CN104553201A - Composite board - Google Patents
Composite board Download PDFInfo
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- CN104553201A CN104553201A CN201510028261.9A CN201510028261A CN104553201A CN 104553201 A CN104553201 A CN 104553201A CN 201510028261 A CN201510028261 A CN 201510028261A CN 104553201 A CN104553201 A CN 104553201A
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- composite board
- poly ester
- modified poly
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a composite board, and mainly aims at solving the problem that an apparatus which is prepared by plastic sucking molding of a polymer board in the prior art is poor in surface decoration effect. By virtue of the technical scheme that the composite board comprises a polymer base material (1) and a surface film (2), wherein the polymer base material (1) is attached to the surface film (2), or the composite board comprises the polymer base material (1), the surface film (2) and a metalized layer (3), wherein the metalized layer (3) is compounded between the polymer base material (1) and the surface film (2), the technical problem is relatively well solved. The composite board can be applied to industrial production of the composite board.
Description
Technical field
The present invention relates to a kind of composite board.
Background technology
Polymer plate conventional in prior art only has single polymeric substrate composition, thus the device that obtains through plastics sucking moulding of sheet material or article surface rough, lack color or lack the surface decoration effect such as metallic luster that people expect.In prior art, in order to obtain metallic luster, usually need a large amount of metal materials, but due to the proportion of metal comparatively large, aluminium alloy is directly used in case and bag by tradition, its cost and empty weight heavier, directly affects use.Market also adopts type metal powder ink, the method for plated metal is produced and had the case and bag plate of metallic luster on Case outer-shell, the former metallic luster weak effect, the metal level of the latter is very easy to wearing and tearing.For solving these technical problems, need the polymer plate that exploitation has surface film badly.
The existing polymeric material for case and bag matrix has a lot.The matrix case and bag of case board can be main modified polymer material with ABS, PC, PP, PETG, PET, PBT and above-mentioned material, and most popular is ABS and PC sheet material.Poisonous during ABS plate burning, PC plate processing difficulties, cost is high.Can by two or more polymer in appropriate ratio under the condition such as uniform temperature and shear stress, formed by melt blending and there is blend polymer or the alloy of new performance.Key prepared by this blend polymer is the compatibility between polymer.If make two or more incompatible polymer reach mutually perhaps partially compatible, Specific Interactions technology etc. can be adopted between compatilizer technology, reactive extrusion technology, Interpenetrating Polymer Network Technology and polymer molecule, and adopts expressing technique to become plate.Modified poly ester raw material is extensive, and nontoxic, environmental protection, can repeatedly reclaim, and is good selection, but the plastic uptake processing characteristics of existing modified poly ester is not ideal enough.
Poly-diacid diol ester, especially PETG (being called for short PET) are conventional thermoplastic polyesters.But different field, varies to the requirement of polyester property, in order to meet the needs of different field different performance, arisen at the historic moment in prior art various different modified poly ester and method of modifying different accordingly.
CN1566180A discloses a kind of method preparing modified poly ester, and it adopts terephthalic acid (TPA), M-phthalic acid and ethylene glycol to be that comonomer obtains by copolymerization taking isophthalic acid as the modified poly ester of modifier.
CN 102964574 A discloses a kind of method of modified poly ester and modification thereof, and it adopts M-phthalic acid, neopentyl glycol, 1,4-CHDM, terephthalic acid (TPA) and ethylene glycol copolymerization to obtain modified poly ester.Because M-phthalic acid, neopentyl glycol and 1,4-CHDM are as modifier, the shrinkage factor of modified poly ester can not only be improved, and its fragility can be reduced, make it as during bottle label, the phenomenons such as fracture can not occur, improve yield rate.
CN 102964575 A discloses a kind of modified poly ester and preparation method thereof, and it adopts M-phthalic acid, neopentyl glycol, terephthalic acid (TPA) and ethylene glycol copolymerization to obtain modified poly ester.M-phthalic acid and neopentyl glycol can not only improve the shrinkage factor of modified poly ester as modifier, and can reduce its fragility, make it as during bottle label, the phenomenons such as fracture can not occur, and improve yield rate.
CN 102964576 A discloses a kind of modified poly ester and preparation method thereof, and it adopts M-phthalic acid, terephthalic acid (TPA), 1,4-CHDM and ethylene glycol copolymerization to obtain modified poly ester, and it has higher film and draws high intensity and elongation at break.
CN 103665352 A discloses the preparation method that environment-friendly type covers the dedicated modified polyester slice of iron, and it adopts ethylene glycol, 1,4-CHDM, neopentyl glycol, terephthalic acid (TPA), M-phthalic acid copolymerization obtains modified poly ester
CN 103755941 A discloses a kind of method of modifying of polyester, and polyester and chain extender carry out being obtained by reacting required modified poly ester by it.
But the sheet material plastic uptake poor processability that modified poly ester of the prior art is obtained.
Summary of the invention
Technical problem to be solved by this invention is the rough problem lacking surface decoration effect of device surface that the polymer plate existed in prior art obtains through plastics sucking moulding, a kind of composite board is provided, this composite board can provide smooth surface, and color or metallic luster etc. can be provided easily as required, there is good surface decoration effect.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of composite board, it is characterized in that described composite board comprises polymeric substrate 1 and surface film 2, and described polymeric substrate 1 fits with described surface film 2; Or the metal layer 3 that described composite board comprises polymeric substrate 1, surface film 2 and is compound between polymeric substrate 1 and surface film 2.
In technique scheme, the material of described base material 1 can be selected from least one polymer in ABS, PC, PP, PETG, PET and PBT or polymer-modified based at least one in them.
In technique scheme, the material of described surface film 2 can be and is selected from least one polymer in PC, PP, PETG, PET and PBT or polymer-modified based at least one in them.In order to give surface film 2 with color, before preparing surface film, required dyestuff or color can be added in surface film 2 process raw material; Also can form at the surface printing of the surface film 2 made, when adopting the mode of printing, surface film 2 not only can be made to have required color, can also give easily by the pattern of Color constitut.
In technique scheme, the thickness of described surface film 2 is not particularly limited, and those skilled in the art can choose reasonable.Thickness such as but not limited to described surface film 2 is 0.05 ~ 0.5mm.
Polymeric substrate 1 and surface film 2 are comprised for composite board described above, the technical scheme that described polymeric substrate 1 fits with described surface film 2, additional or not additional tack coat between polymeric substrate 1 and described surface film, when not additional tack coat, the method that hot pressing can be adopted to fit makes described polymeric substrate 1 and surface film 2 be bonded together formation composite board.
Polymeric substrate 1, surface film 2 are comprised for composite board described above and is compound in the technical scheme of the metal layer 3 between polymeric substrate 1 and surface film 2, described metal layer 3 preparation method can adopt those methods existing in prior art, such as but not limited to the metal layer 3 that methods such as adopting vacuum evaporation metallic film technique, electroplating technology is formed.In order to improve metal layer 3 and the adhesion of surface film 2, appropriate primer can be coated with in advance on surface film 2, then through vacuum evaporation metal.In order to improve the adhesion with base material 1, one deck adhering resin can be coated with on the metal layer.Metal in metal layer 3 is not particularly limited, and can carry out choose reasonable according to required metallic luster.The such as metal of described metal layer 3 is but at least one or multiple be not limited in gold, silver, copper, zinc, chromium and aluminium.The thickness of metal layer 3 is not particularly limited, but selective metal layer thickness is 0.01 ~ 1nm usually.
In technique scheme, described base material 1 and/or surface film 2 are preferably obtained by following modified poly ester composition; Described modified poly ester composition, containing modified poly ester 60 ~ 95wt% and flexibilizer 5 ~ 40wt%; Wherein said modified poly ester, inherent viscosity is 0.7 ~ 1.4dl/g, and fusing point is 170 ~ 240 DEG C, and employing comprises the reaction raw materials copolymerization of crosslinking agent, modifier, terephthalic acid (TPA) and ethylene glycol and obtains; There is in the molecule of described crosslinking agent the functional group that can form at most more than 3 or 3 crosslinked links in described modified poly ester; Described modifier is selected from diacid modifiers and/or glycol modification agent, has 2 hydroxy-acid groups in described modified agent molecule, has 2 alcoholic extract hydroxyl groups in described glycol modification agent molecule; With molar ratio computing (terephthalic acid (TPA)+diacid modifiers): (ethylene glycol+glycol modification agent): crosslinking agent is for 1:(1.1 ~ 2.0): (0.001 ~ 0.005), the mol ratio of diacid modifiers and terephthalic acid (TPA) is a, and the mol ratio of glycol modification agent and ethylene glycol is b; A+b=0.10 ~ 0.45.Now described base material 1 has good plastic uptake processing characteristics.Further preferred surface film 2 also adopts above-mentioned modified poly ester composition to obtain, now polymeric substrate 1 and surface film 2 are comprised for described composite board, the technical scheme that described polymeric substrate 1 fits with described surface film 2, fit more firm between base material 1 and surface film, polymeric substrate 1 is comprised for described composite board, surface film 2 and be compound in the technical scheme of the metal layer 3 between polymeric substrate 1 and surface film 2, combination between polymeric substrate 1 and metal layer 3 is more firm, and combine also more firm between metal layer 3 and surface film 2.
Those skilled in the art will know that, in composite board, the plastic uptake processing characteristics of base material 1 determines the plastic uptake processing characteristics of composite board, the volume that surface film 2 accounts in composite board is very little, and it mainly plays decoration, very micro-on the plastic uptake processing characteristics impact of composite board.Therefore, base material 1 has good blister performance and also just determines described composite board and also have good plastic uptake processing characteristics.
In technique scheme, described inherent viscosity preferably 0.7 ~ 1.2dl/g, more preferably 0.74 ~ 1.0dl/g.
In technique scheme, described fusing point preferably 180 ~ 230 DEG C, most preferably 190 ~ 230 DEG C.
In technique scheme, in a and b, one of them can be 0 can not be all 0 yet.Such as during b=0, technique scheme becomes: (terephthalic acid (TPA)+diacid modifiers): ethylene glycol: crosslinking agent is 1:(1.1 ~ 2.0): (0.001 ~ 0.005), the mol ratio of diacid modifiers and terephthalic acid (TPA) is a, a=0.10 ~ 0.45.Again during such as a=0, technique scheme becomes: terephthalic acid (TPA): (ethylene glycol+glycol modification agent): crosslinking agent is 1:(1.1 ~ 2.0): (0.001 ~ 0.005), the mol ratio of diacid modifiers and terephthalic acid (TPA) is b, b=0.10 ~ 0.45.But when a and b is not all 0, the base material 1 obtained compared with modified poly ester composition described when one of them is 0 in a and b has better plastic uptake processing characteristics.
In technique scheme, with molar ratio computing (terephthalic acid (TPA)+diacid modifiers): (ethylene glycol+glycol modification agent): crosslinking agent is preferably 1:(1.1 ~ 1.5): (0.001 ~ 0.005).
In technique scheme, when composite board base material 1 of the present invention adopt obtained by described modified poly ester composition time, key problem in technology is described modified poly ester, and is not particularly limited the kind of flexibilizer, all can reach the effect of plastic uptake good processability.But described flexibilizer is preferably from LLDPE (LLDPE), ultra-low density polyethylene (VLLDPE), Hydrogenated thermoplastic's butadiene-styrene rubber (SEBS), polypropylene (PP), ethylene-propylene copolymer, ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA), at least one in the butadiene-styrene rubber (SBR-g-MAH) of ethylene-methacrylic acid copolymer (EMMA), ethylene-methyl methacrylate ethylene oxidic ester (GMA) and maleic anhydride graft.
In technique scheme, at least one of described crosslinking agent preferably in the acid anhydrides of polyalcohol, polyacid or polyacid, described polynary be more than 3 yuan or 3 yuan.First number polynary herein can be integer such as but not limited to 3 yuan, 4 members, 5 yuan, 6 yuan, 7 yuan etc.; Unit's number also can be decimal.Can be obtained by mixing in required ratio with the crosslinking agent of different unit.The number of the crosslinked link that the acid anhydrides of described polyalcohol, polyacid or polyacid can be formed at most in described modified poly ester is identical with described first number.
In technique scheme, described crosslinking agent more preferably comprises polyalcohol and polyacid simultaneously, or more preferably comprises the acid anhydrides of polyalcohol and polyacid simultaneously.Now, in the plastics sucking moulding improving modified poly ester base material 1, there is obvious synergy, particularly reducing be full of cracks, hang in stream or the probability that turns white there is obvious synergy.
In technique scheme, at least one of described polyalcohol preferably in pentaerythrite, bipentaerythrite, tripentaerythritol, trimethylolpropane, trimethylolethane and glycerine.
In technique scheme, the acid anhydrides of described polyacid is preferably pyromellitic acid anhydride.
In technique scheme, at least one of described polyacid preferably in trimesic acid and Pyromellitic Acid.
In technique scheme, described diacid modifiers is preferably M-phthalic acid and/or adipic acid; More preferably adopt M-phthalic acid and adipic acid simultaneously, M-phthalic acid and adipic acid reducing be full of cracks, hang stream and in the probability that occurs of turning white, there is synergy.
In technique scheme, described glycol modification agent is preferably neopentyl glycol and/or BDO, more preferably adopts neopentyl glycol and BDO simultaneously, and neopentyl glycol and BDO have synergy reducing to hang in stream and the probability that turns white.
Enumerate as the non-limiting of embodiment, described modified poly ester can be obtained by following embodiment:
Embodiment 1: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pentaerythrite;
Embodiment 2: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pyromellitic acid anhydride;
Embodiment 3: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, ethylene glycol and Pyromellitic Acid;
Embodiment 4: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride;
Embodiment 5: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride;
Embodiment 6: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride;
Embodiment 7: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, adipic acid, neopentyl glycol, ethylene glycol, pentaerythrite and pyromellitic acid anhydride;
Embodiment 8: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, adipic acid, BDO, ethylene glycol, pentaerythrite and pyromellitic acid anhydride;
Embodiment 9: obtained by the reaction raw materials copolymerization comprising terephthalic acid (TPA), M-phthalic acid, adipic acid, neopentyl glycol, BDO, ethylene glycol, pentaerythrite and pyromellitic acid anhydride.
The inherent viscosity of described modified poly ester is adopted and is measured with the following method:
5.1.1 method A (capillary viscosimetry) in GB/T 14190-2008 " fiber polyester chip (PET) test method ".
The fusing point of described modified poly ester is adopted and is measured with the following method:
5.3.1 method A (microscopic method) in GB/T 14190-2008 " fiber polyester chip (PET) test method ".
In technique scheme, described modified poly ester preferably adopts the method preparation comprised the steps:
(1) make described reaction raw materials carry out esterification and obtain carboxylate;
(2) precondensation;
(3) polycondensation.
In technique scheme, the temperature of described esterification is preferably 240 ~ 280 DEG C.
In technique scheme, described esterification preferably proceeds to esterification yield and is at least 95%, and such as 95 ~ 99%.The formula that wherein esterification yield is natural is defined as follows:
The weight of esterification yield %=[esterification actual generation water/(in reaction raw materials hydroxyl and carboxyl by the thorough esterification of metering generate the weight of water)] × 100%.
In technique scheme, the temperature of described prepolymerization reaction is preferably 260 ~ 290 DEG C.
In technique scheme, the reaction time of described prepolymerization reaction is preferably 0.5 ~ 2 hour.
In technique scheme, during prepolymerization reaction, reaction pressure is preferably transitioned into 500 ~ 700Pa gradually from atmospheric pressure.The transition of reaction pressure can be realized by vacuum pumping.
In technique scheme, the condition of described prepolymerization reaction is more optimizedly: the temperature of described prepolymerization reaction is 260 ~ 290 DEG C, the reaction time of described prepolymerization reaction is 0.5 ~ 2 hour, and during prepolymerization reaction, reaction pressure is transitioned into 500 ~ 700Pa gradually from atmospheric pressure.
In technique scheme, the temperature of described polycondensation reaction is preferably 270 ~ 290 DEG C.
In technique scheme, the pressure preferably 60 ~ 100Pa of described polycondensation reaction.
In technique scheme, described polycondensation reaction time preferably 2 ~ 5 hours.
In technique scheme, the condition of described polycondensation reaction more preferably: the temperature of described polycondensation reaction is 270 ~ 290 DEG C, and the pressure preferably 60 ~ 100Pa of described polycondensation reaction, described polycondensation reaction time is 2 ~ 5 hours.
In technique scheme, one skilled in the art will appreciate that esterif iotacation step can add catalyst, also can without catalyst.Precondensation and polycondensation need to add polymerization catalyst usually.Polymerization catalyst is not particularly limited, and conventional those in polyester field all may be used for the present invention.Described polymerization catalyst is such as but is not limited to antimony system polymerization catalyst, titanium system polymerization catalyst.Exemplifying as antimony system polymerization catalyst is nonrestrictive, can be at least one in antimony glycol, antimony oxide or antimony acetate.When esterif iotacation step adds catalyst, polymerization catalyst can be added in esterif iotacation step, these polymerization catalysts also can play the effect of catalyst in esterif iotacation step.As for the consumption of catalyst, be not particularly limited, such as with the gross weight of esterification raw material for benchmark, the consumption of catalyst can be but be not limited to 0.005% ~ 0.1%, more usually 0.01 ~ 0.1%.
After esterif iotacation step (such as but not limited to after esterif iotacation step and precondensation before), can according to the other side performance of modified poly ester need add those common auxiliary agents of this area.These auxiliary agents are such as but are not limited at least one in antioxidant, fire retardant, delustering agent, pigment, ultra-violet stabilizer etc.
In described modified poly ester composition, except modified poly ester and flexibilizer, those additives can also commonly used containing other this area, these additives are such as but are not limited at least one in antioxidant, fire retardant, delustering agent, pigment, ultra-violet stabilizer etc.
After the structure disclosing described composite board, the surface decoration effect of surface film to composite board it is expected to.
Described composite board can make various device or article through plastics sucking moulding, and such as described device or article can be but be not limited to Case outer-shell, automotive trim, inner container of icebox, appliance shell, bumper, crisper, packing box, storage tank etc.
The preparation of the base material 1 of described composite board, the mode that required material pellet or powder can be adopted to be extruded by flat-die after screw extruder is blended obtains, and those skilled in the art will know that double screw extruder is better than single screw extrusion machine.
In the specific embodiment of the invention base material 1 of table 2 composite board performance in involved base material all adopt following preparation method to obtain:
The Korea S SK of the modified poly ester and 20wt% of getting 80wt% produces, the trade mark is the LLDPE of FV149M, the pellet of described modified poly ester and LLDPE is simply mixed, then adopt double screw extruder to carry out blended and flat-die and extrude that to obtain thickness be 2.8mm, width is the base material of 660mm.
Adopt the ZSE 60MAXX type double screw extruder that the auspicious hereby machinery of Leicester (granary) Co., Ltd produces in the specific embodiment of the invention, screw diameter OD is 61.9mm.
The operating parameter of the double screw extruder that the base material related in the specific embodiment of the invention adopts in preparation is: screw rod operating rate is 100rpm, operating temperature (from spout to die head): first paragraph 160 DEG C, second segment 210 DEG C, the 3rd section 230 DEG C, the 4th section and the 5th section 250 DEG C, the 6th section 240 DEG C, the 7th and the 8th section 230 DEG C, the 9th and the tenth section 220 DEG C, the 11 and the 12 section be 210 DEG C.
In the specific embodiment of the invention, the performance test methods of base material 1 is as follows:
Tensile stress (fracture, 23 DEG C), adopts ASTM D256 method;
Elongation strain (fracture, 23 DEG C), adopts ASTM D256 method;
Bending modulus (23 DEG C), adopts ASTM D796 method;
Izod notched impact strength (local fracture, 23 DEG C), adopts ASTM D368 method.
The HL-211 type plastic suction forming apparatus that the plastic uptake processing characteristics data acquisition of the base material 1 of specific embodiment of the invention table 3 manufactures with Ningbo Heng Yan packaging facilities factory, is obtained by following concrete plastic uptake step:
A, corresponding for above-mentioned table 2 base material 1 is cut into the base material unit that thickness is 2.8mm, width is 660mm, length is 860mm;
B, sheet unit is placed in fixed position, is then pressed down by fixture, pin;
C, described base material unit is advanced heating clamber, carry out thermoplastic, heating-up temperature is 150 DEG C, and the heat time is 60 seconds;
D, softening base material unit to be released, with 25 DEG C of compressed air inflations, about 3 seconds inflation time, time delay 1 second;
E, then make by bleeding base material unit and mould fit, and maintain base material unit and the mould time of laminating is 10 seconds;
F, cooling, on shaping base material unit, blown by air-cooler and cool, gassing time about 15 seconds, then carries out water-spraying control, makes base material unit fast cooling;
7, the demoulding, obtains Case outer-shell.
Plastic uptake processing characteristics data in table 3 are that 100 corresponding base material unit carry out 100 parallel plastic uptakes and test the result obtained.
The various phenomenons of not wishing to see occurred in plastic uptake test are different on plastics sucking moulding impact.Endangering maximum is blow quick-fried, directly causes plastics sucking moulding failure; The be full of cracks that the successful basis of plastics sucking moulding occurs, extension are flowed or turn white, the Case outer-shell quality defect causing plastics sucking moulding to obtain.Different according to the probability that corresponding phenomenon occurs, by as follows for result classification:
Best: the probability that corresponding phenomenon occurs is 0% ~ be less than 5%;
Better: the probability that corresponding phenomenon occurs is 5% ~ be less than 20%;
Poor: the probability that corresponding phenomenon occurs is 20% ~ be less than 60%;
The poorest: the probability that corresponding phenomenon occurs is 60% ~ 100%.
Illustrate that the present invention is described in detail with detailed description of the invention below in conjunction with accompanying drawing.
Detailed description of the invention
[embodiment 1]
1, the preparation of modified poly ester
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pentaerythrite, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol: pentaerythrite is for 1:1.2:0.003, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
[comparative example 1]
1, the preparation of modified poly ester
Do not adopt crosslinking agent as different from Example 1, be specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol is for 1:1.2, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
By embodiment in table 2 and table 31 and the data of comparative example 1 are compared known, because modified poly ester adds crosslinking agent in preparation process, improve the tensile stress of base material, draw high strain, bending modulus and impact strength.The more important thing is the plastic uptake processing characteristics that improve base material, be embodied in significantly reduce and blow the raw probability of outburst, and reduce be full of cracks and hang the probability flowing and occur
[embodiment 2]
1, the preparation of modified poly ester
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol: pyromellitic acid anhydride is for 1:1.2:0.003, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
[embodiment 3]
1, the preparation of modified poly ester
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride is for 1:1.2:0.0015:0.0015, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
As can be seen from the plastics sucking moulding result of the test of embodiment 3 and embodiment 1 and embodiment 2, pentaerythrite and pyromellitic acid anhydride reducing be full of cracks, hang in stream or the probability that turns white there is obvious synergy.
[embodiment 4]
1, the preparation of modified poly ester
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride is for 1:1.2:0.0015:0.0015, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .0 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polymerase 17 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
As can be seen from embodiment 4 and embodiment 3 on year-on-year basis, polymerisation reaches 3.5 hours polymerisations and carries out very abundant, then it is less to extend the performance impact of polymerisation to base material.
[comparative example 2]
Be that crosslinking agent adds after polymerization procedure with embodiment 3 main distinction, specific as follows:
1, the preparation of polyester
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid): ethylene glycol is for 1:1.2, the mol ratio of M-phthalic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, at the reaction pressure of 80Pa and the reaction temperature polyase 13 .5 hour of 285 DEG C, add pentaerythrite and the pyromellitic acid anhydride of respective amount in the esterification raw material with embodiment 3, continue at the reaction pressure of 80Pa and the reaction temperature polyase 13 .5 hour of 285 DEG C, water-cooled is cut into slices, and adds the Modified polyester chips of crosslinking agent after obtaining.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
By the data of comparative example in table 32 with embodiment 3 or embodiment 4 are compared and can find out, modified poly ester owing to adding crosslinking agent in esterification raw material, and the plastic uptake processing characteristics of base material is far superior to adopt carries out modification with crosslinking agent to polyester again after polymerisation has completed or substantially completed.
[embodiment 5]
1, the preparation of modified poly ester
Be to replace M-phthalic acid with adipic acid with the main distinction of embodiment 3, be specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+adipic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride is for 1:1.2:0.0015:0.0015, the mol ratio of adipic acid and terephthalic acid (TPA) is 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
[embodiment 6]
1, the preparation of modified poly ester
Be with embodiment 3 main distinction, the diacid modifiers of embodiment 3 only adopts M-phthalic acid, and the diacid modifiers that the present embodiment adopts is M-phthalic acid and adipic acid, is specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride is for 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): the mol ratio of terephthalic acid (TPA) is 0.2, M-phthalic acid: adipic acid mol ratio is 1; Polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
As can be seen from embodiment 6 and embodiment 5 and embodiment 1 on year-on-year basis, M-phthalic acid and adipic acid are in the plastic uptake processing characteristics improving base material, there is the interaction being better than simple superposition, reducing be full of cracks, hang stream and in the probability of generation of turning white, there is synergy both being embodied in.
[embodiment 7]
1, the preparation of modified poly ester
Be to additionally use neopentyl glycol as glycol modification agent with the main distinction of embodiment 6, be specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, neopentyl glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): (ethylene glycol+neopentyl glycol): pentaerythrite: pyromellitic acid anhydride is for 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): the mol ratio of terephthalic acid (TPA) is 0.2, M-phthalic acid: adipic acid mol ratio is 1, neopentyl glycol: ethylene glycol mol ratio is 0.2; Polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
[embodiment 8]
1, the preparation of modified poly ester
Be to adopt BDO to replace neopentyl glycol as glycol modification agent with the main distinction of embodiment 7, be specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, 1,4-butanediol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): (ethylene glycol+1,4-butanediol): pentaerythrite: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): the mol ratio of terephthalic acid (TPA) is 0.2, M-phthalic acid: adipic acid mol ratio is 1, BDO: ethylene glycol mol ratio is 0.2; Polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
[embodiment 9]
1, the preparation of modified poly ester
Be with the main distinction of embodiment 7, the present embodiment adopts BDO and neopentyl glycol as glycol modification agent simultaneously, is specially:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, 1, 4-butanediol, neopentyl glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): (ethylene glycol+1, 4-butanediol+neopentyl glycol): pentaerythrite: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): the mol ratio of terephthalic acid (TPA) is 0.2, M-phthalic acid: adipic acid mol ratio is 1, (1, 4-butanediol+neopentyl glycol): ethylene glycol mol ratio is 0.2, 1, 4-butanediol: neopentyl glycol mol ratio is 1, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen replaces 3 times, carries out esterification at 250 DEG C, steams the water that esterification generates simultaneously, be 97%, obtain esterification material to esterification yield in esterification reaction process.
Then, be 270 DEG C in temperature and carry out prepolymerization reaction under vacuumizing situation and obtain prepolymer in 1.5 hours, between the preshrunk stage of reaction, reaction pressure is evacuated down to 600Pa gradually from atmospheric pressure.
Finally, within .5 hour, obtain modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut into slices, and obtains Modified polyester chips.
2, the mensuration of modified poly ester inherent viscosity and fusing point
For ease of comparing, inherent viscosity and fusing point are listed in table 1.
3, substrate performance test
For ease of comparing, the performance of base material is listed in table 2.
4, plastics sucking moulding test
Prepared base material is used for the test of case and bag plastics sucking moulding, result of the test is listed in table 3.
From embodiment 9 and embodiment 7 and embodiment 8 on year-on-year basis, in the plastic uptake processing characteristics improving base material, BDO and neopentyl glycol have useful synergy, and both have synergy reducing in the probability hung and flow and turn white more specifically.
The feature viscosity of table 1 modified poly ester and fusing point
| Inherent viscosity, dl/g | Fusing point, DEG C | |
| Embodiment 1 | 0.7520 | 202 |
| Comparative example 1 | 0.7625 | 204 |
| Embodiment 2 | 0.7590 | 206 |
| Embodiment 3 | 0.7612 | 200 |
| Embodiment 4 | 0.7710 | 198 |
| Comparative example 2 | 0.7595 | 198 |
| Embodiment 5 | 0.8637 | 205 |
| Embodiment 6 | 0.7625 | 210 |
| Embodiment 7 | 0.7514 | 215 |
| Embodiment 8 | 0.7692 | 220 |
| Embodiment 9 | 0.7533 | 225 |
The performance of table 2 base material
Table 3 plastic uptake processing characteristics
| Blow quick-fried | Be full of cracks | Hang stream | Turn white | |
| Embodiment 1 | Better | Poor | Poor | The poorest |
| Comparative example 1 | The poorest | The poorest | The poorest | The poorest |
| Embodiment 2 | Better | Poor | The poorest | Poor |
| Embodiment 3 | Better | Better | Better | Poor |
| Embodiment 4 | Better | Better | Better | Poor |
| Comparative example 2 | Poor | The poorest | The poorest | The poorest |
| Embodiment 5 | Better | Poor | Better | Poor |
| Embodiment 6 | Better | Better | Better | Better |
| Embodiment 7 | Best | Best | Best | Better |
| Embodiment 8 | Best | Best | Better | Better |
| Embodiment 9 | Best | Best | Best | Best |
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the first structure of composite board of the present invention.
Fig. 2 is the schematic diagram of composite board the second structure of the present invention.
In fig. 1 and 2,1 is the polymeric substrate in composite board, and 2 is the surface film in compound sheet material, and 3 is metal layers.
Claims (10)
1. a composite board, is characterized in that described composite board comprises polymeric substrate (1) and surface film (2), and described polymeric substrate (1) and described surface film (2) fit; Or the metal layer (3) that described composite board comprises polymeric substrate (1), surface film (2) and is compound between polymeric substrate (1) and surface film (2).
2. composite board according to claim 1, is characterized in that the material of described base material (1) is selected from least one polymer in ABS, PC, PP, PETG, PET and PBT or polymer-modified based at least one in them.
3. composite board according to claim 1, is characterized in that the material of described surface film (2) is be selected from least one polymer in PC, PP, PETG, PET and PBT or polymer-modified based at least one in them.
4. composite board according to claim 1, is characterized in that described base material (1) is obtained by modified poly ester composition; Described modified poly ester composition, containing modified poly ester 60 ~ 95wt% and flexibilizer 5 ~ 40wt%; Wherein said modified poly ester, inherent viscosity is 0.7 ~ 1.4dl/g, and fusing point is 170 ~ 240 DEG C, and employing comprises the reaction raw materials copolymerization of crosslinking agent, modifier, terephthalic acid (TPA) and ethylene glycol and obtains; There is in the molecule of described crosslinking agent the functional group that can form at most more than 3 or 3 crosslinked links in described modified poly ester; Described modifier is selected from diacid modifiers and/or glycol modification agent, has 2 hydroxy-acid groups in described modified agent molecule, has 2 alcoholic extract hydroxyl groups in described glycol modification agent molecule; With molar ratio computing (terephthalic acid (TPA)+diacid modifiers): (ethylene glycol+glycol modification agent): crosslinking agent is for 1:(1.1 ~ 2.0): (0.001 ~ 0.005), the mol ratio of diacid modifiers and terephthalic acid (TPA) is a, and the mol ratio of glycol modification agent and ethylene glycol is b; A+b=0.10 ~ 0.45.
5. composite board according to claim 4, is characterized in that described crosslinking agent is selected from least one in the acid anhydrides of polyalcohol, polyacid or polyacid, described polynary be more than 3 yuan or 3 yuan.
6. composite board according to claim 5, is characterized in that described polyalcohol is selected from least one in pentaerythrite, bipentaerythrite, tripentaerythritol, trimethylolpropane, trimethylolethane and glycerine.
7. composite board according to claim 5, is characterized in that the acid anhydrides of described polyacid is pyromellitic acid anhydride.
8. composite board according to claim 4, is characterized in that described diacid modifiers is M-phthalic acid and/or adipic acid.
9. composite board according to claim 4, is characterized in that described glycol modification agent is neopentyl glycol and/or BDO.
10. the composite board according to any one of claim 4 ~ 9, is characterized in that described modified poly ester adopts the method preparation comprised the steps:
(1) make described reaction raw materials carry out esterification and obtain carboxylate;
(2) precondensation;
(3) polycondensation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105146884A (en) * | 2015-09-23 | 2015-12-16 | 浙江银座箱包有限公司 | Production technology for luggage |
| CN105313409A (en) * | 2015-11-04 | 2016-02-10 | 温州市瓯海凯士箱包厂 | Plate for manufacturing of suitcase shell and suitcase |
| CN106839475A (en) * | 2016-12-14 | 2017-06-13 | 池州市小康人家科技有限公司 | A kind of rack of solar water heater composite board |
| CN111584214A (en) * | 2019-02-15 | 2020-08-25 | 南通盛洋电气有限公司 | High-voltage coil internal insulation structure of epoxy cast dry type transformer |
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| CN103946268A (en) * | 2011-11-30 | 2014-07-23 | 拜耳知识产权有限责任公司 | Metallized multilayer structure made of specific polycarbonates with low coefficient of thermal expansion |
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