CN1196698A - Amorphous transparent plate of crystallisable thermoplast with high standard viscosity - Google Patents
Amorphous transparent plate of crystallisable thermoplast with high standard viscosity Download PDFInfo
- Publication number
- CN1196698A CN1196698A CN96197028A CN96197028A CN1196698A CN 1196698 A CN1196698 A CN 1196698A CN 96197028 A CN96197028 A CN 96197028A CN 96197028 A CN96197028 A CN 96197028A CN 1196698 A CN1196698 A CN 1196698A
- Authority
- CN
- China
- Prior art keywords
- thin plate
- pet
- measured
- plate
- crystallisable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
Abstract
The invention relates to a transparent, amorphous plate with a thickness in the 1 to 20 mm range, having as its main component a crystallisable thermoplast and in which the crystallisable thermoplast has a standard viscosity SV (DCA) in the 1800 to 6000 range, a process for its production and its use.
Description
The present invention relates to a kind of thickness in 1 to 20 millimeter scope and have an amorphous, transparent plate of the crystallisable thermoplastic of high standard viscosity.This thin plate is a characteristic with extraordinary optics and mechanical property.And, the invention still further relates to the method for making of this thin plate and the purposes of this thin plate.
Thickness is well known at 1 to 20 millimeter amorphous, transparent plate.These plane works contain amorphous can not the crystallization thermoplastic plastics.For example, this type of representative instance that can be processed into the thermoplastic of thin plate has polyvinyl chloride (PVC)), Merlon (PC) and polymethyl methacrylate (PMMA).These semi-finished product be on so-called extruded threads, make (consult Polymer Werkstoffe[polymeric material], the II volume; Technologie I, the 136th page, Georg Thieme Verlag, Stuttgart, 1984).Powdery or granular feedstock melt in extruder.After the extruding,, make to be easy to be shaped via calender or other forming tools because the viscosity of amorphous thermoplastic reduces and increase continuously along with temperature.After the shaping, the amorphous thermoplastic will have suitable stability, that is high viscosity is so that can the oneself support in the calibration mould.Yet they are still very soft and can't be shaped by mould.Melt viscosity and the intrinsic rigidity of amorphous thermoplastic in the calibration mould is too high, so that semi-finished product can't shrink in the calibration mould at the preceding of cooling.At labile material, among the PVC, be to need special processing aid during its extruding for example, the lubricant that for example anti-processing stabilizers that decomposes reaches anti-excessive internal friction and therefore causes uncontrollably heating.Exterior lubricant also is essential, reaches on the roller to prevent to adhere on the wall.
For example, the processing of PMMA is to use the exhaust extruder to carry out so that can remove moisture.
Need expensive additive when the amorphous thermoplastic is made transparent panel sometimes, examples of such additives adheres to owing to evaporation and on surface of semi-finished and can move and cause manufacturing issue.Some difficulty of the recirculation of PVC plate is perhaps only carried out when using special neutralisation or electrolysis.Similarly, the recirculation of PC and PMMA plate is also very difficult or only just can recycle in loss or the situation of extremely damaging mechanical property.
Except these shortcomings, the PMMA plate also have the resistance to impact of being on duty mutually and fracture or mechanical load under can be cracked.And the PMMA plate burns easily, so they are not useable in indoor application and the exhibition.
Moreover PMMA and PC plate can not cold formings.During the cold forming, the PMMA plate can disintegration and form dangerous sliver, then can hairline occur during the cold forming of PC plate and stress bleaches.
European patent EP-A-0471528 has come out with a kind of method by PET (PET) plate shaping article.The inherent viscosity of used PET is in 0.5 to 1.2 scope.In the temperature range of this PET plate between its glass transition temperature and fusing point, two face of hot-working in the hot forming mould.The PET plate that is shaped is if its crystallization degree can take out from mould in 25 to 50% scopes the time.Be disclosed in the thickness that PET plate among the EP-A-0471528 has 1 to 10 centimetre.Because the hot forming molded that makes from the PET plate is partly crystallization, so no longer be transparent; And the surface characteristic of this molded is by thermo shaping method, and hot forming temperature and mould decide, so used PET plate has what kind of optical characteristics (for example gloss, preformed casse and light transmission) just becomes inessential.Generally speaking, the optical characteristics of these thin plates is all very poor, and need it is perfect.
U.S. Pat-A-3,496,143 disclose the vacuum-thermoform of one 3 millimeters thick PET plates, and its crystallization degree should be in 5 to 25% scopes, however the degree of crystallinity of this hot forming molded is but greater than 25%.Moreover these PET plates do not require optical characteristics yet.Because the degree of crystallinity of used thin plate is between 5 to 25%, so these thin plates are preformed casse shapes and opaque.
Target of the present invention provides an amorphous, transparent plate with 1 to 20 millimeter thickness, and it has good mechanical and optical characteristics.
For example, the good optical characteristic comprises high light transmission, high surface gloss, extremely low preformed casse and high clarity.
The favorable mechanical characteristic comprises high-impact and high fracture strength particularly especially.
Moreover this novelty thin plate should recycle, and can not undermine mechanical property especially, and has low flammability, thereby just can use in indoor application and exhibition.
This target can by one contain crystallisable thermoplastic as main component and thickness in 1 to 20 millimeter scope transparent amorphous plate and reach, wherein this crystallisable thermoplastic has scope at 1800 to 6000 normal viscosity SV (DCA) (recording according to DIN53728) in dichloroacetic acid.
The normal viscosity SV (DCA) of the crystallisable thermoplastic of being surveyed in dichloroacetic acid according to DIN53728 more preferably is 2500 to 4000 preferably 2000 to 5000.
As described below, inherent viscosity IV (DCA) calculates from normal viscosity SV (DCA):
IV(DCA)＝6.67·10
-4SV(DCA)+0.118
Greater than 120, be preferably more than 130 according to the measured surface gloss of DIN67530 (20 ° of measured angular); Greater than 84%, be preferably more than 86% according to the measured light transmission of ASTM D1003; And be less than 15% according to the measured thin plate preformed casse of ASTM D1003, preferably less than 11%.
This transparent amorphous plate contains a crystallisable thermoplastic as main component.For example, suitable thermoplastic crystallizable or partly crystallization has PET, polybutylene terephthalate, cyclic olefin polymer and cyclic olefine copolymer, preferably PET.
According to the present invention, crystallisable thermoplastic is represented-crystallizable homopolymers ,-crystallizable copolymer, and-crystallizable compound ,-crystallizable recycled matter, and-variant of other crystallisable thermoplastics.
According to the present invention, though used crystallisable thermoplastic preferably has 5 to 65% degree of crystallinity, amorphous plate one speech is the amorphous thin plate of expression.Noncrystalline or basically amorphous be meant its degree of crystallinity normally less than 5%, preferably less than 2%, more preferably be 0%.The amorphous plate of this form is not have orientation basically.
The method for making of crystallisable thermoplastic is familiar with by the professional.
For example, PET is prepared by polycondensation in fusion usually, perhaps by two step polycondensations preparations, promptly wherein first step to reach mean molecule quantity-correspond to average characteristics viscosity IV in fusion about 0.5 to 0.7, carry out further condensation by the solid condensation reaction again.Polycondensation reaction is carried out in the presence of known polycondensation catalyst or catalyst system usually.In the solid condensation reaction, the PET fragment under reduced pressure or under protective gas in 180 to 320 ℃ the temperature range heating till required molecular weight.
The preparation of poly-terephthalic acids second diester at length is disclosed in a large amount of patents, for example, JP-A-60-139 717, DE-C-2 429 087, DE-A-27 07 491, DE-A-23 19 089, DEA-16 94 461, JP-63-41 528, JP-62-39 621, DE-A-41 17 825, DE-A-42 26 737, JP-60-141 715, DE-A-27 21501, and US-A-5,296,586.
When liquid heat transfer medium is inertia and does not contain aromatics partly and when having the boiling point of scope at 200 to 320 ℃, have special HMW PET can by in the presence of known polycondensation catalyst and cocondensation modifier in case of necessity in liquid heat transfer medium, and at high temperature make dicarboxylic acids/dihydroxylic alcohols precondensate (oligomer) carry out polycondensation reaction and prepare; Weight ratio between used dicarboxylic acids/dihydroxylic alcohols precondensate (oligomer) and liquid heat transfer medium is in 20: 80 to 80: 20 scopes, and polycondensation reaction is to carry out in the reactant mixture of boiling in the presence of dispersion stabilizer.
Under the situation of PET, measure the charpy impact intensity a of thin plate
nThe time (measuring) according to ISO 179/ID preferably do not rupture.Moreover, the cantilever fine strain of millet formula notched Izod impact strength a of this plate
k(measuring) according to ISO 180/1A preferably 2.0 to 8.0kJ/m
2In the scope, more preferably 4.0 to 6.0kJ/m
2Scope.
Be preferably more than 96% in angle less than 2.5 ° of following measured thin plate clarities (ASTMD 1003), more preferably greater than 97%.
Has crystalline melt point T
m(by DSC (differential scanning calorimetry)) measured with 10 ℃/minute the rate of heat addition) at 220 to 280 ℃, especially 220 ℃ to 260 ℃, preferably 230 ℃ to 250 ℃; Crystallization range T
cFrom 75 ℃ to 280 ℃, preferably 75 ℃ to 260 ℃; Glass transition temperature T
gFrom 65 ℃ to 90 ℃; And according to the measured density of DIN 53479 1.30 to 1.45g/cm
3And degree of crystallinity is the preferred polymers that can be used as the initial substance of making this novelty thin plate at 5 to 65% PET.
The bulk density that rule are measured according to DIN 53466 preferably 0.75 to 1.0kg/dm
3, more preferably 0.80 to 0.90kg/dm
3
Polydispersity M by the measured PET of GPC
w/ M
nBe generally 1.5 to 6, preferably from 2.5 to 6.0, more preferably from 3.0 to 5.0.
In preferred specific embodiments, this novelty thin plate will provide the UV light stabilizer and make bright protective agent.
Bright protective agent concentration is preferably in 0.01 to 5 weight % (based on the weight of crystallisable thermoplastic).
Ultraviolet ray in the light, particularly sunlight partly that is has wavelength in 280 to 400nm scopes, can cause the degraded of thermoplastic, not only can change owing to change color or flavescence cause in appearance, also can have influence on mechanical and physical property unfriendly simultaneously.
Because, be very limited in the possible purposes of the many thermoplastics of other situation, so the inhibition of these photooxidative degradation processes just quite has importance industrial and economically.
For example, PET just can begin to absorb UV light under 360nm, and the absorption below 320nm increases very considerablely, and can be remarkable in the extreme when being lower than 300nm.Absorption maximum 280 and 300nm between.
In the presence of oxygen, mainly can observe the chain cracking, but not have crosslinked action.With the angle of quantity, carbon monoxide, carbon dioxide and carboxylic acid are main photo-oxidation products.Except the direct photolysis of ester group, also must consider oxidation reaction, similarly it also can form carbon dioxide via peroxide radical.
Simultaneously, by the cancellation effect that the alpha-position of ester group is put middle hydrogen, the photooxidation of PET also can produce hydroperoxides and catabolite thereof, and the chain cracking (H.Day of associated, 16 phases of J.Appl.Polym.Sci of D.M.Wiles, 1972, the 203rd page).
UV stabilizing agent and UV absorbent as bright protective agent all are to participate in the physics of photo-induced degradation and the compound of chemical process.Carbon black and other pigment can provide the part protection to light.Yet these materials are unsuitable for transparent panel, because they can cause variable color or change color.For transparent amorphous plate, unique suitable compound is that those make the stable thermoplastic of desire not have or have only the organic and organo-metallic compound of very faint color or change color.
The example of suitable bright protective agent or UV stabilizing agent has 2-hydroxyl-benzophenone, 2-hydroxybenzotriazole, organic nickel compound, salicylate, cinnamate derivates, single benzoic acid resorcinol, oxanilide, hydroxybenzoate, bulky amine and compound in triazine class, preferably 2-hydroxybenzotriazole and compound in triazine class.
In preferred specific embodiments, novel transparent amorphous plate contains crystallizable PET as main component, and 0.01 to 5.0 weight %2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-(hexyl) oxy phenol (as the structure of Fig. 1 a) or 0.01 to 5.0 weight %2,2 '-methylene-two (6-(2H-BTA-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol (as the structure of Fig. 1 b).In preferred specific embodiments; also can use simultaneously the mixture of these two UV stabilizing agents; or the mixture of at least one and other UV stabilizing agents in these two UV stabilizing agents; and the total concentration of bright protective agent 0.01 to 5.0 weight % preferably, with respect to the weight of crystallizable PET.
Weather resistance test demonstrates, this novelty after the stable thin plate of UV uses 5 to 7 years out of doors not or present flavescence rarely, become fragile, lustrous surface loss, skin breakage and undermine mechanical property.
Moreover, fully unexpectedly also can be observed the cold formability that good non-cracking, hairline and/or stress bleach, thereby should the novelty thin plate need not that heat effect can be shaped and crooked.
Except that this, show that through measuring this novel thin plate has low flammability and low combustible, thereby applicable in indoor application and the exhibition.
And this novelty thin plate can recycle easily and not have environmental pollution and also can not undermine tool tool characteristic, and they are applicable to the billboard or the advertising items of imitating in short-term like this.
In the stable specific embodiment of UV, this thin plate has improved weatherability and UV stabilizing agent.This does not have when meaning these thin plates through wind erosion and light or through other UV radiation or only has quite little scope undermined; Thereby these thin plates are just applicable to outdoor utility and/or accurate indoor application.For example, the transparent amorphous plate of this novelty can be made by extruding on extruded threads.
This type of extruded threads reaches as shown in Figure 2, it comprises basically-as the extruder (1) of plasticizing equipment,-as the sheet die (2) of forming tool,-as the calender (3) of calibration mould, roller carrier (5) is cooled off in-cooling bed (4) and/or back ,-handover roller (6),-segment saw (7),-edge clipping device (9), and if need-stacking device (8).
The method comprises the dried if necessary crystallisable thermoplastic, in extruder, make dry polymer fusing when needing (if can with the UV stabilizing agent) then, extrude this fused mass, in calender, calibrate through die head, even up and cool off this thin plate, this thin plate is cut be cut into certain size then.
The method for making of this novel thin plate will be example and in hereinafter describing in detail with the PET.
This PET is preferably following dry 4 to 6 hours at 160 to 180 ℃ before extruding.
Then, this PET of fusing in extruder.The temperature of PET fused mass is preferably in 250 to 320 ℃ of scopes.The temperature of fused mass can be adjusted by the temperature and the fused mass of extruder basically the residence time in extruder.
If use bright protective agent, it can add in advance via raw material manufacturer, or during the manufacturing thin plate in being metered into extruder.
Bright protective agent more preferably adds via the masterbatch technology, and this measure can make bright protective agent fully be scattered in the solid-state carrier material.The suitable carriers material is some resin, crystallisable thermoplastic itself, for example, and PET, or be enough to other polymer compatible with crystallisable thermoplastic.
But importantly, the particle size of masterbatch and bulk density are similar with the particle size and the bulk density of crystallisable thermoplastic, thereby so just can produce uniform distribution and even UV stabilisation is arranged.
Then, this fused mass will leave extruder by die head.This die head is sheet die preferably.
, promptly fully cool off and even up via extruder melts and the PET that is shaped by sheet die with the calibration of level and smooth calender roll.For example, calender roll can I-, F-, L-or S-shape (as Fig. 3) arrange.
Next, on the roller carrier further this PET material of cooling, cut and be cut into the identical size of width, be cut into suitable length again, heap again at last.
The thickness of PET plate basically by the handover element that is arranged in the cooled region least significant end, with transfer element at the chill roll of coupling and be the transporting rate of extruder on the one hand and be that distance between roller decides on the other hand mutually on the speed.
Used extruder can be single screw rod or twin (double) screw extruder.
Preferably include sheet die removable mould main body, antelabium and control width adjustment flow and use limit rod.Thereby this limit rod can the bending by the tension and compression screw rod.Thickness then is to set to adjust antelabium.Importantly must make PET and antelabium have uniform temperature because otherwise the PET fused mass can from each different grooves that flow, flow out with different thickness.
Truing tool, that is level and smooth calender can make the shaping of PET fused mass and determine size.This can and even up and be lower than freezing reaching under the glass transition temperature by cooling.Be shaped and should not be in this situation and carry out, because under this state of cooling, form blemish.Based on this reason, the calender roller preferably jointly drives.The temperature of calender roller must be lower than crystalline melt point, sticks together to avoid the PET fused mass.The PET fused mass leaves sheet die at 240 to 300 ℃.
First level and smooth/chill roll has 50 ℃ to 80 ℃ temperature, decides according to output speed and lamella thickness.Second colder roller then can cool off second or other surface.
In order to obtain to have the homogeneous thin plate of excellent surface characteristic, the most basic is to make the temperature of first level and smooth/chill roll in 50 to 80 ℃ of scopes.
At freezing as far as possible smoothly this thin sheet surface of calibrating element, make the profile cooling when fixed in shape, back cooling device just can make the thin plate temperature be reduced to almost room temperature.Back cooling can be carried out on roller plate.Transferring speed should accurately coincide with calender roller speed, so that prevent defective and thickness fluctuation.
As extra device, the extruded threads of making thin plate can comprise that also all cut thin plate cutting apart saw, side trimmer, heap element and monitoring station to fixed length.Because the thickness of fringe region is also inhomogeneous in some cases, so side or edge trimmer are more useful.Just can measure gauge of sheet and optical characteristics at monitoring station.
Because unexpected many excellent specific properties are arranged, make the transparent amorphous plate of this novelty be highly suitable for various uses, for example, applicable to reaching the exhibition object in indoor room panelling, the exhibition, display board, billboard is used for lighting field, shop assembling and shelf works, as advertisement object, menu holder, basketball backboard, room space bar, data tablet and brochure and newspaper rack.
In the stable specific embodiments of UV, this novel thin plate also is suitable for outdoor utility, for example, and applicable to greenhouse, roof Material system, outdoor sheath, veil, in the structure field, the application of Advertisement with decorative lamp profile, balcony sheath and exit opening.
Therefore the present invention in hereafter, but is not restricted reference example.
Each characteristic is measured according to following standard or method.The measuring method surface gloss:
Surface gloss is measured under 20 ° of measured angular according to DIN67530.Measure the optical parametric of reflector value as thin sheet surface.According to the ASTM-D523-78 and the ISO2813 of standard, incidence angle is set in 20 °.On the test surfaces of under the incidence angle of setting light beam being beaten on the plane, and reflection that makes or scattering.The light beam of beating at photelectric receiver is expressed as with electric weight in direct ratio.Measured value is nondimensional, and must represent with incidence angle.Light transmission:
Light transmission represent the total amount of transmitted light and incident light amount between ratio.
Light transmission is according to ASTM D1003 and use " Hazegard plus " instrument to measure.Preformed casse and clarity;
Preformed casse represents that average deflection incident ray is greater than 2.5 ° transmitted light percentage.Clarity is measured less than 2.5 ° of angles the time.
Preformed casse and clarity are according to ASTM D1003 and use " Hazegard plus " instrument to measure.Blemish:
Blemish is judged with naked eyes.Charpy impact intensity a
n:
Its size is measured according to ISO179/1D.Beam type notched Izod impact strength a
k:
This beam type notched Izod impact strength a
kMeasure according to ISO180/1A.Density:
Density is measured according to DIN53479.SV (DCA) and IV (DCA):
Normal viscosity SV (DCA) measures in dichloroacetic acid according to DIN53728.
Inherent viscosity (IV) is then calculated from normal viscosity (SV) and is got:
IV (DCA)=6.67 * 10
-4SV (DCA)+0.118 thermal characteristics:
Thermal characteristics is as crystalline melt point T
m, crystallization range T
c, the back (cold)-crystallization temperature T
CN, and glass transition temperature T
gMeasure with 10 ℃/minute the rate of heat addition according to differential scanning calorimetry (DSC).Molecular weight and polydispersity:
Molecular weight M
wAnd M
nAnd the polydispersity M of gained
w/ M
nMeasure by gel permeation chromatography (GPC).Wind erosion (on the two sides), UV stability:
UV stability is tested in the following instructions according to ISO4892 test specification: test apparatus: Atlas Ci65 Weather-Ometer experimental condition: ISO 4892, that is artificial wind erosion irradiation time: 1000 hours (every face) irradiation: 0.5W/m
2, 340nm temperature: 63 ℃ of relative atmospheric humidity 50% xenon lamps: the interior external filter exposure period of being made by borosilicate: 102 minutes UV light had water then in 18 minutes and sprays sample
UV light, then in addition 102 minutes UV light, etc.Change color:
The change color of wind erosion back sample is according to DIN 5033 and use spectrophotometer to measure.
Following mark is used: Δ L: luminance difference
+ Δ L; Sample is brighter than standard
-Δ L: sample is than the dark Δ A of standard: red-green area difference
+ Δ A: sample is redder than standard
-Δ A: sample is than the green Δ B of standard: the blue-yellow area difference
+ Δ B: sample is than standard Huang
-Δ B: sample is than standard blue Δ E: total change color
Bigger with the standard value amount of deflection, the difference of color is just higher.
Numerical value≤0.3 o'clock can neglect, and is meaning without any significant change color.Yellow value degree;
Yellow value degree G is from colourless and deviation " yellow ", measures according to DIN6167.Yellow value degree≤5th, invisible.
Each all relates to the single-layer and transparent plate made from different-thickness in embodiment hereinafter and the comparing embodiment on above-mentioned extruded threads.Embodiment 1
The PET that can manufacture transparent panel has 3490 normal viscosity SV (DCA), is 2.45dl/g corresponding to inherent viscosity IV (DCA).Moisture content is＜0.2% and density (DIN 53479) is 1.35g/cm
3Degree of crystallinity is 19%, and is 243 ℃ according to the crystalline melt point of dsc measurement.Crystallization range T
cBetween 82 ℃ and 243 ℃.The polydispersity M of PET
w/ M
nBe 4.3, M wherein
wBe 225070g/mol and M
nBe 52400g/mol.Glass transition temperature is 82 ℃.
Before the extruding, earlier under 170 ℃ in drier dried this PET 5 hours of making an uproar, be that extruding makes and arrives by sheet die on the level and smooth calender that its roller is arranged in S-shape in 292 ℃ the single-screw extrusion machine in extrusion temperature then, and even up to obtain the thin plate of 3 millimeters of thickness.The temperature of first calender roller be 73 ℃ and subsequently each roller each all have 67 ℃ of temperature.Transferring speed and calender roller speed is 6.5 meters/minute.
After the back cooling, use and cut apart the edge that saw is pruned the clear PET plate of 3 millimeters of thickness, and cut and be cut into certain-length and heap again.
The clear PET plate that this makes has following characteristic :-thickness: 3 millimeters-surface gloss, and first: second of 215 (20 ° of measured angular): 214-light transmission: 94%-clarity: every square metre of blemish of 100%-preformed casse: 0.8%-(spot, orange peel, foaming etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.6kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Embodiment 2
Be similar to embodiment 1 and use PET to make transparent panel :-SV (DCA): 2717-IV (DCA): 1.93dl/g-density: 1.38g/cm with following characteristic
3-degree of crystallinity: 44%-M
w: 175640g/mol-M
n: 49580g/mol-crystalline melt point T
m: 245 ℃-crystallization temperature T
c: 82 ℃ to 245 ℃-polydispersity M
w/ M
n: 3.54-glass transition temperature: 82 ℃
Extrusion temperature is 280 ℃.The temperature of first calender roller is 66 ℃, and roller respectively is 60 ℃ of temperature subsequently.Transferring speed and calender roller speed is 2.9 meters/minute.
The clear PET plate that this makes has following characteristic :-thickness: 6 millimeters-surface gloss, first: second of 192 (20 ° of measured angular): 190-light transmission: 92.1%-clarity: every square metre of blemish of 99.8%-preformed casse: 2.0%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.8kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Embodiment 3
Be similar to embodiment 2 and make transparent panel.Extrusion temperature is 275 ℃.The temperature of first calender roller is 57 ℃, and roller respectively is 50 ℃ of temperature subsequently.Transferring speed and calender roller speed is 1.7 meters/minute.
This makes the PET plate and has following characteristic :-thickness: 10 millimeters-surface gloss, first: second of 173 (20 ° of measured angular): 171-light transmission: 88.5%-clarity: every square metre of blemish of 99.4%-preformed casse: 3.2%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
nNo section-beam type notched Izod impact strength a
k: 5.0kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Embodiment 4
Be similar to embodiment 3 and use PET to make transparent panel :-SV (DCA): 3173-IV (DCA): 2.23dl/g-density: 1.34g/cm with following properties
3-degree of crystallinity: 12%-crystalline melt point T
m: 240 ℃-crystallization range T
c: 82 ℃ to 240 ℃-polydispersity M
w/ M
n: 3.66-glass transition temperature: 82 ℃-M
w: 204660g/mol-M
n: 55952g/mol
Extrusion temperature is 274 ℃.The temperature of first calender roller is 50 ℃, and roll temperature is 45 ℃ subsequently.Transferring speed and calender roller speed is 1.2 meters/minute.
This prepared PET plate has following characteristic :-thickness: 15 millimeters-surface gloss, first: second of 162 (20 ° of measured angular): 159-light transmission: 89.3%-clarity: every square metre of blemish of 98.9%-preformed casse: 5.8%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: no section-beam type notched Izod impact strength a
k: 5.1kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Embodiment 5
Be similar to embodiment 2 and make transparent panel.But with 70% take from embodiment 2 PET and 20% recirculation after this PET be blended together.
This prepared PET plate has following characteristic :-thickness: 6 millimeters-surface gloss, first: second of 188 (20 ° of measured angular): 186-light transmission: 92.2%-clarity: every square metre of blemish of 99.6%-preformed casse: 2.2%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.7kJ/m
2-cold forming: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3Embodiment 6
Be similar to embodiment 1 manufacturing one and contain the main component of PET conduct and 1.0 weight %UV stabilizing agent 2-(4,6-diphenyl-1,3,5-triazines-2-the yl)-5-hexyl of taking from embodiment 1) oxy phenol (
Tinuvin 1577, take from Ciba-Geigy company), and thickness is 3 millimeters transparent amorphous plate.The fusing point of Tinuvin 1577 is 149 ℃, and high still is heat endurance to about 330 ℃.
The UV stabilizing agent of 10 weight % directly is incorporated in this PET via raw material manufacturer.
Drying, extruding and technological parameter such as embodiment 1 select.
The clear PET plate that this makes has following characteristic :-thickness: 3 millimeters-surface gloss, first: second of 208 (20 ° of measured angular): 205-light transmission: 92%-clarity: every square metre of blemish of 100%-preformed casse: 1.0%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.6kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3
Use Altas Ci65 Weather-Ometer after every wind erosion 1000 hours, this PET plate shows following properties :-thickness: 3 millimeters-surface gloss, first: second of 202 (20 ° of measured angular): 200-light transmission: 91.7%-clarity: the total variable color Δ of 100%-preformed casse: 1.2%-E: 0.22-is dark-coloured become Δ L :-0.18-red-green variable color Δ A :-0.08-basket-xanthiochromatic Δ B: 0.10-blemish (shattered crack, embrittlement): nothing-yellow value degree G: 4-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.1kJ/m
2-cold formability: good embodiment 7
Being similar to embodiment 6, to make thickness be 3 millimeters transparent amorphous plate.UV stabilizing agent 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-(hexyl) oxy phenol (
Tinuvin 1577) be metered into the masterbatch form.This masterbatch is by 5 weight % as active constituent
Iinuvin 1577 and 95 weight % take from the PET of embodiment 1 and form.
Before the extruding, the dry 80 weight % under 170 ℃ of elder generation take from PET and 20 these masterbatches of weight % of embodiment 1.Extruding and thin plate manufacturing are similar to embodiment 1 and carry out.
This transparent amorphous PET plate that makes has following characteristic :-thickness: 3 millimeters-surface gloss, first: second of 204 (20 ° of measured angular): 201-light transmission: 91.8%-clarity: every square metre of blemish of 100%-preformed casse: 0.9%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.0kJ/m
2-cold formability: good-degree of crystallinity: 0%-density: 1.33g/cm
3
Use Atlas Ci65 Weather-OMeter after every wind erosion 1000 hours, this PET plate shows following properties :-thickness: 3 millimeters-surface gloss, first: second of 200 (20 ° of measured angular): 198-light transmission: 91.7%-clarity: the total variable color Δ of 100%-preformed casse: 1.0%-E: 0.24-is dark-coloured become Δ L :-0.19-red-green variable color Δ A :-0.08-basket-xanthiochromatic Δ B: 0.12-blemish (shattered crack, embrittlement): nothing-yellow value degree G: 5-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.0kJ/m
2-cold formability: good embodiment 8
Be similar to embodiment 2 manufacturings one and contain the UV stabilizing agent 2 of embodiment 2 described PETs as main components and 0.6 weight % (with respect to polymer weight), 2 '-methylene-two (6-(2H-BTA-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol) (
Tinuvin 360, take from Ciba-Geigy company), and thickness is at 6 centimetres transparent amorphous plate.Tinuvin 360 has 195 ℃ fusing point and also have heat endurance when height to 250 ℃.
UV stabilizing agent as embodiment 6,0.6 weight % directly mixes in this PET via raw material manufacturer.
Extrusion temperature is 280 ℃.The temperature of first calender roller is 66 ℃, and the temperature of each roller then is 60 ℃ subsequently.Transferring speed and calender roller speed is 2.9 meters/minute.
This prepared clear PET plate has following characteristic :-thickness: 6 millimeters-surface gloss, first: second of 187 (20 ° of measured angular): 185-light transmission: 91.8%-clarity: every square metre of blemish of 99.6%-preformed casse: 2.5%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
n: 4.8kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
2
Use Atlas Ci65 Weather-Ometer after wind erosion on every 1000 hours, this PET plate shows following properties :-thickness: 6 millimeters-surface gloss, first: second of 182 (20 ° of measured angular): 179-light transmission: 90.9%-clarity: the total variable color Δ of 99.5%-preformed casse: 2.7%-E: 0.56-is dark-coloured become Δ L :-0.21-red-green variable color Δ A :-0.11-basket-xanthiochromatic Δ B :+0.51-blemish (shattered crack, embrittlement): nothing-yellow value degree G: 6-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.6kJ/m
2-cold formability: good, zero defect embodiment 9
Make a transparent amorphous plate as embodiment 8.Extrusion temperature is 275 ℃, and the temperature of first calender roller is 57 ℃, and the temperature of each roller is 50 ℃ subsequently.Transferring speed and calender roller speed is 1.7 meters/minute.This thin plate is as stabilisation as described in the embodiment 3.
This prepared clear PET plate has following characteristic :-thickness: 10 millimeters-surface gloss, first: second of 168 (20 ° of measured angular): 167-light transmission: 88.5%-clarity: every square metre of blemish of 99.2%-preformed casse: 3.95%-(spot, orange peel, foaming, etc.): nothing-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 5.1kJ/m
2-cold formability: good, zero defect-degree of crystallinity: 0%-density: 1.33g/cm
3
Use Atlas Ci65 Weather-Ometer after every wind erosion 1000 hours, this PET plate shows following properties :-thickness: 10 millimeters-surface gloss, first: second of 164 (20 ° of measured angular): 162-light transmission: 88.2%-clarity: the total variable color Δ of 99.1%-preformed casse: 5.0%-E: 0.47-is dark-coloured become Δ L :-0.18-red-green variable color Δ A :-0.09-basket-xanthiochromatic Δ B :+0.42-blemish (shattered crack, embrittlement): nothing-yellow value degree G: 5-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 4.5kJ/m
2-cold formability: good, zero defect comparing embodiment 1
Be similar to embodiment 1 and make transparent panel.Used PET has normal viscosity SV (DCA) 760, corresponding to inherent viscosity IV (DCA) 0.62dl/g.Other characteristics all characteristic with the PET of embodiment 1 are identical, and all in the certainty of measurement scope.Technological parameter and temperature are to select as embodiment 1.Because its viscosity is low, causes the thin plate manufacturing to become infeasible.Fused mass stability is not enough, so that just caves on the calender roller before the fused mass cooling.Comparing embodiment 2
Be similar to embodiment 2, also use the PET of embodiment 2 to make transparent panel.The temperature of first calender roller is 98 ℃, and the temperature of each roller is 92 ℃ subsequently.
Prepared thin plate is very muddy.Light transmission, clarity and glossiness also reduce significantly.This thin plate has blemish and structure.For clear applications, its optical characteristics is unacceptable.
This thin plate that makes has following characteristic :-thickness: 6 millimeters-surface gloss, first: second of 95 (20 ° of measured angular): 93-light transmission: 74%-clarity: every square metre of blemish of 90%-preformed casse: 52%-(spot, orange peel, foaming etc.): bubble orange peel-charpy impact intensity a
n: non-cracking-beam type notched Izod impact strength a
k: 5.0kJ/m
2-cold formability: good-degree of crystallinity: about 8%-density: 1.34g/cm
3
Claims (26)
1. transparent amorphous plate, thickness is in 1 to 20 millimeter scope and contain a crystallisable thermoplastic as main component, wherein this crystallisable thermoplastic according to DIN53728 in dichloroacetic acid measured normal viscosity SV (DCA) in 1800 to 6000 scopes; But except be that one to contain normal viscosity SV (DCA) be 1800 the crystallisable thermoplastic thin plate as main component and UV stabilizing agent.
2. thin plate as claimed in claim 1, wherein this normal viscosity is in 2000 to 5000 scopes.
3. thin plate as claimed in claim 1, wherein this normal viscosity is in 2500 to 4000 scopes.
4. as the thin plate of claim 1-3, wherein surface gloss is greater than 120 according to DIN67530 measurement (20 ° of measured angular).
5. each thin plate of claim as described above, wherein light transmission is measured as greater than 84% according to ASTM D1003.
6. each thin plate of claim as described above, wherein preformed casse is measured as less than 15% according to ASTM D1003.
7. each thin plate of claim as described above, wherein used crystallisable thermoplastic are selected from PET, polybutylene terephthalate, cyclic olefin polymer, and cyclic olefine copolymer.
8. thin plate as claimed in claim 7, wherein used crystallisable thermoplastic is a PET.
9. thin plate as claimed in claim 8, wherein PET contains the PET of recirculation.
10. as the thin plate of claim 8 or 9, wherein measure charpy impact intensity a according to ISO179/1D
nFracture appears in Shi Buhui.
11. as each thin plate of claim 8-10, wherein beam type notched Izod impact strength a
kBe measured as 2.0 to 8.0kJ/m according to ISO180/1A
2In the scope.
12. as each thin plate of claim 8-11, wherein clarity is measured as greater than 96% under less than 2.5 ° of angles according to ASTMD1003.
13. as each thin plate of claim 8-12, wherein the crystalline melt point of PET is by DSC and be measured as under 10 ℃ of/minute rates of heat addition in 220 ° to 280 ℃ scopes.
14. as each thin plate of claim 8-13, wherein the crystallization range of PET is by DSC and be measured as under 10 ℃ of/minute rates of heat addition in 75 ° to 280 ℃ scopes.
15. as each thin plate of claim 8-14, wherein used PET has the degree of crystallinity in 5 to 65% scopes.
16., wherein contain at least a UV light stabilizer and make bright protective agent as each thin plate of claim.
17. as the thin plate of claim 16, wherein the concentration of UV stabilizing agent is in 0.01 to 5 weight %, with respect to the weight of this crystallisable thermoplastic.
18. as the thin plate of claim 16 or 17, wherein the UV stabilizing agent is selected from 2-hydroxyl-benzotriazole compound and compound in triazine class.
19. each the method for transparent amorphous plate of manufacturing such as claim 1-18, the method is included in and melts crystallisable thermoplastic in the extruder, fused mass is pressed through a die head, be furnished with calibration in the calender of at least two rollers, level and smooth and cooling and this thin plate cut in one subsequently and be cut into certain size, wherein first roller of calender has 50 to 80 ℃ temperature.
20. as the method for claim 19, wherein crystallisable thermoplastic and UV stabilizing agent one arise from the extruder and melt.
21. as the method for claim 19 or 20, wherein crystallisable thermoplastic carries out drying before fusing.
22. as each method of claim 19 to 21, wherein crystallisable thermoplastic is PET (PET).
23. as the method for claim 22, wherein PET is following dry 4 to 6 hours at 160 to 180 ℃ before extruding.
24. as the method for claim 22 or 23, wherein the temperature of PET fused mass is in 250 to 320 ℃ of scopes.
25. as each method of claim 20-24, wherein the UV stabilizing agent adds via the masterbatch technology.
26. as each transparent amorphous plate of claim 1-18 in indoor and outdoor application.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19528336.8 | 1995-08-02 | ||
| DE19528336A DE19528336A1 (en) | 1995-08-02 | 1995-08-02 | Amorphous, transparent plate made of a crystallizable thermoplastic with high standard viscosity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1196698A true CN1196698A (en) | 1998-10-21 |
Family
ID=7768478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96197028A Pending CN1196698A (en) | 1995-08-02 | 1996-07-15 | Amorphous transparent plate of crystallisable thermoplast with high standard viscosity |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0842039A1 (en) |
| JP (1) | JPH11510112A (en) |
| KR (1) | KR19990036024A (en) |
| CN (1) | CN1196698A (en) |
| AU (1) | AU6699096A (en) |
| BG (1) | BG102212A (en) |
| BR (1) | BR9610186A (en) |
| CA (1) | CA2228364A1 (en) |
| CZ (1) | CZ30098A3 (en) |
| DE (1) | DE19528336A1 (en) |
| HU (1) | HUP9802435A2 (en) |
| NO (1) | NO980393L (en) |
| OA (1) | OA10662A (en) |
| PL (1) | PL324868A1 (en) |
| TW (1) | TW355718B (en) |
| WO (1) | WO1997004948A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19535180A1 (en) * | 1995-09-22 | 1997-03-27 | Hoechst Ag | Use of thermoplastic, amorphous polyethylene terephthalate plates in refrigeration systems |
| US6063465A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester container and method for making same |
| US6025061A (en) * | 1998-04-23 | 2000-02-15 | Hna Holdings, Inc. | Sheets formed from polyesters including isosorbide |
| US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
| US6140422A (en) * | 1998-04-23 | 2000-10-31 | E.I. Dupont De Nemours And Company | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
| US5958581A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyester film and methods for making same |
| US6063495A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester fiber and methods for making same |
| US5959066A (en) * | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
| US6126992A (en) * | 1998-04-23 | 2000-10-03 | E.I. Dupont De Nemours And Company | Optical articles comprising isosorbide polyesters and method for making same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK120505B (en) * | 1964-12-03 | 1971-06-07 | Glanzstoff Ag | Process for the preparation by the vacuum deep drawing method of moldings of polyethylene terephthalate. |
| CA965895A (en) * | 1969-10-09 | 1975-04-08 | Herbert F. Kuhfuss | Transparent crystalline polyester film |
| CH550060A (en) * | 1972-03-01 | 1974-06-14 | Ciba Geigy Ag | PROCESS FOR MANUFACTURING POLYESTER DEEP-DRAWING MOLDED PARTS. |
| US3950301A (en) * | 1974-08-01 | 1976-04-13 | General Electric Company | Light stabilized polyester resin composition |
| US4230656A (en) * | 1975-10-23 | 1980-10-28 | Allied Chemical Corporation | Transparent sheets and containers formed from polycarbonate-polyester blends and formation thereof |
| DE2928055A1 (en) * | 1978-07-12 | 1980-01-31 | Eastman Kodak Co | METHOD FOR IMPROVING THE RESISTANCE OF POLYESTER MOLDED BODIES TO DEGRADATION BY U.V. LIGHT |
| JPS57212053A (en) * | 1981-06-23 | 1982-12-27 | Nippon Sheet Glass Co Ltd | Laminated panel |
| JP2918616B2 (en) * | 1990-03-27 | 1999-07-12 | ポリプラスチックス株式会社 | Transparent polyester container and method for producing the same |
| IE68430B1 (en) * | 1990-08-12 | 1996-06-12 | Polysheet Ireland Ltd | A method and apparatus for forming an article of PET material |
-
1995
- 1995-08-02 DE DE19528336A patent/DE19528336A1/en not_active Withdrawn
-
1996
- 1996-07-15 CZ CZ98300A patent/CZ30098A3/en unknown
- 1996-07-15 KR KR1019980700689A patent/KR19990036024A/en not_active Application Discontinuation
- 1996-07-15 JP JP9507164A patent/JPH11510112A/en active Pending
- 1996-07-15 HU HU9802435A patent/HUP9802435A2/en unknown
- 1996-07-15 EP EP96927002A patent/EP0842039A1/en not_active Withdrawn
- 1996-07-15 CA CA002228364A patent/CA2228364A1/en not_active Abandoned
- 1996-07-15 WO PCT/EP1996/003089 patent/WO1997004948A1/en not_active Application Discontinuation
- 1996-07-15 BR BR9610186A patent/BR9610186A/en not_active Application Discontinuation
- 1996-07-15 PL PL96324868A patent/PL324868A1/en unknown
- 1996-07-15 AU AU66990/96A patent/AU6699096A/en not_active Abandoned
- 1996-07-15 CN CN96197028A patent/CN1196698A/en active Pending
- 1996-07-30 TW TW085109483A patent/TW355718B/en active
-
1998
- 1998-01-28 BG BG102212A patent/BG102212A/en unknown
- 1998-01-29 NO NO980393A patent/NO980393L/en unknown
- 1998-02-02 OA OA9800018A patent/OA10662A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO980393D0 (en) | 1998-01-29 |
| TW355718B (en) | 1999-04-11 |
| BG102212A (en) | 1998-10-30 |
| WO1997004948A1 (en) | 1997-02-13 |
| KR19990036024A (en) | 1999-05-25 |
| BR9610186A (en) | 1999-07-06 |
| AU6699096A (en) | 1997-02-26 |
| JPH11510112A (en) | 1999-09-07 |
| DE19528336A1 (en) | 1997-02-06 |
| OA10662A (en) | 2002-11-20 |
| EP0842039A1 (en) | 1998-05-20 |
| HUP9802435A2 (en) | 1999-02-01 |
| CZ30098A3 (en) | 1998-07-15 |
| CA2228364A1 (en) | 1997-02-13 |
| NO980393L (en) | 1998-01-29 |
| PL324868A1 (en) | 1998-06-22 |
| MX9800940A (en) | 1998-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2169158C2 (en) | Method of manufacturing transparent amorphous plate from crystallizable thermoplastic, and plate manufactured by this method | |
| RU2164926C2 (en) | Amorphous transparent plate from crystallizable thermoplastic and method of manufacture thereof | |
| ES2536545T3 (en) | Method of manufacturing a sheet or a strip of sheet from a polymer mixture of vinyl chloride or polyvinyl chloride and sheet produced with it | |
| JP5972406B2 (en) | Hydrolysis resistant polyester film | |
| RU2160666C2 (en) | Amorphous transparently dyed plate of crystallizable plastic, method for its manufacture and use | |
| CN1196698A (en) | Amorphous transparent plate of crystallisable thermoplast with high standard viscosity | |
| CN107474442A (en) | A kind of PVC board and its preparation technology | |
| CN102892819B (en) | Laser-transparent polyester | |
| CN103619931A (en) | Laser-transparent polyester containing alkali nitrites | |
| US11198781B2 (en) | Polyvinyl chloride, polycarbonate and copolyester compositions and articles made using these compositions | |
| CN113166511B (en) | Polyvinyl chloride, polycarbonate and copolyester compositions and articles made using these compositions | |
| EP3642278B1 (en) | Polyvinyl chloride and copolyester compositions and articles made using these compositions | |
| CN1660937A (en) | Black lighttight type polyester film and preparation method | |
| KR20000017460A (en) | Fiber-reinforced polyester resin molding material and its production process and molded product | |
| JPH11512667A (en) | Amorphous molded product manufactured from polyethylene terephthalate sheet | |
| KR20230025445A (en) | Polyvinyl chloride, polycarbonate and copolyester compositions and articles made using these compositions | |
| MXPA98000940A (en) | Lamina amorfa transparent of a crystallized thermoplastic with a normal viscosity a | |
| JPH07126404A (en) | Uv absorber-containing resin molded product and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1022314 Country of ref document: HK |