CN104553201B - Composite board - Google Patents
Composite board Download PDFInfo
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- CN104553201B CN104553201B CN201510028261.9A CN201510028261A CN104553201B CN 104553201 B CN104553201 B CN 104553201B CN 201510028261 A CN201510028261 A CN 201510028261A CN 104553201 B CN104553201 B CN 104553201B
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- composite board
- acid
- poly ester
- modified poly
- esterification
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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
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of composite board, the mainly problem of the device surface decorative effect difference that polymer plate prepares through plastics sucking moulding present in solution prior art, by using a kind of composite board, described composite board includes that polymeric substrate (1) and surface film (2), described polymeric substrate (1) fit with described surface film (2)；Or described composite board includes polymeric substrate (1), surface film (2) and the technical scheme of metal layer (3) being compound between polymeric substrate (1) and surface film (2), preferably solve this technical problem, can be used in the industrial production of composite board.
Description
Technical field
The present invention relates to a kind of composite board.
Background technology
Polymer plate commonly used in the prior art only has single polymeric substrate composition, and thus sheet material is through plastic uptake
Device that shaping prepares or article surface is rough, lack color or lack it is intended that the incrustation such as metallic luster effect
Really.In prior art, in order to obtain metallic luster, it usually needs substantial amounts of metal material, but owing to the proportion of metal is relatively big, pass
Aluminium alloy is directly used in case and bag by system, and its cost and empty weight are heavier, directly affects use.Printing gold it is also adopted by market
Belong to powder ink, on Case outer-shell, the method for plated metal produces the case and bag plate with metallic luster, and the former metallic luster is imitated
The poorest, the metal level of the latter is very easy to abrasion.For solving these technical problems, need exploitation badly and there is the polymer of surface film
Sheet material.
The existing polymeric material for case and bag matrix has a lot.Can use on the matrix case and bag of case board ABS,
PC, PP, PETG, PET, PBT and above-mentioned material are main modified polymer material, and most popular is ABS and PC sheet material.
ABS plate is poisonous when burning, PC plate processing difficulties, and cost is high.Can be by two or more polymer in appropriate ratio
Under the conditions of uniform temperature and shear stress etc., formed blend polymer or the conjunction with new performance by melt blending
Gold.Prepared by this blend polymer it is crucial that compatibility between polymer.If making the incompatible poly-of two or more
Compound reaches the most perhaps partially compatible, can use compatilizer technology, reactive extrusion technology, Interpenetrating Polymer Network Technology and gather
Specific Interactions technology etc. between adduct molecule, and use expressing technique to become plate.Modified poly ester raw material is extensive, nontoxic, and environmental protection can
Repeatedly reclaim, be preferably to select, but the plastic uptake processing characteristics of existing modified poly ester is not ideal enough.
Poly-diacid diol ester, especially polyethylene terephthalate (are called for short PET), are conventional thermoplastic polyester trees
Fat.But different field, the requirement to polyester property varies, in order to meet the needs of different field different performance, existing skill
Arisen at the historic moment in art various different modified poly ester and the most different method of modifying.
CN1566180A discloses a kind of method preparing modified poly ester, its use terephthalic acid (TPA), M-phthalic acid and
Ethylene glycol is that comonomer obtains the modified poly ester with isophthalic acid as modifying agent by copolymerization.
A kind of method that CN 102964574 A discloses modified poly ester and modification thereof, it uses isophthalic diformazan
Acid, neopentyl glycol, 1,4 cyclohexane dimethanol, terephthalic acid (TPA) and ethylene glycol copolymerization obtain modified poly ester.Due to isophthalic diformazan
Acid, neopentyl glycol and 1,4-CHDM, as modifying agent, can not only improve the shrinkage factor of modified poly ester, and can
Reduce its fragility so that it is the phenomenons such as fracture will not occur during as bottle label, improve yield rate.
CN 102964575 A discloses a kind of modified poly ester and preparation method thereof, its use M-phthalic acid, new penta 2
Alcohol, terephthalic acid (TPA) and ethylene glycol copolymerization obtain modified poly ester.M-phthalic acid and neopentyl glycol can not only as modifying agent
Improve the shrinkage factor of modified poly ester, and its fragility can be reduced so that it is during as bottle label, the phenomenons such as fracture will not occur,
Improve yield rate.
CN 102964576 A discloses a kind of modified poly ester and preparation method thereof, and it uses M-phthalic acid, to benzene two
Formic acid, 1,4-CHDM and ethylene glycol copolymerization obtain modified poly ester, and it has higher film and draws high intensity and fracture
Percentage elongation.
CN 103665352 A discloses the preparation method of environment-friendlyspecial special modified polyester chip for iron coating, and it uses second two
Alcohol, 1,4-CHDM, neopentyl glycol, terephthalic acid (TPA), M-phthalic acid copolymerization obtain modified poly ester
CN 103755941 A discloses the method for modifying of a kind of polyester, and polyester and chain extender are carried out reaction and obtain institute by it
The modified poly ester needed.
But the sheet material plastic uptake poor processability that modified poly ester of the prior art prepares.
Summary of the invention
The technical problem to be solved is that polymer plate prepares through plastics sucking moulding present in prior art
The rough problem lacking surface decoration effect of device surface, it is provided that a kind of composite board, this composite board can provide smooth
Surface, and color or metallic luster etc. can be provided the most easily, there is preferable surface decoration effect.
For solving above-mentioned technical problem, technical scheme is as follows: a kind of composite board, it is characterized in that described compound
Sheet material includes that polymeric substrate 1 and surface film 2, described polymeric substrate 1 fit with described surface film 2；Or institute
State composite board include polymeric substrate 1, surface film 2 and be compound in the metal between polymeric substrate 1 and surface film 2
Change layer 3.
In technique scheme, the material of described base material 1 is selected from least in ABS, PC, PP, PETG, PET and PBT
Kind of polymer or polymer-modified based at least one in them.
In technique scheme, the material of described surface film 2 can be in PC, PP, PETG, PET and PBT extremely
Few a kind of polymer or polymer-modified based at least one in them.In order to give surface film 2 with color, permissible
In the processing raw material of surface film 2, required dyestuff or color is added before preparing surface film；Can also be at the table made
The surface printing of face film 2 forms, and when using the mode of printing, is possible not only to make surface film 2 have required color, also
Can 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 be reasonable
Select.Thickness such as but not limited to described surface film 2 is 0.05～0.5mm.
Polymeric substrate 1 and surface film 2, described polymeric substrate 1 and institute are included for composite board described above
Stating the technical scheme that surface film 2 fits, between polymeric substrate 1 and described surface film, additional or the most additional tack coat is equal
Can, when the most additional tack coat, the method that hot pressing can be used to fit makes described polymeric substrate 1 and surface film 2 be bonded in
Form composite board together.
Polymeric substrate 1, surface film 2 are included for composite board described above and is compound in polymeric substrate 1 and
The technical scheme of the metal layer 3 between surface film 2, described metal layer 3 preparation method can use in prior art
Those methods having, such as but not limited to the metallization using the methods such as vacuum evaporation metallic film technique, electroplating technology to be formed
Layer 3.In order to improve the adhesion of metal layer 3 and surface film 2, appropriate primer can be coated with in advance on surface film 2, then
Through vacuum evaporation metal.In order to improve and the adhesion of base material 1, one layer of adhering resin can be coated with on the metal layer.Metal layer 3
In metal be not particularly limited, rationally can select according to required metallic luster.The most described metal layer 3
Metal is but not limited at least one in gold, silver, copper, zinc, chromium and aluminium or multiple.The thickness of metal layer 3 limits the most especially
System, but usual optional metallization layer thickness is 0.01～1nm.
In technique scheme, described base material 1 and/or surface film 2 are preferably prepared by following modified poly ester composition；
Described modified poly ester composition, containing modified poly ester 60～95wt% and toughener 5～40wt%；Wherein said modified poly ester,
Inherent viscosity is 0.7～1.4dl/g, and fusing point is 170～240 DEG C, uses and includes crosslinking agent, modifying agent, terephthalic acid (TPA) and second
Glycol obtains in interior reaction raw materials copolymerization；The molecule of described crosslinking agent has in described modified poly ester, at most can form 3
Individual or more than 3 functional groups cross-linking link；Described modifying agent is selected from diacid modifiers and/or glycol modification agent, described
Modified agent molecule has 2 hydroxy-acid groups, described glycol modification agent molecule has 2 alcoholic extract hydroxyl groups；With molar ratio computing
(terephthalic acid (TPA)+diacid modifiers): (ethylene glycol+glycol modification agent): crosslinking agent is 1:(1.1～2.0): (0.001～
0.005), diacid modifiers is a with the mol ratio of terephthalic acid (TPA), and glycol modification agent is b with the mol ratio of ethylene glycol；A+b=
0.10～0.45.Now described base material 1 has good plastic uptake processing characteristics.Further preferably surface film 2 is also adopted by
Stating modified poly ester composition to prepare, include polymeric substrate 1 and surface film 2 at this point for described composite board, described is poly-
The technical scheme that compound base material 1 fits with described surface film 2, fits more firm between base material 1 and surface film, right
Include polymeric substrate 1, surface film 2 in described composite board and be compound between polymeric substrate 1 and surface film 2
The technical scheme of metal layer 3, the combination between polymeric substrate 1 and metal layer 3 is more firm, and metal layer 3 and table
Combine the most firm between face film 2.
One skilled in the art will appreciate that the plastic uptake processing characteristics of base material 1 in composite board determines the plastic uptake of composite board
Processing characteristics, the volume that surface film 2 accounts in composite board is the least, and it primarily serves decoration, adds the plastic uptake of composite board
Work performance impact is little.Therefore, base material 1 has good blister performance and the most 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 also not to be 0.Such as during b=0, above-mentioned technology
Scheme becomes: (terephthalic acid (TPA)+diacid modifiers): ethylene glycol: crosslinking agent is 1:(1.1～2.0): (0.001～0.005),
Diacid modifiers is a, a=0.10～0.45 with the mol ratio of terephthalic acid (TPA).The most such as during a=0, technique scheme becomes
For: terephthalic acid (TPA): (ethylene glycol+glycol modification agent): crosslinking agent is 1:(1.1～2.0): (0.001～0.005), diacid changes
Property agent and terephthalic acid (TPA) mol ratio be b, b=0.10～0.45.But when a and b is not 0, in relatively a and b one of them
The base material 1 that when being 0, described modified poly ester composition prepares has more preferable 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 the composite board base material 1 of the present invention uses and is prepared by described modified poly ester composition,
Key problem in technology is described modified poly ester, and the kind of toughener is not particularly limited, and all can reach plastic uptake processing characteristics
Good effect.But described toughener preferably is selected from LLDPE (LLDPE), ultra-low density polyethylene (VLLDPE), hydrogen
Change thermoplastic styrene butadiene rubber (SEBS), polypropylene (PP), ethylene-propylene copolymer, ethylene-acrylic acid copolymer (EAA), second
Alkene-vinyl acetate co-polymer (EVA), ethylene-methacrylic acid copolymer (EMMA), ethylene-methyl methacrylate glycidol
At least one in the butadiene-styrene rubber (SBR g MAH) of ester (GMA) and maleic anhydride grafting.
In technique scheme, described crosslinking agent preferably is selected from the acid anhydrides of polyalcohol, polyacid or polyacid at least
One, described polynary be 3 yuan or more than 3 yuan.The most polynary first number can be integer such as but not limited to 3 yuan, 4 members, 5
Unit, 6 yuan, 7 yuan etc.；Unit's number can also be decimal.Can be obtained by mixing in required ratio with the crosslinking agent of different units.Described polynary
The number of the crosslinking link that the acid anhydrides of alcohol, polyacid or polyacid at most can be formed in described modified poly ester and described unit number phase
With.
In technique scheme, described crosslinking agent includes polyalcohol and polyacid the most simultaneously, or wraps the most simultaneously
Include the acid anhydrides of polyalcohol and polyacid.Now, there is in terms of improving the plastics sucking moulding of modified poly ester base material 1 the most collaborative work
With, particularly there is in terms of reducing be full of cracks, hanging the probability flowing or turning white significantly synergy.
In technique scheme, described polyalcohol preferably is selected from pentaerythrite, bipentaerythrite, tripentaerythritol, three hydroxyls
At least one in methylpropane, trimethylolethane and glycerine.
In technique scheme, the acid anhydrides of described polyacid is preferably pyromellitic acid anhydride.
In technique scheme, described polyacid preferably is selected from least one in trimesic acid and Pyromellitic Acid.
In technique scheme, described diacid modifiers is preferably M-phthalic acid and/or adipic acid；More preferably simultaneously
Use M-phthalic acid and adipic acid, M-phthalic acid and adipic acid in terms of reducing be full of cracks, hanging stream and the probability occurred that turns white
There is synergy.
In technique scheme, described glycol modification agent is preferably neopentyl glycol and/or BDO, more preferably same
Shi Caiyong neopentyl glycol and BDO, neopentyl glycol and BDO have in terms of the probability flowing and turning white is hung in reduction
Synergy.
Non-limiting as embodiment is enumerated, and described modified poly ester can be obtained by following embodiment:
Embodiment 1: by the reaction raw materials including terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pentaerythrite
Copolymerization and obtain；
Embodiment 2: anti-by including terephthalic acid (TPA), M-phthalic acid, ethylene glycol and pyromellitic acid anhydride
Material copolymerization is answered to obtain；
Embodiment 3: former by the reaction including terephthalic acid (TPA), M-phthalic acid, ethylene glycol and Pyromellitic Acid
Expect that copolymerization obtains；
Embodiment 4: by including terephthalic acid (TPA), M-phthalic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride
Obtain in interior reaction raw materials copolymerization；
Embodiment 5: by including terephthalic acid (TPA), adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride
Reaction raw materials copolymerization and obtain；
Embodiment 6: by including terephthalic acid (TPA), M-phthalic acid, adipic acid, ethylene glycol, pentaerythrite and equal benzene four
Formic acid dianhydride obtains in interior reaction raw materials copolymerization；
Embodiment 7: by including terephthalic acid (TPA), M-phthalic acid, adipic acid, neopentyl glycol, ethylene glycol, pentaerythrite
Obtain in interior reaction raw materials copolymerization with pyromellitic acid anhydride；
Embodiment 8: by including terephthalic acid (TPA), M-phthalic acid, adipic acid, 1,4-butanediol, ethylene glycol, Ji Wusi
Alcohol and pyromellitic acid anhydride obtain in interior reaction raw materials copolymerization；
Embodiment 9: by including terephthalic acid (TPA), M-phthalic acid, adipic acid, neopentyl glycol, 1,4-butanediol, second two
Alcohol, pentaerythrite and pyromellitic acid anhydride obtain in interior reaction raw materials copolymerization.
The inherent viscosity of described modified poly ester is adopted and is measured with the following method:
5.1.1 method A (capillary viscosity in GB/T 14190-2008 " fiber polyester chip (PET) test method "
Meter 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 employs the method comprised the steps to be prepared:
(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 is preferably carried out to esterification yield and is at least 95%, such as 95～99%.Its
The natural formula of middle esterification yield is defined as follows:
Esterification yield %=[esterification actually generates that the weight of water/(in reaction raw materials, hydroxyl and carboxyl are by measuring thorough ester
Change the weight reacting generated 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 preferably from atmospheric pressure be gradually transitions 500～
700Pa.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, during prepolymerization reaction reaction pressure from atmospheric pressure by
Gradual transition is to 500～700Pa.
In technique scheme, the temperature of described polycondensation reaction is preferably 270～290 DEG C.
In technique scheme, the pressure of described polycondensation reaction preferably 60～100Pa.
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, the pressure of described polycondensation reaction preferably 60～100Pa, 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, it is also possible to need not urge
Agent.Precondensation and polycondensation typically require addition polymerization catalyst.Polymerization catalyst is not particularly limited, and polyester field is normal
Those may be incorporated for the present invention.Described polymerization catalyst is such as but not limited to antimony system polymerization catalyst, the polymerization of titanium system
Catalyst.Enumerate as antimony system polymerization catalyst is nonrestrictive, can be in antimony glycol, antimony oxide or antimony acetate
At least one.When esterif iotacation step adds catalyst, polymerization catalyst can be added in esterif iotacation step, these polymerization catalysts
Also the effect of catalyst can be played in esterif iotacation step.As for the consumption of catalyst, it is not particularly limited, such as former with esterification
On the basis of the gross weight of material, the consumption of catalyst can be but not limited to 0.005%～0.1%, more usually 0.01～
0.1%.
(such as but not limited to after esterif iotacation step and before precondensation) after esterif iotacation step, can gather according to modification
The needing of the other side performance of ester adds common those auxiliary agents in this area.These auxiliary agents be such as but not limited to antioxidant,
At least one in fire retardant, delustering agent, pigment, ultra-violet stabilizer etc..
In described modified poly ester composition, in addition to modified poly ester and toughener, it is also possible to normal containing other this area
Those additives, these additives are such as but not limited to antioxidant, fire retardant, delustering agent, pigment, ultra-violet stabilizer
At least one in Deng.
After the structure disclosing described composite board, surface film is permissible to the surface decoration effect of composite board
Intended.
Described composite board can make various device or article through plastics sucking moulding, and the most described device or article are permissible
It is but 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, can use required material pellet or powder through screw extruder altogether
The mode extruded by flat-die after Hun obtains, and those skilled in the art will know that double screw extruder is better than single screw extrusion machine.
Base material involved in the performance of the base material 1 of table 2 composite board in the specific embodiment of the invention all uses as follows
Preparation method obtain:
The Korea S SK of the modified poly ester and 20wt% that take 80wt% produces, the trade mark is the LLDPE of FV149M, by described modification
The pellet of polyester and LLDPE is simply mixed, and then uses double screw extruder to carry out being blended and flat-die extrusion obtains thickness and is
2.8mm, width is the base material of 660mm.
The specific embodiment of the invention uses the auspicious ZSE 60MAXX that hereby mechanical (granary) Co., Ltd produces of Leicester
Type double screw extruder, 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 uses in preparation
Be: screw rod operating rate is 100rpm, operation 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,
11st and the 12nd section is 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), uses ASTM D256 method；
Elongation strain (fracture, 23 DEG C), uses ASTM D256 method；
Bending modulus (23 DEG C), uses ASTM D796 method；
Izod notched impact strength (local fracture, 23 DEG C), uses ASTM D368 method.
The plastic uptake processing characteristics data acquisition Ningbo Heng Yan packaging facilities factory of the base material 1 of specific embodiment of the invention table 3
The HL-211 type plastic suction forming apparatus manufactured, is obtained by following concrete plastic uptake step:
A, the above-mentioned corresponding base material 1 of table 2 is cut into thickness be 2.8mm, width be 660mm, the base material of a length of 860mm
Unit；
B, sheet unit is placed in fixed position, is then pressed by under fixing device, pin；
C, described base material unit advance heating chamber, carry out thermoplastic, heating-up temperature is 150 DEG C, and the heat time is 60
Second；
D, the base material unit softened is 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 to maintain base material unit be 10 with the mould laminating time
Second；
F, cooling, on the base material unit of shaping, blown by air-cooler and cool down, and then gassing time about 15 seconds sprays
Water cooling so that 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 the test of 100 parallel plastic uptakes and obtain
Result.
The various phenomenons being not intended to see occurred in plastic uptake is tested are on plastics sucking moulding impact difference.What harm was maximum is
Blow quick-fried, directly result in plastics sucking moulding failure；The be full of cracks, the extension that occur on the basis of plastics sucking moulding is successful flow or turn white, and cause
The Case outer-shell quality defect that plastics sucking moulding obtains.Different, by as follows for result classification according to the probability that corresponding phenomenon occurs:
Best: the probability that corresponding phenomenon occurs is 0%～less than 5%；
Preferable: the probability that corresponding phenomenon occurs is 5%～less than 20%；
Poor: the probability that corresponding phenomenon occurs is 20%～less than 60%；
Worst: the probability that corresponding phenomenon occurs is 60%～100%.
The present invention is described in detail with detailed description of the invention in explanation below in conjunction with the accompanying drawings.
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 are
Metal layer.
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 to benzene
Dioctyl phthalate, M-phthalic acid, ethylene glycol and pentaerythrite, esterification raw material gross weight 400 kilograms, with molar ratio computing (to benzene two
Formic acid+M-phthalic acid): the mol ratio of ethylene glycol: pentaerythrite is 1:1.2:0.003, M-phthalic acid and terephthalic acid (TPA)
Being 0.2, polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification, ester at 250 DEG C
Change and course of reaction steams the water that esterification generates simultaneously, be 97% to esterification yield, obtain being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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
The most do not use crosslinking agent, particularly as follows:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, M-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+isophthalic
Dioctyl phthalate): ethylene glycol is 1:1.2, and M-phthalic acid is 0.2 with the mol ratio of terephthalic acid (TPA), and polymerization catalyst is antimony acetate,
Consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steams esterification raw in esterification reaction process simultaneously
The water become, is 97% to esterification yield, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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 embodiment 1 in table 2 and table 3 with comparative example 1 are compared, owing to modified poly ester is in preparation
During add crosslinking agent, improve the tensile stress of base material, draw high strain, bending modulus and impact strength.Prior
It is the plastic uptake processing characteristics that improve base material, is embodied in significantly reduce and blows the probability that outburst is raw, and reduce be full of cracks
With the probability hanging stream generation
[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 to benzene
Dioctyl phthalate, 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 1:1.2:0.003, M-phthalic acid with to benzene two
The mol ratio of formic acid is 0.2, and polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out at 250 DEG C
Esterification, steams the water that esterification generates simultaneously, is 97% to esterification yield in esterification reaction process, obtain being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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 to benzene
Dioctyl phthalate, 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 1:1.2:0.0015:
0.0015, M-phthalic acid is 0.2 with the mol ratio of terephthalic acid (TPA), and polymerization catalyst is antimony acetate, and consumption is 200 grams.Beat
Slurry, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steams the water that esterification generates, to esterification in esterification reaction process simultaneously
Rate is 97%, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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 the plastics sucking moulding result of the test of embodiment 3 and embodiment 1 and embodiment 2 it can be seen that pentaerythrite and equal benzene
Tetracarboxylic acid dianhydride has significantly synergy in terms of reducing be full of cracks, hanging the probability flowing or turning white.
[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 to benzene
Dioctyl phthalate, 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 1:1.2:0.0015:
0.0015, M-phthalic acid is 0.2 with the mol ratio of terephthalic acid (TPA), and polymerization catalyst is antimony acetate, and consumption is 200 grams.Beat
Slurry, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steams the water that esterification generates, to esterification in esterification reaction process simultaneously
Rate is 97%, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .0 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polymerase 17 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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 4 and embodiment 3 on year-on-year basis it can be seen that polymerisation reaches 3.5 hours polymerisations carries out the most very
Fully, then to extend polymerisation less to the performance impact of base material.
[comparative example 2]
Differ primarily in that crosslinking agent adds after polymerization procedure with embodiment 3, 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 to benzene
Dioctyl phthalate, M-phthalic acid and ethylene glycol, esterification raw material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+isophthalic
Dioctyl phthalate): ethylene glycol is 1:1.2, and M-phthalic acid is 0.2 with the mol ratio of terephthalic acid (TPA), and polymerization catalyst is antimony acetate,
Consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steams esterification raw in esterification reaction process simultaneously
The water become, is 97% to esterification yield, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, at reaction temperature polyase 13 .5 hour of the reaction pressure of 80Pa and 285 DEG C, the esterification with embodiment 3 is added
The pentaerythrite of respective amount and pyromellitic acid anhydride in reaction raw materials, continue in the reaction pressure of 80Pa and the reaction of 285 DEG C
Temperature polymerizations 3.5 hours, water-cooled is cut into slices, is added the Modified polyester chips of crosslinking agent after obtaining.
2, modified poly ester inherent viscosity and the mensuration of 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 it can be seen that modified poly ester by
In adding crosslinking agent in esterification raw material, it is the completeest in polymerisation that the plastic uptake processing characteristics of base material is far superior to employing
With crosslinking agent, polyester is modified again after becoming or being basically completed.
[embodiment 5]
1, the preparation of modified poly ester
M-phthalic acid is replaced with adipic acid with differring primarily in that of embodiment 3, particularly as follows:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400 kilograms, with mole
Than meter (terephthalic acid (TPA)+adipic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015,
Adipic acid is 0.2 with the mol ratio of terephthalic acid (TPA), and polymerization catalyst is antimony acetate, and consumption is 200 grams.Making beating, nitrogen displacement 3
Secondary, carry out esterification at 250 DEG C, esterification reaction process steams the water that esterification generates simultaneously, is 97% to esterification yield, obtains
Esterification material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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
Differring primarily in that with embodiment 3, the diacid modifiers of embodiment 3 is adopted only with M-phthalic acid, the present embodiment
Diacid modifiers be M-phthalic acid and adipic acid, particularly as follows:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, M-phthalic acid, adipic acid, ethylene glycol, pentaerythrite and pyromellitic acid anhydride, esterification raw material gross weight 400
Kilogram, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): ethylene glycol: pentaerythrite: pyromellitic acid anhydride
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 is replaced 3 times, is carried out ester at 250 DEG C
Change reaction, esterification reaction process steams the water that esterification generates simultaneously, is 97% to esterification yield, obtain being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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 6 and embodiment 5 and embodiment 1 on year-on-year basis it can be seen that M-phthalic acid and adipic acid are improving base material
Plastic uptake processing characteristics aspect, there is the interaction being better than simple superposition, be embodied in both reduce be full of cracks, hang stream and
The probability aspect occurred of turning white has synergy.
[embodiment 7]
1, the preparation of modified poly ester
Neopentyl glycol is additionally used as glycol modification agent with differring primarily in that of embodiment 6, particularly as follows:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, M-phthalic acid, adipic acid, ethylene glycol, neopentyl glycol, pentaerythrite and pyromellitic acid anhydride, esterification is former
Material gross weight 400 kilograms, with molar ratio computing (terephthalic acid (TPA)+M-phthalic acid+adipic acid): (ethylene glycol+neopentyl glycol): season penta
Tetrol: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): terephthalic acid (TPA) mole
Ratio is 0.2, M-phthalic acid: adipic acid mol ratio is 1, neopentyl glycol: ethylene glycol mol ratio is 0.2；Polymerization catalyst is vinegar
Acid antimony, consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steam in esterification reaction process simultaneously
The water that esterification generates, is 97% to esterification yield, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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
With embodiment 7 differ primarily in that employing BDO replace neopentyl glycol as glycol modification agent, specifically
For:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, M-phthalic acid, adipic acid, ethylene glycol, BDO, 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+BDO):
Pentaerythrite: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (M-phthalic acid+adipic acid): terephthalic acid (TPA)
Mol ratio is 0.2, M-phthalic acid: adipic acid mol ratio is 1, BDO: ethylene glycol mol ratio is 0.2；Polymerization catalyzed
Agent is antimony acetate, and consumption is 200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, same in esterification reaction process
Time steam esterification generate water, be 97% to esterification yield, obtain be esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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
With differring primarily in that of embodiment 7, the present embodiment uses BDO and neopentyl glycol as glycol simultaneously
Modifying agent, particularly as follows:
Esterification raw material and polymerization catalyst is added in the reactor of 1000 liters.Wherein esterification raw material is to benzene
Dioctyl phthalate, M-phthalic acid, adipic acid, ethylene glycol, BDO, 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+Isosorbide-5-Nitrae-
Butanediol+neopentyl glycol): pentaerythrite: pyromellitic acid anhydride is 1:1.2:0.0015:0.0015, (M-phthalic acid+oneself
Diacid): the mol ratio of terephthalic acid (TPA) is 0.2, M-phthalic acid: adipic acid mol ratio is 1, (BDO+new penta 2
Alcohol): ethylene glycol mol ratio is 0.2, BDO: neopentyl glycol mol ratio is 1；Polymerization catalyst is antimony acetate, and consumption is
200 grams.Making beating, nitrogen is replaced 3 times, is carried out esterification at 250 DEG C, steams what esterification generated in esterification reaction process simultaneously
Water, is 97% to esterification yield, obtains being esterified material.
Then, it is 270 DEG C in temperature and carries out prepolymerization reaction in the case of vacuumizing and obtain prepolymer, preshrunk in 1.5 hours
During reaction, reaction pressure is gradually evacuated down to 600Pa from atmospheric pressure.
Finally, within .5 hour, obtaining modified poly ester in the reaction pressure of 80Pa and the reaction temperature polyase 13 of 285 DEG C, water-cooled is cut
Sheet, obtains Modified polyester chips.
2, modified poly ester inherent viscosity and the mensuration of 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.
Understand on year-on-year basis with embodiment 7 and embodiment 8 from embodiment 9, in terms of the plastic uptake processing characteristics of raising base material, Isosorbide-5-Nitrae-
Butanediol and neopentyl glycol have useful synergy, and more specifically both have in terms of the probability flowing and turning white is hung in reduction
Synergy.
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 | Preferably | Poor | Poor | Worst |
| Comparative example 1 | Worst | Worst | Worst | Worst |
| Embodiment 2 | Preferably | Poor | Worst | Poor |
| Embodiment 3 | Preferably | Preferably | Preferably | Poor |
| Embodiment 4 | Preferably | Preferably | Preferably | Poor |
| Comparative example 2 | Poor | Worst | Worst | Worst |
| Embodiment 5 | Preferably | Poor | Preferably | Poor |
| Embodiment 6 | Preferably | Preferably | Preferably | Preferably |
| Embodiment 7 | Best | Best | Best | Preferably |
| Embodiment 8 | Best | Best | Preferably | Preferably |
| Embodiment 9 | Best | Best | Best | Best |
Claims (8)
1. a composite board, is characterized in that described composite board includes polymeric substrate (1) and surface film (2), described
Polymeric substrate (1) fits with described surface film (2)；Or described composite board includes that polymeric substrate (1), surface are thin
Film (2) and the metal layer (3) being compound between polymeric substrate (1) and surface film (2)；
Described base material (1) is prepared by modified poly ester composition；Described modified poly ester composition, containing modified poly ester 60～
95wt% and toughener 5～40wt%；Wherein said modified poly ester, inherent viscosity is 0.7～1.4 dl/g, and fusing point is 170 ~ 240
DEG C, use the reaction raw materials copolymerization including crosslinking agent, modifying agent, terephthalic acid (TPA) and ethylene glycol to obtain；Described crosslinking agent
Molecule in there are in described modified poly ester formation 3 or more than 3 functional groups cross-linking link；Described crosslinking agent is simultaneously
Including polyalcohol and polyacid, or described crosslinking agent includes the acid anhydrides of polyalcohol and polyacid simultaneously；Described modifying agent choosing
There is in diacid modifiers and/or glycol modification agent, described modified agent molecule 2 hydroxy-acid groups, described glycol modification
Agent molecule has 2 alcoholic extract hydroxyl groups；With molar ratio computing (terephthalic acid (TPA)+diacid modifiers): (ethylene glycol+glycol modification agent):
Crosslinking agent is 1:(1.1～2.0): (0.001～0.005), diacid modifiers is a with the mol ratio of terephthalic acid (TPA), and glycol changes
Property agent and ethylene glycol mol ratio be b；a+b=0.10~0.45.
Composite board the most according to claim 1, it is characterized in that the material of described surface film (2) for selected from PC, PP,
At least one polymer in PETG, PET and PBT or polymer-modified based at least one in them.
Composite board the most according to claim 1, is characterized in that the polyalcohol in described crosslinking agent, polyacid or polynary
Acid acid anhydrides described in polynary be 3 yuan or more than 3 yuan.
Composite board the most according to claim 3, is characterized in that described polyalcohol is selected from pentaerythrite, double Ji Wusi
At least one in alcohol, tripentaerythritol, trimethylolpropane, trimethylolethane and glycerine.
Composite board the most according to claim 3, is characterized in that the acid anhydrides of described polyacid is pyromellitic acid anhydride.
Composite board the most according to claim 1, it is characterized in that described diacid modifiers be M-phthalic acid and/or oneself
Diacid.
Composite board the most according to claim 1, it is characterized in that described glycol modification agent be neopentyl glycol and/or Isosorbide-5-Nitrae-
Butanediol.
8. the composite board according to any one of claim 1～7, is characterized in that described modified poly ester uses and comprises the steps
Method prepare:
(1) make described reaction raw materials carry out esterification and obtain carboxylate；
(2) precondensation；
(3) polycondensation.
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| CN1309608A (en) * | 1998-04-28 | 2001-08-22 | 通用电气公司 | Multilayer plastic articles |
| CN102993421A (en) * | 2011-09-14 | 2013-03-27 | 中国石油化工股份有限公司 | Preparation method of foamable polyethylene terephthalate copolyester |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309608A (en) * | 1998-04-28 | 2001-08-22 | 通用电气公司 | Multilayer plastic articles |
| CN102993421A (en) * | 2011-09-14 | 2013-03-27 | 中国石油化工股份有限公司 | Preparation method of foamable polyethylene terephthalate copolyester |
| 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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