solvent resistance and by uviolizing, therefore in the present invention, use be that the CHDM ratio is the PETG below 40 % by mole.
More preferably 25～40 % by mole of CHDM ratios among the PETG, more preferably 30～34 % by mole.In addition, as the ratio of the cis/trans of CHDM, preferably its trans ratios is about 70%.
Wherein, preferred characteristics viscosity (IV value) is the PETG more than 0.70.
(metal oxide (C))
The CHDM ratio is that PETG and the PC resin blend system below 40 % by mole is known as the non-conforming system, but finds may make said two devices compatible by mixing the metal oxide (C) of appointment.
As the metal oxide that can be used for consisting of this resin combination (C), be preferably oxide compound or the composite oxides of metal more than a kind that are selected from copper, molybdenum, tin and the antimony.Wherein, be preferably the composite oxides of metal more than 2 kinds that are selected from copper, molybdenum, tin and the antimony.This wherein preferably comprises the composite oxides of copper and molybdenum.
As the preferred specific examples of metal oxide (C), can enumerate with CuOxMoO
3YSnO
2ZSb
2O
5The composite oxides of (x in the formula, y and z are any number) expression etc.
Wherein, the composite oxides of described metal are the oxide compounds that comprises metal ion more than 2 kinds, are to have made up oxide compound more than 2 kinds and each metal ion have formed respectively ionic lattice in the slit of the closeest filling of O ion sosoloid.
Volume average particle size (D50) for metal oxide there is no particular restriction, but is preferably 0.1 μ m～10 μ m, is particularly preferably 0.1 μ m～3 μ m.
Described volume average particle size (D50) is that the volume accumulated value that utilizes Mai Qike (Microtrac) particle size distribution device to measure is 50% granularity.
Above-mentioned composite oxide of metal can obtain by following method: pending compound feed metal oxide material is made the homogeneous drying composite, fire under the high temperature more than 600 ℃.Through after firing, can carry out arbitrarily the pulverizing of wet type or dry type or further implement annealing etc.
Metal oxide (C) can be to utilize known various mineral compound, organic compound, metal to carry out the surface-treated compound.As the metal of this moment, can enumerate such as Si, Al, Zn, Co, Fe, Ni, Cr, Mn, W, Ti, Zr, Y, Hf, V, Nb, Ta, Sb, Sn etc.
(blending ratio)
Blending ratio as polycarbonate resin in this resin combination (A), polyester resin (B) and metal oxide (C), preferably with 10: 90～90: 10 mass ratio mixed polycarbonate resinoid (A) and polyester resin (B), especially, more preferably with 30: 70～70: 30 ratio both are mixed.
In addition, with respect to the total amount of polycarbonate resin (A) with polyester resin (B), preferably mix the metal oxide (C) of 0.01～1 quality %, especially, more preferably mix 0.05～0.2 quality %.
(second-order transition temperature)
Usually, PC resin and CHDM ratio are that the co-mixing system of the PETG below 40 % by mole is incompatible, therefore, when measuring second-order transition temperature (hereinafter referred to as " Tg "), can clearly occur the Tg (approximately 150 ℃) of PC resin and PETG Tg (approximately 80 ℃) the two.This non-conforming system combination during long-time the placement, can occur softening or distortion under surpassing 80 ℃ temperature, therefore, if will be placed on for a long time by the card that said composition is made in the car in summer for example, may cause card to shrink or crooked.Thus, it is not suitable for for example receiving management of the in-car TV so possibly long-time card purposes of placing in car of card.
But clear and definite following result: when adding specific metal oxide (C), can become compatible system, the maximum value of its Tg and tan δ can become one.And find: in this case, be adjusted in the stated limit by the maximum value with Tg and tan δ, can obtain to be specially adapted to the resin combination of card purposes.
This resin combination is the composition with single second-order transition temperature (Tg).
In the present invention, this resin combination has single second-order transition temperature (Tg) and refers to: by measuring main peak that disperses of out-of-phase modulus existence that (Measurement of Dynamic Viscoelasticity of JISK-7198A method) records in strain 0.1%, frequency 10Hz, 3 ℃/minutes lower temperature dispersion of carrying out dynamic viscoelastic of heat-up rate, in other words, there is simple spike.It is that loss tangent (tan δ) exists 1 maximum value that this situation can also be said into.In addition, can also say into be based on the JISK7121 standard, use differential scanning calorimeter with 10 ℃ of rate of heating/when minute measuring second-order transition temperature, the flex point of 1 expression second-order transition temperature only occurs.
The second-order transition temperature of polymer blend compositions (or maximum value of loss tangent) is one, means that the resin of mixing is in the compatible state of Nano grade (molecular level), can regard as compatible system.
The second-order transition temperature of this resin combination (Tg) is the value of showing with following thermometer: the temperature of the main scatter display peak value of the out-of-phase modulus that the temperature dispersion by above-mentioned dynamic viscoelastic records, this temperature (Tg) is particularly important 90～140 ℃ scope.
The second-order transition temperature of this resin combination is more than 90 ℃ the time, and the dimensional change in the time of it can being carried out taking care of for a long time under 90 ℃ is suppressed at quite little degree.On the other hand, if the second-order transition temperature of this resin combination is too high, surpass 140 ℃, then can cause the hot pressing excess Temperature when making card, make difficult.
Consider from above-mentioned viewpoint, more preferably the second-order transition temperature of this resin combination is 95～135 ℃, is particularly preferably 110～130 ℃.
(manufacture method)
Manufacture method for this resin combination there is no particular restriction, for example, can carry out heating and melting, mixing by other composition (D) to polycarbonate resin (A), polyester resin (B), metal oxide (C) and as required use, obtain this resin combination.
As the form of this resin combination, can be the arbitrary shapes such as particulate state, film/sheet.
It is pointed out that in above-mentioned Production Example, the Heating temperature when carrying out heating and melting is preferably 230 ℃～280 ℃, is particularly preferably 240 ℃～260 ℃.
For the second-order transition temperature (Tg) of regulating this resin combination, can enumerate the method that the blending ratio of polycarbonate resin (A) and polyester resin (B) is regulated.
As above-mentioned other composition (D), can enumerate such as pigment, filler, slipping agent, modified impact agent, oxidation inhibitor etc.
For example, as the example of filler, can enumerate the filler that talcum, kaolin, calcium carbonate, aluminum oxide, glass fibre etc. use usually in resin.
As slipping agent, can enumerate wax class, alkylbenzene sulfonate and the various tensio-active agents etc. such as higher alcohols, fatty amide, higher fatty acid and ester or metal-salt, montanate.
(purposes)
Because therefore the excellent heat resistance of this resin combination can be used as heat-stable material and uses.For example, by being made sheet by this resin combination, and with this sheet stack on various or plate, can improve the thermotolerance of described various or plate.
In addition, can also be with this resin combination as the starting material of various plastic cards, such as the raw material of transparent emulsion sheet or white core sheet etc.Particularly preferably with do to thermotolerance have the plastic cards of requirement raw material, such as the receiving management of ETC card or digital broadcasting etc. with card etc. can be in car the raw material of the long-time card that uses.By this resin combination is shaped to sheet, can make card, such as the receiving management card of ETC card or digital broadcasting etc., particularly make the core sheet of these cards.
In addition, can also come with this resin combination the three-dimensionally shaped things such as moulding such as container, lid, pipeline, parts.These forming composition can be the forming composition with multilayered structure, also can be parts that consists of the parts of composite molding thing.
Forming method as this moment can adopt the known methods such as injection moulding, extrusion moulding, slush molding, rotary press modelling, powder compacting, vacuum forming.
As the specific examples of described forming composition, can enumerate such as various parts, material of construction etc. such as the container of food, washing composition, medicine, makeup, beverage product etc. and lid class thereof, trolley part, electronic unit, electrical element, motor component, mechanical parts.
In addition, can also come the various films of moulding with this resin combination.
As the forming method of this moment, the in length and breadth synchronous bidirectional stretching method that can adopt the processing of blowing processing, multilayer blow moulding, the processing of T-shaped die head film, carries out based on flat embrane method or the known method such as step by step two-way stretch method, periosteum method in length and breadth.
The identical field, field that the film that utilizes aforesaid method to obtain can be applied to food product pack, fiber packing, groceries packing, drug class packing, band (tape), insulating material, plastic film for agricultural use, various sheet material, variously seals, label, card etc. use thermoplastic resin film usually.
(term explanation)
Usually, described " film " refers to: compare with length and width, its thickness is minimum, and the goods of the Bao Erping that limited arbitrarily of maximum ga(u)ge, the goods that the form that typically refers to roll up is supplied to (JISK6900 of Japanese Industrial Standards); Usually, described " sheet " refers to: thin and flat goods in the definition in JIS, and its thickness is less for length and width usually.But sheet and film do not have clear and definite boundary, there is no need both are distinguished in description of the invention, and therefore, the situation that in the present invention, is called " film " also comprises " sheet ", and the situation that is called " sheet " also comprises " film ".
In the present invention, when explaining with " principal constituent ", in the situation that not special record comprises following implication: in the scope of the function that does not hinder this principal constituent, allow and contain other composition.Be not to containing of this principal constituent of proportional the restriction, but this principal constituent (for composition more than 2 kinds as the situation of principal constituent, refer to their total amount) in composition, preferably account for more than the 50 quality %, particularly preferably account for more than the 70 quality %, wherein especially preferably account for more than the 90 quality % and (comprise 100%).
In addition, in this manual, in the situation that there is not specified otherwise, when being denoted as " X～Y " (X, Y are Any Digit), its implication is " X is above and Y is following ", also comprises the implication of " being preferably greater than X " or " preferably less than Y " simultaneously.
Embodiment
Below, enumerate embodiment the present invention is described in more detail, but the present invention is not limited to these embodiment, in the scope that does not break away from technical key point of the present invention, can carry out various application.
(1) measuring method of second-order transition temperature
Utilize visco-elasticity spectrometer DVA-200 (IT instrumentation control Co., Ltd. system), under the condition of 3 ℃/minutes of strains 0.1%, frequency 10Hz, heat-up rate, carry out the dynamic viscoelastic temperature dispersion and measure.Wherein, disperse the temperature at peak as second-order transition temperature (Tg) with the master who demonstrates out-of-phase modulus.
(embodiment 1-5)
Polycarbonate resin (A), polyester resin (B) and metal oxide (C) are mixed respectively as shown in table 1ly, and utilize the double-exhaust port formula parallel dual-screw extruding machine of diameter 65mm, under 260 ℃ of design temperatures, obtain the sheet of thickness 0.3mm by T-shaped mould extrusion molding.
(comparative example 1)
Except in embodiment 1 not mixed metal oxide (C), and ground as shown in table 1 mixed polycarbonate resinoid (A) and polyester resin (B), obtain mixture (compound) according to the method identical with embodiment 1.
Need to prove, the weight-average molecular weight of the polycarbonate resin that uses in embodiment and the comparative example (A) is about 21000, and the melt flow rate (MFR) of measuring under 300 ℃, 1.2kg load based on JISK7210 is 15.
In addition, polyester resin (B) is the PETG that is obtained by following diol component and the dicarboxylic acid composition polycondensation take terephthalic acid as principal constituent, its limiting viscosity IV is 0.76, wherein, described diol component is made of 66 % by mole of ethylene glycol, 32 % by mole of 1,4 cyclohexane dimethanols and 2 % by mole of Diethylene Glycols.
As metal oxide (C), use be with CuOxMoO
3YSnO
2ZSb
2O
5The composite oxides of (in the formula, x=2, y=1, z=1) expression.These composite oxides obtain by following method: pending compound feed metal oxide material is made the homogeneous drying composite, and fire under 800 ℃.
[table 1]
(investigation)
In the situation of the embodiment 1～5 that contains metal oxide (C), second-order transition temperature (Tg) is one, and confirmed following result: different from the ratio of polyester resin (B) according to polycarbonate resin (A), can the scope between the Tg of the Tg of polycarbonate resin (A) (approximately 140 ℃) and polyester resin (B) (approximately 80 ℃) be regulated by its second-order transition temperature.This shows, the two is in compatible state.
On the other hand, in the situation of the comparative example 1 that does not contain metal oxide (C), have respectively 2 second-order transition temperatures (Tg) corresponding with the Tg of the Tg of polycarbonate resin (A) and polyester resin (B), hence one can see that, and the two is the non-conforming state.
Wherein, the Measurement of Dynamic Viscoelasticity data of embodiment 2 and comparative example 1 respectively as shown in Figure 1 and Figure 2.In these graphic representations, Er is that storage modulus, Ei are that out-of-phase modulus, tan δ are the data of loss tangent.
Make resin combination according to the method identical with embodiment 1～5, and utilize the resin combination that obtains to make the core sheet that is used for card, confirm it and be suitable for result as card material.Therefore, in the situation of the Tg scope of the resin combination that in considering embodiment 1～5, obtains (sheet), can think, when Tg is in 90～140 ℃ of scopes, can be suitable for use as card material.In addition, in embodiment 1～5, embodiment 2,3,4 result are good especially, in the situation that consider this result, can think, when Tg was in 105～130 ℃ of scopes, it was suitable for use as card material more.
In the above-described embodiments, as metal oxide (C), used with CuOxMoO
3YSnO
2ZSb
2O
5The composite oxides of (in the formula, x=2, y=1, z=1) expression if consider above test-results of carrying out, use oxide compound or the composite oxides of metal more than a kind that are selected from copper, molybdenum, tin and the antimony should also can expect to obtain and CuOxMoO
3YSnO
2ZSb
2O
5(in the formula, x=2, y=1, z=1) same effect, wherein, use be selected from copper, molybdenum, tin and the antimony more than 2 kinds metal composite oxides, especially use when comprising the composite oxides of copper and molybdenum, can expect to obtain desirable effect.
Claims (5)
1. resin combination, it comprises polycarbonate resin (A), polyester resin (B) and metal oxide (C), described polyester resin (B) is by dicarboxylic acid composition and diol component polycondensation and the resin that obtains, it is principal constituent that described dicarboxylic acid composition comprises terephthalic acid, in described diol component, with respect to as 80～60 % by mole of the ethylene glycol of principal constituent, contain 20～40 % by mole 1, the 4-cyclohexanedimethanol, and described ethylene glycol and described 1, the 4-cyclohexanedimethanol amounts to 100 % by mole, wherein
Described metal oxide (C) is with CuO2MoO
3SnO
2Sb
2O
5The composite oxides of expression,
When measuring with the temperature dispersion of 3 ℃ of strains 0.1%, frequency 10Hz, heat-up rate/minute this resin combination is carried out dynamic viscoelastic, the out-of-phase modulus that records exists one mainly to disperse the peak, and show this peak value temperature, be Tg 90～140 ℃ scope.
2. formed body, it is that right to use requires 1 described resin combination and forms.
3. sheet, it is that right to use requires 1 described resin combination and forms.
4. card sheet, it is that right to use requires 1 described resin combination to form.
5. card, it is the card that right to use requires 4 described formation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP073792/08 | 2008-03-21 | ||
| JP2008073792A JP5390112B2 (en) | 2008-03-21 | 2008-03-21 | Resin composition |
| PCT/JP2009/001239 WO2009116297A1 (en) | 2008-03-21 | 2009-03-19 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101977993A CN101977993A (en) | 2011-02-16 |
| CN101977993B true CN101977993B (en) | 2013-04-17 |
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| CN200980110355.3A Active CN101977993B (en) | 2008-03-21 | 2009-03-19 | Resin composition |
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| JP (1) | JP5390112B2 (en) |
| KR (1) | KR101215661B1 (en) |
| CN (1) | CN101977993B (en) |
| HK (1) | HK1148763A1 (en) |
| MY (1) | MY174405A (en) |
| TW (1) | TWI444429B (en) |
| WO (1) | WO2009116297A1 (en) |
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| CN101864161B (en) * | 2010-06-24 | 2011-12-21 | 上海达凯塑胶有限公司 | Makrolon/modified polyester blending rolling base material and preparation method thereof |
| CN104693704B (en) * | 2015-03-16 | 2018-04-13 | 南京工业大学 | Amorphous transparent PETG copolyester functional film and preparation method thereof |
| CN104744916B (en) * | 2015-04-08 | 2016-06-08 | 台州市元嘉工业有限公司 | A kind of makrolon material of nanocrystal composite oxide modified and preparation method thereof |
| CN106317829B (en) * | 2016-08-26 | 2019-05-24 | 沈丽媛 | A kind of PC alloy material and its preparation method and application |
| KR102013019B1 (en) * | 2016-12-30 | 2019-08-21 | 롯데첨단소재(주) | Thermal conductive resin composition and composite comprising the same |
| CN111662486A (en) * | 2020-07-10 | 2020-09-15 | 上海叶心材料科技有限公司 | Method for improving tensile strength of bio-based degradable material |
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| JP4596788B2 (en) * | 2004-02-12 | 2010-12-15 | 三菱樹脂株式会社 | Resin-coated metal sheet, method for producing the same, and resin-coated metal sheet using the sheet |
| JP2005232435A (en) * | 2004-01-20 | 2005-09-02 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable film |
| US20070129470A1 (en) * | 2005-12-05 | 2007-06-07 | Kuvshinnikova Olga I | Weatherable resinous composition with low heat storage and method |
-
2008
- 2008-03-21 JP JP2008073792A patent/JP5390112B2/en active Active
-
2009
- 2009-03-10 TW TW098107625A patent/TWI444429B/en active
- 2009-03-19 MY MYPI2010004359A patent/MY174405A/en unknown
- 2009-03-19 CN CN200980110355.3A patent/CN101977993B/en active Active
- 2009-03-19 KR KR1020107023413A patent/KR101215661B1/en active IP Right Grant
- 2009-03-19 WO PCT/JP2009/001239 patent/WO2009116297A1/en active Application Filing
-
2011
- 2011-03-23 HK HK11102921.7A patent/HK1148763A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054179A (en) * | 2003-07-23 | 2005-03-03 | Sumitomo Bakelite Co Ltd | Core sheet for card, and heat-resistant card using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100123772A (en) | 2010-11-24 |
| TW200946593A (en) | 2009-11-16 |
| JP2009227788A (en) | 2009-10-08 |
| KR101215661B1 (en) | 2012-12-26 |
| WO2009116297A1 (en) | 2009-09-24 |
| JP5390112B2 (en) | 2014-01-15 |
| TWI444429B (en) | 2014-07-11 |
| HK1148763A1 (en) | 2011-09-16 |
| CN101977993A (en) | 2011-02-16 |
| MY174405A (en) | 2020-04-16 |
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