CN101967272A - Method for preparing polyester film for solar cell backsheet film - Google Patents

Abstract

The invention discloses a method for preparing a polyester film for a solar cell backsheet film, which is characterized by comprising the following steps of: mixing 200 to 400 mass parts of binary acid, 80 to 160 mass parts of dihydric alcohol, 0.01 to 0.5 mass part of highly-branched polyatomic alcohol, an esterification catalyst for synthesis of polyester, a polycondensation catalyst and a stabilizing agent and carrying out an esterification reaction; adding 0. 1 to 1.0 mass part of high-grade polyenoic fatty acid or alcohol, continuously esterifying, filtering materials and pressing into a polycondensation kettle for a pre-polycondensation reaction so as to prepare modified polyester resin slices; mixing the modified polyester resin slices and master batch polyester slices according to a mass ratio of 100:5-30; and drying, melting, filtering, extruding, cooling a cast piece, biaxially drawing, performing molding treatment and the like so as to prepare the polyester film for the solar cell backsheet film. The film product has excellent mechanical and electrical performances, heat and humidity resistance, dimensional stability, flame retardant property and water vapor permeability resistance.

Description

The manufacture method of solar cell backboard polyester for film film

Technical field

The invention belongs to the manufacture method of the component of solar facilities, relate to a kind of manufacture method of solar cell backboard polyester for film film with material.The polyester film that makes is suitable for the middle layer (or claiming basement membrane) of making the solar cell backboard film, mainly is as main supporting role, to improve the life-span that solar cell uses out of doors.

Background technology

In the prior art, composite solar battery backboard film both domestic and external mainly contains following several:

TPT (this composite membrane is by the PVF polyvinyl fluoride thin film layer on two sides, i.e. du pont company Tedlar rete, and intermediary PET laminated polyester film is made by compound, is called for short TPT);

TPE (this composite membrane is by the PVF thin film layer of one side, and Yi Mian EVA ethene-vinyl acetate copolymerization thin film layer, and intermediary PET laminated polyester film is in addition made by compound, is called for short TPE);

KPK (this composite membrane gathers inclined to one side fluorine divinyl thin film layer by the PVDF on two sides, the promptly French Kynar of Arkema rete, and intermediary PET laminated polyester film is made abbreviation KPK by compound).

TPT, TPE, KPK composite membrane are that ideal protective structures material is gone up in solar cell encapsulation so far.As relevant patent: CN101123278 " compound film for solar battery rear board and preparation method thereof "; CN101431108 " novel solar battery backboard "; CN101037584 " a kind of solar energy battery back board packaging material and preparation method thereof " etc.Existing solar cell both domestic and external manufacturing enterprise all adopts TPT, TPE, KPK composite membrane (solar cell backboard film) to make the substrate material of solar cell basically.Solar cell backboard film (TPT, TPE, KPK composite membrane etc.) requires not only to have " plastics king " fluoroplastics (ageing-resistant, corrosion-resistant, anti-solvent, resistant hydrophobic etc.) performance, polyester (machinery, high-low temperature resistant, ageing-resistant, do not chap, excellent electrical isolation) performance, intercept and the low water absorbable energy but also will improve its water vapor, prevent that hazardous medium (especially water, oxygen, corrodibility gas-liquid, acid rain etc.) is to eva film layer erosive performance, to guarantee solar battery sheet generating efficiency and predicted life thereof.

But owing to PVF polyvinyl fluoride thin film, the poly-inclined to one side fluorine divinyl film of PVDF etc. contains fluorine film mainly by offshore company's monopolization, price is high; At present domestic main backboard film manufacturer begins the application type solar cell backboard film that development is made at polyester film single face (another side coating EVA ethene-vinyl acetate copolymerization thin film layer) or double spread fluoro-containing coating.

With regard to polyester film itself, be meant the biaxially oriented film of polyethylene terephthalate, PEN especially, because of mechanical electric performance, thermotolerance, chemical resistant properties are preferably arranged, numerous areas such as magnetic recording, sensitization (optics) material, electronic component-use film, electric insulation film, metal laminate thin film, adhering film to glass, packing decoration have been applied to.The laminated polyester film that uses in compound film for solar battery rear board is produced both at home and abroad at present, common polyethylene terephthalate (PET) film of general employing, though it is cheap that this polyester film has, advantages such as mechanical electric performance, thermotolerance, chemical resistant properties preferably, but obviously not enough on aspect humidity resistance, anti-steam breathability and the flame retardant resistance.Such as, under 85 ℃, 85% humidity condition through 1000 hours aging after, film just becomes fragile; Usual thickness specification 0.250mm polyester film under 38 ℃, 90% humidity condition its water vapour permeability at 2.5g/m ².24h more than; Flame retardant resistance does not reach UL94VTM-2 (if add fire retardant, its flame retardant properties reaches UL94VTM-2, but will be poorer on its humidity resistance); Be difficult to satisfy the performance requriements of solar cell backboard films such as TPT, TPE, KPK composite membrane.

Summary of the invention

Purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, and a kind of manufacture method of solar cell backboard polyester for film film is provided.Play high performance PE T (polyethylene terephthalate) or PEN (PEN) or PETG (pure modified PET copolyesters) or PETA (sour modified PET copolyesters) or other copolyesters thin film layer materials in support, insulation and iris action middle layer to provide a kind of energy satisfy to make solar cell backboard film (composite solar battery backboard films such as TPT, TPE, KPK, and the application type solar cell backboard film of making at polyester film single or double coating fluoro-containing coating).

The manufacture method of solar cell backboard polyester for film film of the present invention, be to mix with certain proportion by synthesis modification polyester slice and masterbatch polyester slice, drying, melt extrude the casting sheet, make solar cell backboard polyester for film film through biaxial stretch-formed heat setting type again.

Content of the present invention is: a kind of manufacture method of solar cell backboard polyester for film film is characterized in that comprising the following steps:

A, the section of synthesis modification vibrin:

(a) main diprotic acid with 200～400 mass parts, the dibasic alcohol of 80～160 mass parts, 0.01 the polyvalent alcohol of the high side chain of～0.5 mass parts, 0.01 the synthetic esterifying catalyst of using of the polyester of～0.04 mass parts, 0.04 the stablizer of the polycondensation catalyst of～0.12 mass parts and 0.01～0.06 mass parts adds in the pulping tank, start stirrer, after mixing 15～30 minutes with the making beating of 50～100 rev/mins speed, progressively add an esterifying kettle, esterification reaction temperature is controlled at 245～260 ℃, reaction times is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, after 15～40 minutes, when aquifer yield reaches 95% when above of theoretical aquifer yield, esterification finishes, and changes material over to two esterifying kettles;

Described diprotic acid is a terephthalic acid, 2, any one or two kinds of mixture in the 6-naphthalic acid;

Described dibasic alcohol is an ethylene glycol;

The polyvalent alcohol of described high side chain is to contain 3～12 carbon and contain in the polyvalent alcohol of 3 and above activity hydroxy any;

Described polyester is synthetic to be one or more mixture in Cobaltous diacetate, sodium-acetate, the magnesium acetate with esterifying catalyst;

Described polycondensation catalyst is an antimonous oxide;

Described stablizer is one or more the mixture in trimethyl phosphite 99, triphenylphosphate, the phosphoric acid;

(b) add the polyenoid higher fatty acid or the alcohol of 0.1～1.0 mass parts, start stirrer and stir, keep temperature in the kettle, continue esterification after 15～40 minutes, material is filtered and be pressed into polycondensation vessel through filter at 250～265 ℃ with 50～80 rev/mins speed;

Described polyenoid higher fatty acid or alcohol are for containing 16 carbon and above contain diene or triethenoid fatty acid or contain 16 carbon and the above any one or two kinds of above mixtures that contain in diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18);

(c) after entering polycondensation vessel, material begins to carry out prepolymerization reaction: start stirrer, with 40～60 rev/mins speed in 30～70 minutes with behind still temperature rise to 270～280 ℃, stop to heat up, simultaneously vacuum drop is reduced to 100～150Pa from normal pressure, then stirrer is reduced to 10～30 rev/mins speed, vacuum control to 0～100Pa carries out the high vacuum polymerization; After high vacuum polymerization in 2～4 hours, when limiting viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging; Promptly make modified polyester resin section, the fusing point of the modified polyester resin section that obtains is 0.60～0.75g/dl greater than 250 ℃, limiting viscosity;

B, manufacturing polyester film:

Synthesis modification vibrin section is mixed by 100: 5～30 mass ratioes with the masterbatch polyester slice,, when the water ratio of mixture is lower than 50ppm, enter forcing machine in 140～180 ℃ of dryings 1～5 hour; 250～310 ℃ of fusions, through 150～300 order strainer coarse filtrations, the smart filtration of 400～1500 order strainers, head is extruded; With 15～30 ℃ of cold drum cooling casting sheets; Carry out 2.5～4.0 times of longitudinal stretchings at 70～100 ℃; Carry out 2.5～4.0 times of cross directional stretchs at 100～150 ℃; Carry out heat setting type processing back rolling in 170～230 ℃ and cut, promptly make solar cell backboard polyester for film film;

Described masterbatch vibrin section is for containing barium sulfate (BaSO ₄) and the particle diameter of barium sulfate be that the mass percentage content of 0.2～0.4 μ m, barium sulfate is 30%～80% polyester masterbatch section (products production enterprise has: Linyi City is cherished bright plastics company limited, the triumphant company of U.S.'s Aomei, the yellow river of Dongguan City sun titanizing worker plastic cement firm), contain titanium dioxide (TiO ₂) and the particle diameter of titanium dioxide be that the mass percentage content of 0.2～0.4 μ m, titanium dioxide is 30%～80% polyester masterbatch section (products production enterprise has: Britain Weir soil Bedwas company, Clariant chemical industry (China) company limited, the color gorgeous limited-liability company in Guangzhou), and contain silicon-dioxide (SiO ₂) and the particle diameter of silicon-dioxide be that the mass percentage content of 2～3.5 μ m, silicon-dioxide is that (products production enterprise has: any one or two kinds of above mixtures abundant magnificent polyester company limited of Nanjing Hao Yuan chemical industry company limited, Clariant chemical industry (China) company limited, Zhuhai) for the polyester masterbatch section of 2500～3500ppm; Each polyester masterbatch section is market outsourcing product (being the commercial goods).

In the content of the present invention: described in the step (a) in the diprotic acid, the diprotic acid of 0.01～5 mass parts wherein can be replaced with the m-phthalic acid, phthalic acid, hexanodioic acid, sebacic acid, 4,4 of 0.01～5 mass parts '-any one or two kinds of above mixtures in the biphenyl dicarboxylic acid.

In the content of the present invention: described in the step (a) in the dibasic alcohol, the dibasic alcohol of 0.01～5 mass parts wherein can be replaced with 1 of 0.01～5 mass parts, ammediol, 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, 1, any one or two kinds of above mixtures in 6-hexylene glycol, glycol ether, neopentyl glycol, the polyalkylene glycol.

In the content of the present invention: the polyvalent alcohol of high side chain described in the step (a) can be glycerol, the tetramethylol methane, 1,3 that contains 3 and above activity hydroxy, any one or two kinds of above mixtures in 5 phloroglucitols.

In the content of the present invention: containing 16 carbon and above containing diene or triethenoid fatty acid can be along 9 in described polyenoid higher fatty acid of step (b) or the alcohol, along 12, along the 15-punicic acid, along 6, along 9, along the 12-punicic acid or along 9, along the 12-octadecadienoic acid.

In the content of the present invention: contain 16 carbon in described polyenoid higher fatty acid of step (b) or the alcohol and above contain diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18) can be along 9, along 12-18 carbon dienols or along 9, along 12, along the 15-octadecatrienol.

The performance perameter that adopts the product of the present invention's preparation to have is: prepared polyester film under 85 ℃, 85% humidity condition through 3000 hours aging after, the tensile strength of polyester film, extension at break conservation rate are (IEC61215-2005 international standard " ground is identified with the Crystalline Silicon PV Module design and finalized the design ") 50% or more; The polyester film of usual thickness specification 0.250mm its water vapour permeability under 38 ℃, 90% humidity condition is lower than 1g/m ².24h (GB1037-1988 " plastics film and the cup type method of sheet material water vapor permeability test method "); Flame retardant resistance reaches UL94VTM-2 (ANST/UL94-1985 " U.S.'s fire retardant material standard and testing method ").

The basement membrane of the application type solar cell backboard film that adopts the product-solar cell backboard polyester for film film of the present invention's preparation to be suitable for to do TPT, TPE, KPK composite solar battery backboard film and make at polyester film single face (another side coating EVA rete) or double spread fluoro-containing coating.

Compared with prior art, the present invention has following characteristics and beneficial effect:

What (1) adopt among the present invention is that one or more dicarboxylic acid and one or more dibasic alcohol carry out polymerization and the polymkeric substance that makes, has improved the crystal property and the crystal configuration of polyester; The introducing of a small amount of polyenoid higher fatty acid or alcohol, the terminal hydroxy group to polyester when polymerization carries out end-blocking, to reduce the water-absorbent of polyester film, has reduced the water vapour permeability of polyester film.The introducing of the polyvalent alcohol of a small amount of high side chain, because of containing the activity hydroxy more than at least 3, in synthesizing polyester, increase the sterically hindered of ester bond, reduce water, the thermal destruction of ester bond, improve humidity resistance, the flame retardant resistance of polyester film, reduced the water vapour permeability of polyester film;

(2) the present invention is by masterbatch vibrin section, with the introducing of the inorganic additives particle of a certain amount of and particle diameter, fills polyester film noncrystalline domain space, reduced the water vapour permeability of polyester film;

(3) do not adopt interpolation phosphorus system or other based flame retardant among the present invention, got rid of the humidity resistance problem that influences polyester film because of the hydrolytic resistance difference of fire retardant.

(4) effect comparison of product water vapour permeability of the present invention:

Water vapour permeability (38 ℃, 90% relative humidity condition under) contrast

Film thickness	Existing PET film	Polyester of the present invention or copolyesters film
			0.250mm	＞2.5g/m 2.24h	＜1g/m 2.24h
0.188mm	＞3.0g/m 2.24h	＜1.3g/m 2.24h
			0.150mm	＞3.5g/m 2.24h	＜1.5g/m 2.24h
0.125mm	＞4g/m 2.24h	＜1.8g/m 2.24h

(5) the present invention adopts section of synthesis modification vibrin and masterbatch polyester slice, through biaxial stretch-formed one-tenth polyester film; Synthesizing of modified polyester resin section, use or also use by multiple diprotic acid or dibasic alcohol list, and a small amount of one or more polyenoid higher fatty acid or alcohol have been increased, and the polyvalent alcohol of one or more high side chains on a small quantity, obtain improving the modified polyester resin section of solar cell backboard polyester for film film performance; The polyester film that adopts the present invention to make has excellent physical and mechanical performance, wet-hot aging performance, dimensional stability, electrical insulation capability, flame retardant properties, anti-steam breathability;

(6) preparation technology of the present invention is simple, and operation is practical easily.

Embodiment

Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.

Embodiment 1:

The production of modified polyester resin section: with 2 of the terephthalic acid of 200 mass parts, 50 mass parts, the antimonous oxide of the isoamyl tetrol of the hexanodioic acid of the ethylene glycol of 6-naphthalic acid, 96 mass parts, 0.01 mass parts, 0.5 mass parts, the Cobaltous diacetate of 0.09 mass parts, 0.10 mass parts and the triphenylphosphate of 0.02 mass parts add pulping tank, start stirrer, with the making beating of 60 rev/mins of speed after 25 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.3 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 80 rev/mins speed, keep temperature in the kettle at 255～260 ℃, continue esterification 30 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, stir 15 minutes with 60 rev/mins speed after, progressively heat up and fall vacuum and carry out prepolymerization reaction, in 40～60 minutes, stop to heat up with behind still temperature rise to 270～275 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 256 ℃ of fusing points, limiting viscosity 0.65g/dl after testing.

The section of masterbatch vibrin is prepared: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 30%).

Synthetic modified polyester resin section is mixed by 100: 30 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 140～150 ℃ drying 5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 250～270 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 400 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 70～80 ℃, carry out 2.5 times of longitudinal stretchings; Under 100～130 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 170～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 2:

The production of modified polyester resin section: with 1 of the ethylene glycol of the terephthalic acid of 400 mass parts, 155 mass parts, 5 mass parts, the antimonous oxide of the isoamyl tetrol of ammediol, 0.01 mass parts, the Cobaltous diacetate of 0.07 mass parts, 0.04 mass parts and the phosphoric acid of 0.03 mass parts add pulping tank, start stirrer with the making beating of 50 rev/mins speed after 30 minutes, progressively add an esterifying kettle, esterification is controlled at 245～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 1.0 mass parts along 6, along 9,, start stirrer along the 12-punicic acid, stir with 50 rev/mins speed, keep temperature in the kettle at 250～255 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 40 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～275 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 30 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 258 ℃ of fusing points, limiting viscosity 0.68g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3000ppm).

Synthesis modification vibrin section is mixed by 100: 15 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 170～180 ℃ of dryings 1 hour down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 250～290 ℃ of fusions, through 200 order strainer coarse filtrations, the smart filtration of 600 order strainers, head is extruded; With 25～30 ℃ of cold drum cooling casting sheets; Under 85～100 ℃, carry out 4.0 times of longitudinal stretchings; Under 135～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 170～220 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 3:

The production of modified polyester resin section: with the terephthalic acid of 50 mass parts, 2 of 350 mass parts, the 6-naphthalic acid, the ethylene glycol of 130 mass parts, the neopentyl glycol of 2 mass parts, 0.1 the isoamyl tetrol of mass parts, 0.1 1 of mass parts, 3,5 phloroglucitols, 0.08 the Cobaltous diacetate of mass parts, sodium-acetate mixture (Cobaltous diacetate: sodium-acetate=1: 3), 0.09 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.06 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 252～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.03 mass parts along 6, along 9, along the suitable 9-hexadecenol of 12-punicic acid and 0.07 mass parts, start stirrer, stir, keep temperature in the kettle at 250～260 ℃ with 60 rev/mins speed, continue esterification after 30～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 275～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.70g/dl after testing.

The preparation of masterbatch vibrin section: (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 60%).

Synthesis modification vibrin section is mixed by 100: 15 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 160～170 ℃ drying 3 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 280～300 ℃ of fusions, through 250 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 70～100 ℃, carry out 3.0 times of longitudinal stretchings; Under 120～150 ℃, carry out 3.5 times of cross directional stretchs; After carrying out heat setting type under 190～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 4:

The production of modified polyester resin section: with the terephthalic acid of 200 mass parts, 2 of 50 mass parts, the 6-naphthalic acid, the ethylene glycol of 95 mass parts, 1 of 2 mass parts, the 4-butyleneglycol, 0.1 the glycerol of mass parts, 0.4 1 of mass parts, 3,5 phloroglucitols, 0.07 the sodium-acetate of mass parts, 0.07 the phosphoric acid of the antimonous oxide of mass parts and 0.03 mass parts adds pulping tank, start stirrer, with the making beating of 70 rev/mins of speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 253～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.3 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 70 rev/mins speed, keep temperature in the kettle at 255～265 ℃, continue esterification after 30～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, stir 15 minutes with 50 rev/mins speed after, progressively heat up and fall vacuum and carry out prepolymerization reaction.In 40～60 minutes,, stop to heat up with behind still temperature rise to 275～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 257 ℃ of fusing points, limiting viscosity 0.66g/dl after testing.

The preparation of masterbatch vibrin section: barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 40%).

Synthetic modified polyester resin section is mixed by 100: 5 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 165～175 ℃ drying 2 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 295～300 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1000 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 80～100 ℃, carry out 4.0 times of longitudinal stretchings; Under 100～130 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 180～220 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 5:

The production of modified polyester resin section: with 2 of the terephthalic acid of 200 mass parts, 50 mass parts, the antimonous oxide of the isoamyl tetrol of the ethylene glycol of 6-naphthalic acid, 98 mass parts, 0.3 mass parts, the Cobaltous diacetate of 0.12 mass parts, 0.06 mass parts and the trimethyl phosphite 99 of 0.06 mass parts add pulping tank, start stirrer, with the making beating of 60 rev/mins speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.6 mass parts along 9, along the 12-octadecadienoic acid, start stirrer, stir with 60 rev/mins speed, keep temperature in the kettle at 250～255 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes, vacuum is dropped in the 100Pa, best? control in the 20Pa, stir and reduce to 20 rev/mins, carry out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 257 ℃ of fusing points, limiting viscosity 0.67g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2500ppm).

Synthesis modification vibrin section is mixed by 100: 10 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 165～175 ℃ drying 2.5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 250～285 ℃ of fusions, through 200 order strainer coarse filtrations, the smart filtration of 1200 order strainers, head is extruded; With 20～30 ℃ of cold drum cooling casting sheets; Under 75～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 120～150 ℃, carry out 3.5 times of cross directional stretchs; After carrying out heat setting type under 190～230 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 6:

The production of modified polyester resin section: with 1 of the glycerol of the ethylene glycol of the terephthalic acid of 400 mass parts, 160 mass parts, 0.1 mass parts, 0.3 mass parts, 3, the antimonous oxide of the magnesium acetate of 5 phloroglucitols, 0.04 mass parts, 0.04 mass parts and 0.01 phosphoric acid add pulping tank, start stirrer, with the making beating of 50 rev/mins speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add suitable 9 of 0.2 mass parts, along suitable 6 of 12-octadecadienoic acid and 0.1 mass parts, along 9, along the 12-punicic acid, start stirrer, stir, keep temperature in the kettle at 255～265 ℃ with 60 rev/mins speed, continue esterification after 35 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 273～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 30 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 255 ℃ of fusing points, limiting viscosity 0.66g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 50%).

Synthetic modified polyester resin section is mixed by 100: 20 proportioning with the section of masterbatch vibrin, dropped in the dry basin under 155～165 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 290～300 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1500 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 75～95 ℃, carry out 3.5 times of longitudinal stretchings; Under 110～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 170～205 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 7:

The production of modified polyester resin section: with the terephthalic acid of 400 mass parts, the ethylene glycol of 160 mass parts, 0.1 the glycerol of mass parts, 0.3 1 of mass parts, 3,5 phloroglucitols, 0.1 the isoamyl tetrol of mass parts, 0.05 the sodium-acetate of mass parts, 0.05 the triphenylphosphate of the antimonous oxide of mass parts and 0.05 mass parts adds pulping tank, start stirrer, with the making beating of 50 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 245～253 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.8 mass parts along 6, along 9,, start stirrer along the 12-punicic acid, stir with 60 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 20 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 275～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 30 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 255 ℃ of fusing points, limiting viscosity 0.75g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3500ppm) and titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 80%) the quality proportioning be 1: 10.

Synthetic modified polyester resin section is mixed by 100: 25 proportioning with the section of masterbatch vibrin, dropped in the dry basin under 150～160 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 280～300 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 22～27 ℃ of cold drum cooling casting sheets; Under 80～100 ℃, carry out 3.0 times of longitudinal stretchings; Under 120～150 ℃, carry out 4.0 times of cross directional stretchs; After carrying out heat setting type under 200～220 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 8:

The production of modified polyester resin section: with 2 of the terephthalic acid of 50 mass parts, 350 mass parts, the antimonous oxide of the isoamyl tetrol of the glycol ether of the ethylene glycol of 6-naphthalic acid, 130 mass parts, 2 mass parts, 0.4 mass parts, the Cobaltous diacetate of 0.09 mass parts, 0.011 mass parts and the trimethyl phosphite 99 of 0.04 mass parts add pulping tank, start stirrer, with the making beating of 90 rev/mins speed after 25 minutes, progressively add an esterifying kettle, esterification is controlled at 251～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.2 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 80 rev/mins speed, keep temperature in the kettle at 250～265 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 40 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 251 ℃ of fusing points, limiting viscosity 0.60g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3000ppm).

Synthetic modified polyester resin section is mixed by 100: 10 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 155～165 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 270～290 ℃ of fusions, through 250 order strainer coarse filtrations, the smart filtration of 1500 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 70～90 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～140 ℃, carry out 3.0 times of cross directional stretchs; After carrying out heat setting type under 190～230 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 9:

The production of modified polyester resin section: with 2 of 360 mass parts, the 6-naphthalic acid, the ethylene glycol of 110 mass parts, 0.2 the isoamyl tetrol of mass parts, 0.08 the magnesium acetate of mass parts, 0.04 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.03 mass parts, triphenylphosphate, phosphate mixture (trimethyl phosphite 99: triphenylphosphate: phosphoric acid=1: 3: 2) add pulping tank, start and stir 90 rev/mins, pull an oar after 18 minutes, progressively add an esterifying kettle, esterification is controlled at 252～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add suitable 9 of 0.2 mass parts, along 12, along suitable 9 of 15-punicic acid and 0.1 mass parts, along the 12-octadecadienoic acid, start stirrer, stir, keep temperature in the kettle at 250～255 ℃ with 50 rev/mins speed, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 40 rev/mins speed stirrings.In 50 minutes,, stop to heat up with after the still temperature rise to 278 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 262 ℃ of fusing points, limiting viscosity 0.71g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2900ppm).

Synthetic modified polyester resin section is mixed by 100: 30 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 160～170 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 270～300 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 18～25 ℃ of cold drum cooling casting sheets; Under 90～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～140 ℃, carry out 3.0 times of cross directional stretchs; After carrying out heat setting type under 190～220 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 10:

The production of modified polyester resin section: with the terephthalic acid of 50 mass parts, 2 of 350 mass parts, the 6-naphthalic acid, the ethylene glycol of 130 mass parts, 1 of 2 mass parts, the 4-cyclohexanedimethanol, 0.1 the isoamyl tetrol of mass parts, 0.1 the glycerol of mass parts, 0.05 the Cobaltous diacetate of mass parts, 0.05 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.03 mass parts adds pulping tank, start stirrer, with the making beating of 80 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.2 mass parts along 9, along the 12-octadecadienoic acid, start stirrer, stir with 70 rev/mins speed, keep temperature in the kettle at 255～265 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 259 ℃ of fusing points, limiting viscosity 0.67g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2800ppm).

Synthesis modification vibrin section is mixed by 100: 10 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 145～155 ℃ drying 5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 290～210 ℃ of fusions, through 200 order strainer coarse filtrations, the smart filtration of 1200 order strainers, head is extruded; With 18～23 ℃ of cold drum cooling casting sheets; Under 80～90 ℃, carry out 3.0 times of longitudinal stretchings; Under 100～130 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 200～220 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 11:

The production of modified polyester resin section: with 2 of the terephthalic acid of 100 mass parts, 300 mass parts, 1 of the ethylene glycol of 6-naphthalic acid, 140 mass parts, 0.4 mass parts, 3, the phosphoric acid of the antimonous oxide of the sodium-acetate of 5 phloroglucitols, 0.09 mass parts, 0.06 mass parts and 0.03 mass parts adds pulping tank, start stirrer, with the making beating of 90 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.7 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 60 rev/mins speed, keep temperature in the kettle at 255～265 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.70g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3200ppm) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 40%) the quality proportioning be 1: 6.

Synthesis modification vibrin section is mixed by 100: 20 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 170～180 ℃ of dryings 1.5 hours down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 280 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 500 order strainers, head is extruded; With 23～28 ℃ of cold drum cooling casting sheets; Under 80～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 120～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 195～225 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 12:

The production of modified polyester resin section: 2 of 350 mass parts, 1 of the ethylene glycol of 6-naphthalic acid, 110 mass parts, 0.2 mass parts, 3, the triphenylphosphate of the antimonous oxide of the magnesium acetate of 5 phloroglucitols, 0.06 mass parts, 0.07 mass parts and 0.04 mass parts adds pulping tank, start stirrer, with the making beating of 80 rev/mins speed after 25 minutes, progressively add an esterifying kettle, esterification is controlled at 251～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.5 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 70 rev/mins speed, keep temperature in the kettle at 254～264 ℃, continue esterification after 15～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 274～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.71g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3000ppm) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 30%) the quality proportioning be 1: 15.

Synthesis modification vibrin section is mixed by 100: 15 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 170～180 ℃ of dryings 2 hours down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 285～305 ℃ of fusions, through 180 order strainer coarse filtrations, the smart filtration of 600 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 70～90 ℃, carry out 3.0 times of longitudinal stretchings; Under 130～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 185～215 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 13:

The production of modified polyester resin section: with the terephthalic acid of 50 mass parts, 2 of 350 mass parts, the 6-naphthalic acid, the ethylene glycol of 130 mass parts, 0.01 the isoamyl tetrol of mass parts, 0.10 the Cobaltous diacetate of mass parts, sodium-acetate, magnesium acetate mixture (Cobaltous diacetate: sodium-acetate: magnesium acetate=1: 1: 1), 0.07 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.05 mass parts adds pulping tank, start stirrer, with the making beating of 80 rev/mins speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 255～262 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 1.0 mass parts along 9, along 12-18 carbon dienols, start stirrer, stir with 50 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 40 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～278 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 261 ℃ of fusing points, limiting viscosity 0.67g/dl after testing.

The section of masterbatch vibrin is prepared: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 75%) and silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2800ppm) the quality proportioning be 1: 1.

Synthetic modified polyester resin section is mixed by 100: 30 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 145～155 ℃ drying 5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 290～310 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 900 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 90～100 ℃, carry out 2.5 times of longitudinal stretchings; Under 100～140 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 180～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 14:

The production of modified polyester resin section: with the terephthalic acid of 125 mass parts, the m-phthalic acid of 2 mass parts, 2 of 70 mass parts, the 6-naphthalic acid, the hexanodioic acid of 3 mass parts, the ethylene glycol of 80 mass parts, 0.1 the isoamyl tetrol of mass parts, 0.2 the glycerol of mass parts, 0.09 the sodium-acetate of mass parts, 0.04 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.04 mass parts, phosphate mixture (trimethyl phosphite 99: phosphoric acid=2: 1) add pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.6 mass parts along 9, along 12-18 carbon dienols, start stirrer, stir with 50 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.66g/dl after testing.

The section of masterbatch vibrin is prepared: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 65%) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 55%) the quality proportioning be 1: 2.

The section of synthetic modified polyester resin is mixed by 100: 15 quality proportioning with the masterbatch polyester slice, drop in the dry basin to descend dry 3 hours, when the water ratio of polyester slice is lower than 50ppm, inject forcing machine at 155～165 ℃; 280～300 ℃ of fusions, through 250 order strainer coarse filtrations, the smart filtration of 1200 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 70～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～130 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 200～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 15:

The production of modified polyester resin section: with the terephthalic acid of 50 mass parts, 2 of 350 mass parts, the 6-naphthalic acid, the ethylene glycol of 130 mass parts, 0.1 the isoamyl tetrol of mass parts, 0.1 1 of mass parts, 3,5 phloroglucitols, 0.2 the glycerol of mass parts, 0.11 the magnesium acetate of mass parts, 0.04 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.05 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.1 mass parts along 9, along 12,, start stirrer along the 15-punicic acid, stir with 60 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 259 ℃ of fusing points, limiting viscosity 0.68g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2500ppm), titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 35%) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 50%) the quality proportioning be 1: 3: 4.

Synthesis modification vibrin section is mixed by 100: 15 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 170～180 ℃ of dryings 1 hour down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 250～280 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 25～30 ℃ of cold drum cooling casting sheets; Under 75～100 ℃, carry out 4.0 times of longitudinal stretchings; Under 125～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 170～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 16:

The production of modified polyester resin section: 2 of 350 mass parts, the 6-naphthalic acid, the ethylene glycol of 110 mass parts, 0.1 the isoamyl tetrol of mass parts, 0.2 1 of mass parts, 3,5 phloroglucitols, 0.1 the glycerol of mass parts, 0.5 the sodium-acetate of mass parts, magnesium acetate mixture (sodium-acetate: magnesium acetate=1: 4), 0.08 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.02 mass parts adds pulping tank, start stirrer, with the making beating of 80 rev/mins speed after 25 minutes, progressively add an esterifying kettle, esterification is controlled at 252～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 35 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add suitable 9 of 0.2 mass parts, along 12, along suitable 9 of 15-punicic acid and 0.1 mass parts, along 12-18 carbon dienols, start stirrer, stir, keep temperature in the kettle at 250～255 ℃ with 70 rev/mins speed, continue esterification after 35～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with after the still temperature rise to 280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 261 ℃ of fusing points, limiting viscosity 0.68g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3000ppm), titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 80%) quality proportioning is 1: 7.

Synthesis modification vibrin section is mixed by 100: 5 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 165～175 ℃ of dryings 2 hours down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 255～295 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1000 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 70～95 ℃, carry out 4.0 times of longitudinal stretchings; Under 115～150 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 205～230 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 17:

The production of modified polyester resin section: with the terephthalic acid of 40 mass parts, 2 of 360 mass parts, the 6-naphthalic acid, the ethylene glycol of 130 mass parts, 0.01 the neopentyl glycol of mass parts, 0.2 the isoamyl tetrol of mass parts, 0.1 1 of mass parts, 3,5 phloroglucitols, 0.10 the Cobaltous diacetate of mass parts, 0.05 the triphenylphosphate of the antimonous oxide of mass parts and 0.01 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.2 mass parts pure and mild 0.1 mass parts of suitable 9-cetene along 6, along 9, along the 12-punicic acid, start stirrer, stir, keep temperature in the kettle at 255～262 ℃ with 70 rev/mins speed, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 30 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.69g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 35%) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 35%) the quality proportioning is 1: 1.

Synthetic modified polyester resin section is mixed by 100: 5 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 165～175 ℃ drying 3 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 265～295 ℃ of fusions, through 200 order strainer coarse filtrations, the smart filtration of 1500 order strainers, head is extruded; With 22 ℃ of cold drum cooling casting sheets; Under 75～95 ℃, carry out 3.0 times of longitudinal stretchings; Under 100～145 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 210～225 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 18:

The production of modified polyester resin section: with the terephthalic acid of 30 mass parts, 2 of 370 mass parts, the 6-naphthalic acid, the ethylene glycol of 128 mass parts, 1 of 2 mass parts, the 6-hexylene glycol, 0.3 1 of mass parts, 3,5 phloroglucitols, 0.09 the magnesium acetate of mass parts, 0.08 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.05 mass parts, triphenylphosphate mixture (trimethyl phosphite 99: triphenylphosphate=1: 2) add pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add suitable 6 of 0.1 mass parts, along 9, along suitable 9 of 12-punicic acid, 0.2 mass parts, along 12, the suitable 9-hexadecenol along 15-punicic acid and 0.1 mass parts starts stirrer, stir with 80 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 15～25 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 20 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～275 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 30 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.The modified copolyester resin slicer is 258 ℃ of fusing points, limiting viscosity 0.65g/dl after testing.

The section of masterbatch vibrin is prepared: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 65%) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 35%) the quality proportioning be 2: 5.

Synthetic modified polyester resin section is mixed by 100: 5 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 140～150 ℃ drying 5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 250～285 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1200 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 70～90 ℃, carry out 2.5 times of longitudinal stretchings; Under 100～140 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 170～205 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 19:

The production of modified polyester resin section: with the terephthalic acid of 200 mass parts, 2 of 50 mass parts, the 6-naphthalic acid, 4 of 5 mass parts, 4 '-biphenyl dicarboxylic acid, the ethylene glycol of 98 mass parts, 1 of 2 mass parts, the 4-butyleneglycol, 0.6 the glycerol of mass parts, 0.4 1 of mass parts, 3,5 phloroglucitols, 0.06 the Cobaltous diacetate of mass parts, 0.05 the phosphoric acid of the antimonous oxide of mass parts and 0.03 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, and reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add suitable 6 of 0.1 mass parts, along 9, along suitable 9 of 12-punicic acid and 0.2 mass parts, along 12,, start stirrer along the 15-punicic acid, stir with 70 rev/mins speed, keep temperature in the kettle at 256～262 ℃, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 260 ℃ of fusing points, limiting viscosity 0.74g/dl after testing.

The preparation of masterbatch vibrin section: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3500ppm), titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 80%), barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 70%) the quality proportioning be 1: 3: 2.

Synthetic modified polyester resin section is mixed by 100: 25 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 165～175 ℃ drying 2.5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 285～305 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 1000 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 85～100 ℃, carry out 3.0 times of longitudinal stretchings; Under 110～145 ℃, carry out 3.0 times of cross directional stretchs; After carrying out heat setting type under 180～215 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 20:

The production of modified polyester resin section: with the terephthalic acid of 400 mass parts, 2 of 30 mass parts, the 6-naphthalic acid, the ethylene glycol of 173 mass parts, 1 of 2 mass parts, the 4-butyleneglycol, 0.5 1 of mass parts, 3,5 phloroglucitols, 0.2 the isoamyl tetrol of mass parts, 0.01 the Cobaltous diacetate of mass parts, sodium-acetate mixture (Cobaltous diacetate: sodium-acetate=1: 1), 0.12 the antimonous oxide of mass parts and 0.01 triphenylphosphate add pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 245～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add the suitable 9-hexadecenol of 0.7 mass parts, start stirrer, stir, keep temperature in the kettle, continue esterification after 35～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure at 255～265 ℃ with 50 rev/mins speed.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 264 ℃ of fusing points, limiting viscosity 0.71g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 55%), barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 40%) and silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3500ppm) the quality proportioning be 3: 5: 1.

Synthetic modified polyester resin section is mixed by 100: 15 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 145～155 ℃ drying 5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 260～295 ℃ of fusions, through 200 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 15～20 ℃ of cold drum cooling casting sheets; Under 80～95 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～135 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 195～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 21:

The production of modified polyester resin section: with the terephthalic acid of 400 mass parts, the ethylene glycol of 170 mass parts, 0.4 1 of mass parts, 3,5 phloroglucitols, 0.3 the isoamyl tetrol of mass parts, 0.05 the sodium-acetate of mass parts, 0.07 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.04 mass parts, triphenylphosphate, phosphate mixture (trimethyl phosphite 99: triphenylphosphate: phosphoric acid=3: 1: 1) add pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 252～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 35 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.2 mass parts pure and mild 0.6 mass parts of suitable 9-cetene along 9, along 12, along the 15-punicic acid, start stirrer, stir, keep temperature in the kettle at 250～265 ℃ with 60 rev/mins speed, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 263 ℃ of fusing points, limiting viscosity 0.72g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 60%), barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 45%) and silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 2500ppm) the quality proportioning be 2: 6: 1.

Synthetic modified polyester resin section is mixed by 100: 25 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 150 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 290 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1200 order strainers, head is extruded; With 20 ℃ of cold drum cooling casting sheets; Under 80 ℃, carry out 4.0 times of longitudinal stretchings; Under 100 ℃, carry out 3.5 times of cross directional stretchs; After carrying out heat setting type under 205 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 22:

The production of modified polyester resin section: with the terephthalic acid of 240 mass parts, 2 of 150 mass parts, the 6-naphthalic acid, the ethylene glycol of 150 mass parts, 0.5 1 of mass parts, 3,5 phloroglucitols, 0.2 the isoamyl tetrol of mass parts, 0.08 the Cobaltous diacetate of mass parts, sodium-acetate, magnesium acetate mixture (Cobaltous diacetate: sodium-acetate: magnesium acetate=1: 2: 2), 0.12 the phosphoric acid of the antimonous oxide of mass parts and 0.06 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 249～258 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add the suitable 9-hexadecenol of 0.5 mass parts, start stirrer, stir, keep temperature in the kettle, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure at 250～255 ℃ with 50 rev/mins speed.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 20 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 259 ℃ of fusing points, limiting viscosity 0.71g/dl after testing.

The section of masterbatch vibrin is prepared: silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3000ppm) and titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m, content 70%) the quality proportioning be 1: 5.

Synthesis modification vibrin section is mixed by 100: 20 quality proportionings with the section of masterbatch vibrin, drop in the dry basin 170～180 ℃ of dryings 2.5 hours down, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 275～300 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 600 order strainers, head is extruded; With 20～25 ℃ of cold drum cooling casting sheets; Under 75～95 ℃, carry out 4.0 times of longitudinal stretchings; Under 110～140 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 175～205 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 23:

The production of modified polyester resin section: with the terephthalic acid of 140 mass parts, 2 of 130 mass parts, the 6-naphthalic acid, the ethylene glycol of 100 mass parts, 0.2 the glycerol of mass parts, 0.3 the isoamyl tetrol of mass parts, 0.12 the sodium-acetate of mass parts, 0.08 the triphenylphosphate of the antimonous oxide of mass parts and 0.03 mass parts adds pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 254～262 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add the suitable 9-hexadecenol of 0.7 mass parts, start stirrer, stir, keep temperature in the kettle, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure at 250～265 ℃ with 80 rev/mins speed.Start stirrer, after 15 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～280 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 262 ℃ of fusing points, limiting viscosity 0.73g/dl after testing.

The section of masterbatch vibrin is prepared: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 50%) and silicon-dioxide (SiO ₂) polyester masterbatch section (SiO ₂Particle diameter 2～3.5 μ m, content 3500ppm) the quality proportioning be 8: 1.

Synthetic modified polyester resin section is mixed by 100: 30 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 145～165 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 275～295 ℃ of fusions, through 150 order strainer coarse filtrations, the smart filtration of 800 order strainers, head is extruded; With 23～28 ℃ of cold drum cooling casting sheets; Under 85～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～130 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 190～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 24:

The production of modified polyester resin section: with the terephthalic acid of 200 mass parts, 2 of 119 mass parts, the 6-naphthalic acid, the own dioctyl phthalate of 1 mass parts, the ethylene glycol of 120 mass parts, 0.01 1 of mass parts, the 4-cyclohexanedimethanol, 0.1 the glycerol of mass parts, 0.2 the isoamyl tetrol of mass parts, 0.1 1 of mass parts, 3,5 phloroglucitols, 0.06 the magnesium acetate of mass parts, 0.04 the triphenylphosphate of the antimonous oxide of mass parts and 0.02 mass parts, the mixture of phosphoric acid (triphenylphosphate: phosphoric acid=3: 1) add pulping tank, start stirrer, with the making beating of 100 rev/mins speed after 15 minutes, progressively add an esterifying kettle, esterification is controlled at 250～255 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.5 mass parts pure and mild 0.1 mass parts of suitable 9-cetene along 6, along 9, along the 12-punicic acid, start stirrer, stir, keep temperature in the kettle at 255～265 ℃ with 60 rev/mins speed, continue esterification after 35～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 25 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 50 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with behind still temperature rise to 270～278 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 258 ℃ of fusing points, limiting viscosity 0.70g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 45%), barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 35%) the quality proportioning be 1: 3.

Synthetic modified polyester resin section is mixed by 100: 25 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 165～175 ℃ drying 3.5 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 280～300 ℃ of fusions, through 300 order strainer coarse filtrations, the smart filtration of 1500 order strainers, head is extruded; With 21 ℃ of cold drum cooling casting sheets; Under 90～100 ℃, carry out 3.5 times of longitudinal stretchings; Under 100～145 ℃, carry out 4.0 times of cross directional stretchs; After carrying out heat setting type under 200～230 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 25:

The production of modified polyester resin section: with the terephthalic acid of 300 mass parts, 2 of 50 mass parts, the 6-naphthalic acid, the ethylene glycol of 140 mass parts, 0.1 the isoamyl tetrol of mass parts, 0.1 the glycerol of mass parts, 0.2 1 of mass parts, 3,5 phloroglucitols, 0.04 the Cobaltous diacetate of mass parts, 0.04 the trimethyl phosphite 99 of the antimonous oxide of mass parts and 0.01 mass parts adds pulping tank, start stirrer, with the making beating of 90 rev/mins speed after 20 minutes, progressively add an esterifying kettle, esterification is controlled at 255～260 ℃, reaction is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, about 30 minutes,, assert that esterification finishes, and changes two esterifying kettles over to when aquifer yield reaches 95% when above of theoretical aquifer yield.Add 0.3 mass parts along 6, along 9,, start stirrer along the 12-punicic acid, stir with 70 rev/mins speed, keep temperature in the kettle at 250～260 ℃, continue esterification after 25～40 minutes, material is gone into polycondensation vessel through the filter filtration pressure.Start stirrer, after 20 minutes, progressively heat up, fall vacuum and carry out prepolymerization reaction with 60 rev/mins speed stirrings.In 40～60 minutes,, stop to heat up with after the still temperature rise to 278 ℃; In 40～60 minutes vacuum is dropped in the 100Pa, preferably control in the 20Pa, stirrer is reduced to 10 rev/mins, carries out the high vacuum polymerization.After polymerization in 2～4 hours, when viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging.Modified polyester resin cut into slices 261 ℃ of fusing points, limiting viscosity 0.72g/dl after testing.

The preparation of masterbatch vibrin section: titanium dioxide (TiO ₂) polyester masterbatch section (TiO ₂Particle diameter 0.2～0.4 μ m content 30%) and barium sulfate (BaSO ₄) polyester masterbatch section (BaSO ₄Particle diameter 0.2～0.4 μ m, content 30%) the quality proportioning be 1: 6.

Synthetic modified polyester resin section is mixed by 100: 15 quality proportioning with the section of masterbatch vibrin, dropped in the dry basin under 155～165 ℃ drying 4 hours, when the water ratio of polyester slice is lower than 50ppm, the injection forcing machine; 270～295 ℃ of fusions, through 250 order strainer coarse filtrations, the smart filtration of 1500 order strainers, head is extruded; With 25 ℃ of cold drum cooling casting sheets; Under 80～95 ℃, carry out 2.5 times of longitudinal stretchings; Under 100～120 ℃, carry out 2.5 times of cross directional stretchs; After carrying out heat setting type under 195～210 ℃ and handling,, just made solar cell backboard polyester for film film again through rolling with cut.

Embodiment 26:

A kind of manufacture method of solar cell backboard polyester for film film comprises the following steps:

A, the section of synthesis modification vibrin:

(a) (unit is kilogram with 200 mass parts, the back with) the polyester of polyvalent alcohol, 0.01 mass parts of dibasic alcohol, the high side chain of 0.01 mass parts of diprotic acid, 80 mass parts syntheticly add in the pulping tank with the polycondensation catalyst of esterifying catalyst, 0.04 mass parts and the stablizer of 0.01 mass parts, start stirrer, after mixing 15 minutes with the making beating of 50～100 rev/mins speed, progressively add an esterifying kettle, esterification reaction temperature is controlled at 245～260 ℃, reaction times is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, after 15～40 minutes, when aquifer yield reaches 95% when above of theoretical aquifer yield, esterification finishes, and changes material over to two esterifying kettles;

Described diprotic acid is a terephthalic acid, 2, any one or two kinds of mixture in the 6-naphthalic acid;

Described dibasic alcohol is an ethylene glycol;

The polyvalent alcohol of described high side chain is to contain 3～12 carbon and contain in the polyvalent alcohol of 3 and above activity hydroxy any;

Described polyester is synthetic to be one or more mixture in Cobaltous diacetate, sodium-acetate, the magnesium acetate with esterifying catalyst;

Described polycondensation catalyst is an antimonous oxide;

Described stablizer is one or more the mixture in trimethyl phosphite 99, triphenylphosphate, the phosphoric acid;

(b) add the polyenoid higher fatty acid or the alcohol of 0.1 mass parts, start stirrer and stir, keep temperature in the kettle, continue esterification after 15 minutes, material is filtered and be pressed into polycondensation vessel through filter at 250～265 ℃ with 50～80 rev/mins speed;

Described polyenoid higher fatty acid or alcohol are for containing 16 carbon and above contain diene or triethenoid fatty acid or contain 16 carbon and the above any one or two kinds of above mixtures that contain in diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18);

(c) after entering polycondensation vessel, material begins to carry out prepolymerization reaction: start stirrer, with 40～60 rev/mins speed in 30～70 minutes with behind still temperature rise to 270～280 ℃, stop to heat up, simultaneously vacuum drop is reduced to 100～150Pa from normal pressure, then stirrer is reduced to 10～30 rev/mins speed, vacuum control to 0～100Pa carries out the high vacuum polymerization; After high vacuum polymerization in 2～4 hours, when limiting viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging; Promptly make modified polyester resin section, the fusing point of the modified polyester resin section that obtains is 0.60～0.75g/dl greater than 250 ℃, limiting viscosity;

B, manufacturing polyester film:

Synthesis modification vibrin section is mixed by 100: 5 mass ratioes with the masterbatch polyester slice,, when the water ratio of mixture is lower than 50ppm, enter forcing machine in 140～180 ℃ of dryings 1～5 hour; 250～310 ℃ of fusions, through 150～300 order strainer coarse filtrations, the smart filtration of 400～1500 order strainers, head is extruded; With 15～30 ℃ of cold drum cooling casting sheets; Carry out 2.5～4.0 times of longitudinal stretchings at 70～100 ℃; Carry out 2.5～4.0 times of cross directional stretchs at 100～150 ℃; Carry out heat setting type processing back rolling in 170～230 ℃ and cut, promptly make solar cell backboard polyester for film film;

Described masterbatch vibrin section is for containing barium sulfate (BaSO ₄) and the particle diameter of barium sulfate can be 30%～80% polyester masterbatch section (products production enterprise has: Linyi City is cherished bright plastics company limited, the triumphant company of U.S.'s Aomei, the yellow river of Dongguan City sun titanizing worker plastic cement firm) for the mass percentage content of 0.2～0.4 μ m, barium sulfate, contain titanium dioxide (TiO ₂) and the particle diameter of titanium dioxide be that the mass percentage content of 0.2～0.4 μ m, titanium dioxide is 30%～80% polyester masterbatch section (products production enterprise has: Britain Weir soil Bedwas company, Clariant chemical industry (China) company limited, the color gorgeous limited-liability company in Guangzhou), and contain silicon-dioxide (SiO ₂) and the particle diameter of silicon-dioxide be that the mass percentage content of 2～3.5 μ m, silicon-dioxide is that (products production enterprise has: any one or two kinds of above mixtures abundant magnificent polyester company limited of Nanjing Hao Yuan chemical industry company limited, Clariant chemical industry (China) company limited, Zhuhai) for the polyester masterbatch section of 2500～3500ppm; Each polyester masterbatch section is market outsourcing product.

Embodiment 27:

A kind of manufacture method of solar cell backboard polyester for film film comprises the following steps:

A, the section of synthesis modification vibrin:

(a) mainly (unit is kilogram with 400 mass parts, the back with) the polyester of polyvalent alcohol, 0.04 mass parts of dibasic alcohol, the high side chain of 0.5 mass parts of diprotic acid, 160 mass parts syntheticly add in the pulping tank with the polycondensation catalyst of esterifying catalyst, 0.12 mass parts and the stablizer of 0.06 mass parts, start stirrer, after mixing 30 minutes with the making beating of 50～100 rev/mins speed, progressively add an esterifying kettle, esterification reaction temperature is controlled at 245～260 ℃, reaction times is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, after 15～40 minutes, when aquifer yield reaches 95% when above of theoretical aquifer yield, esterification finishes, and changes material over to two esterifying kettles;

Described diprotic acid is a terephthalic acid, 2, any one or two kinds of mixture in the 6-naphthalic acid;

Described dibasic alcohol is an ethylene glycol;

The polyvalent alcohol of described high side chain is to contain 3～12 carbon and contain in the polyvalent alcohol of 3 and above activity hydroxy any;

Described polyester is synthetic to be one or more mixture in Cobaltous diacetate, sodium-acetate, the magnesium acetate with esterifying catalyst;

Described polycondensation catalyst is an antimonous oxide;

Described stablizer is one or more the mixture in trimethyl phosphite 99, triphenylphosphate, the phosphoric acid;

(b) add the polyenoid higher fatty acid or the alcohol of 1.0 mass parts, start stirrer and stir, keep temperature in the kettle, continue esterification after 40 minutes, material is filtered and be pressed into polycondensation vessel through filter at 250～265 ℃ with 50～80 rev/mins speed;

Described polyenoid higher fatty acid or alcohol are for containing 16 carbon and above contain diene or triethenoid fatty acid or contain 16 carbon and the above any one or two kinds of above mixtures that contain in diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18);

(c) after entering polycondensation vessel, material begins to carry out prepolymerization reaction: start stirrer, with 40～60 rev/mins speed in 30～70 minutes with behind still temperature rise to 270～280 ℃, stop to heat up, simultaneously vacuum drop is reduced to 100～150Pa from normal pressure, then stirrer is reduced to 10～30 rev/mins speed, vacuum control to 0～100Pa carries out the high vacuum polymerization; After high vacuum polymerization in 2～4 hours, when limiting viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging; Promptly make modified polyester resin section, the fusing point of the modified polyester resin section that obtains is 0.60～0.75g/dl greater than 250 ℃, limiting viscosity;

B, manufacturing polyester film:

Synthesis modification vibrin section is mixed by 100: 30 mass ratioes with the masterbatch polyester slice,, when the water ratio of mixture is lower than 50ppm, enter forcing machine in 140～180 ℃ of dryings 1～5 hour; 250～310 ℃ of fusions, through 150～300 order strainer coarse filtrations, the smart filtration of 400～1500 order strainers, head is extruded; With 15～30 ℃ of cold drum cooling casting sheets; Carry out 2.5～4.0 times of longitudinal stretchings at 70～100 ℃; Carry out 2.5～4.0 times of cross directional stretchs at 100～150 ℃; Carry out heat setting type processing back rolling in 170～230 ℃ and cut, promptly make solar cell backboard polyester for film film;

Described masterbatch vibrin section is for containing barium sulfate (BaSO ₄) and the particle diameter of barium sulfate can be 30%～80% polyester masterbatch section for the mass percentage content of 0.2～0.4 μ m, barium sulfate, contain titanium dioxide (TiO ₂) and the particle diameter of titanium dioxide be that the mass percentage content of 0.2～0.4 μ m, titanium dioxide is 30%～80% polyester masterbatch section, and contain silicon-dioxide (SiO ₂) and the particle diameter of silicon-dioxide be that the mass percentage content of 2～3.5 μ m, silicon-dioxide is any one or two kinds of above mixtures in the polyester masterbatch section of 2500～3500ppm; Each polyester masterbatch section is market outsourcing product.

Embodiment 28:

A kind of manufacture method of solar cell backboard polyester for film film comprises the following steps:

A, the section of synthesis modification vibrin:

(a) mainly (unit is kilogram with 300 mass parts, the back with) the polyester of polyvalent alcohol, 0.02 mass parts of dibasic alcohol, the high side chain of 0.3 mass parts of diprotic acid, 120 mass parts syntheticly add in the pulping tank with the polycondensation catalyst of esterifying catalyst, 0.08 mass parts and the stablizer of 0.03 mass parts, start stirrer, after mixing 20 minutes with the making beating of 50～100 rev/mins speed, progressively add an esterifying kettle, esterification reaction temperature is controlled at 245～260 ℃, reaction times is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, after 15～40 minutes, when aquifer yield reaches 95% when above of theoretical aquifer yield, esterification finishes, and changes material over to two esterifying kettles;

Described diprotic acid is a terephthalic acid, 2, any one or two kinds of mixture in the 6-naphthalic acid;

Described dibasic alcohol is an ethylene glycol;

The polyvalent alcohol of described high side chain is to contain 3～12 carbon and contain in the polyvalent alcohol of 3 and above activity hydroxy any;

Described polyester is synthetic to be one or more mixture in Cobaltous diacetate, sodium-acetate, the magnesium acetate with esterifying catalyst;

Described polycondensation catalyst is an antimonous oxide;

Described stablizer is one or more the mixture in trimethyl phosphite 99, triphenylphosphate, the phosphoric acid;

(b) add the polyenoid higher fatty acid or the alcohol of 0.5 mass parts, start stirrer and stir, keep temperature in the kettle, continue esterification after 25 minutes, material is filtered and be pressed into polycondensation vessel through filter at 250～265 ℃ with 50～80 rev/mins speed;

Described polyenoid higher fatty acid or alcohol are for containing 16 carbon and above contain diene or triethenoid fatty acid or contain 16 carbon and the above any one or two kinds of above mixtures that contain in diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18);

(c) after entering polycondensation vessel, material begins to carry out prepolymerization reaction: start stirrer, with 40～60 rev/mins speed in 30～70 minutes with behind still temperature rise to 270～280 ℃, stop to heat up, simultaneously vacuum drop is reduced to 100～150Pa from normal pressure, then stirrer is reduced to 10～30 rev/mins speed, vacuum control to 0～100Pa carries out the high vacuum polymerization; After high vacuum polymerization in 2～4 hours, when limiting viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging; Promptly make modified polyester resin section, the fusing point of the modified polyester resin section that obtains is 0.60～0.75g/dl greater than 250 ℃, limiting viscosity;

B, manufacturing polyester film:

Synthesis modification vibrin section is mixed by 100: 16 mass ratioes with the masterbatch polyester slice,, when the water ratio of mixture is lower than 50ppm, enter forcing machine in 140～180 ℃ of dryings 1～5 hour; 250～310 ℃ of fusions, through 150～300 order strainer coarse filtrations, the smart filtration of 400～1500 order strainers, head is extruded; With 15～30 ℃ of cold drum cooling casting sheets; Carry out 2.5～4.0 times of longitudinal stretchings at 70～100 ℃; Carry out 2.5～4.0 times of cross directional stretchs at 100～150 ℃; Carry out heat setting type processing back rolling in 170～230 ℃ and cut, promptly make solar cell backboard polyester for film film;

Described masterbatch vibrin section is for containing barium sulfate (BaSO ₄) and the particle diameter of barium sulfate can be 30%～80% polyester masterbatch section (products production enterprise has: Linyi City is cherished bright plastics company limited, the triumphant company of U.S.'s Aomei, the yellow river of Dongguan City sun titanizing worker plastic cement firm) for the mass percentage content of 0.2～0.4 μ m, barium sulfate, contain titanium dioxide (TiO ₂) and the particle diameter of titanium dioxide be that the mass percentage content of 0.2～0.4 μ m, titanium dioxide is 30%～80% polyester masterbatch section (products production enterprise has: Britain Weir soil Bedwas company, Clariant chemical industry (China) company limited, the color gorgeous limited-liability company in Guangzhou), and contain silicon-dioxide (SiO ₂) and the particle diameter of silicon-dioxide be that the mass percentage content of 2～3.5 μ m, silicon-dioxide is that (products production enterprise has: any one or two kinds of above mixtures abundant magnificent polyester company limited of Nanjing Hao Yuan chemical industry company limited, Clariant chemical industry (China) company limited, Zhuhai) for the polyester masterbatch section of 2500～3500ppm; Each polyester masterbatch section is market outsourcing product.

In the foregoing description 26,27 or 28: described in the step (a) in the diprotic acid, the diprotic acid of 0.01～5 mass parts wherein can be replaced with the m-phthalic acid, phthalic acid, hexanodioic acid, sebacic acid, 4,4 of 0.01～5 mass parts '-any one or two kinds of above mixtures in the biphenyl dicarboxylic acid.

In the foregoing description 26,27 or 28: described in the step (a) in the dibasic alcohol, the dibasic alcohol of 0.01～5 mass parts wherein can be replaced with 1 of 0.01～5 mass parts, ammediol, 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, 1, any one or two kinds of above mixtures in 6-hexylene glycol, glycol ether, neopentyl glycol, the polyalkylene glycol.

In the foregoing description 26,27 or 28: the polyvalent alcohol of high side chain described in the step (a) can be glycerol, the tetramethylol methane, 1,3 that contains 3 and above activity hydroxy, any one or two kinds of above mixtures in 5 phloroglucitols.

In the foregoing description 26,27 or 28: containing 16 carbon and above containing diene or triethenoid fatty acid can be along 9 in described polyenoid higher fatty acid of step (b) or the alcohol, along 12, along the 15-punicic acid, along 6, along 9, along the 12-punicic acid or along 9, along the 12-octadecadienoic acid.

In the foregoing description 26,27 or 28: contain 16 carbon in described polyenoid higher fatty acid of step (b) or the alcohol and above contain diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18) can be along 9, along 12-18 carbon dienols or along 9, along 12, along the 15-octadecatrienol.

Method of the foregoing description and the solar cell backboard polyester for film film product that makes have the affiliated characteristics of content of the present invention, effect and superperformance.

The invention is not restricted to the foregoing description, content of the present invention is described all can implement and have described good result.

Claims (6)

1. the manufacture method of a solar cell backboard polyester for film film is characterized in that comprising the following steps:

A, the section of synthesis modification vibrin:

(a) main diprotic acid with 200～400 mass parts, the dibasic alcohol of 80～160 mass parts, 0.01 the polyvalent alcohol of the high side chain of～0.5 mass parts, 0.01 the synthetic esterifying catalyst of using of the polyester of～0.04 mass parts, 0.04 the stablizer of the polycondensation catalyst of～0.12 mass parts and 0.01～0.06 mass parts adds in the pulping tank, start stirrer, after mixing 15～30 minutes with the making beating of 50～100 rev/mins speed, progressively add an esterifying kettle, esterification reaction temperature is controlled at 245～260 ℃, reaction times is controlled in 3～4 hours and adds, and is incubated 250～265 ℃, pressurize 1 * 10 ⁵～2 * 10 ⁵Pa, after 15～40 minutes, when aquifer yield reaches 95% when above of theoretical aquifer yield, esterification finishes, and changes material over to two esterifying kettles;

Described diprotic acid is a terephthalic acid, 2, any one or two kinds of mixture in the 6-naphthalic acid;

Described dibasic alcohol is an ethylene glycol;

The polyvalent alcohol of described high side chain is to contain 3～12 carbon and contain in the polyvalent alcohol of 3 and above activity hydroxy any;

Described polyester is synthetic to be one or more mixture in Cobaltous diacetate, sodium-acetate, the magnesium acetate with esterifying catalyst;

Described polycondensation catalyst is an antimonous oxide;

Described stablizer is one or more the mixture in trimethyl phosphite 99, triphenylphosphate, the phosphoric acid;

(b) add the polyenoid higher fatty acid or the alcohol of 0.1～1.0 mass parts, start stirrer and stir, keep temperature in the kettle, continue esterification after 15～40 minutes, material is filtered and be pressed into polycondensation vessel through filter at 250～265 ℃ with 50～80 rev/mins speed;

Described polyenoid higher fatty acid or alcohol are for containing 16 carbon and above contain diene or triethenoid fatty acid or contain 16 carbon and the above any one or two kinds of above mixtures that contain in diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18);

(c) after entering polycondensation vessel, material begins to carry out prepolymerization reaction: start stirrer, with 40～60 rev/mins speed in 30～70 minutes with behind still temperature rise to 270～280 ℃, stop to heat up, simultaneously vacuum drop is reduced to 100～150Pa from normal pressure, then stirrer is reduced to 10～30 rev/mins speed, vacuum control to 0～100Pa carries out the high vacuum polymerization; After high vacuum polymerization in 2～4 hours, when limiting viscosity reaches 0.60～0.75g/dl, stop to stir and vacuumizing, charge into the nitrogen discharging; Promptly make modified polyester resin section, the fusing point of the modified polyester resin section that obtains is 0.60～0.75g/dl greater than 250 ℃, limiting viscosity;

B, manufacturing polyester film:

Synthesis modification vibrin section is mixed by 100: 5～30 mass ratioes with the masterbatch polyester slice,, when the water ratio of mixture is lower than 50ppm, enter forcing machine in 140～180 ℃ of dryings 1～5 hour; 250～310 ℃ of fusions, through 150～300 order strainer coarse filtrations, the smart filtration of 400～1500 order strainers, head is extruded; With 15～30 ℃ of cold drum cooling casting sheets; Carry out 2.5～4.0 times of longitudinal stretchings at 70～100 ℃; Carry out 2.5～4.0 times of cross directional stretchs at 100～150 ℃; Carry out heat setting type processing back rolling in 170～230 ℃ and cut, promptly make solar cell backboard polyester for film film;

The section of described masterbatch vibrin is that the mass percentage content of 0.2～0.4 μ m, barium sulfate is 30%～80% polyester masterbatch section for the particle diameter that contains barium sulfate and barium sulfate, the particle diameter that contains titanium dioxide and titanium dioxide is that the mass percentage content of 0.2～0.4 μ m, titanium dioxide is the section of 30%～80% polyester masterbatch, and the particle diameter that contains silicon-dioxide and silicon-dioxide is that the mass percentage content of 2～3.5 μ m, silicon-dioxide is any one or two kinds of above mixtures in the polyester masterbatch section of 2500～3500ppm.

2. press the manufacture method of the described solar cell backboard polyester for film of claim 1 film, it is characterized in that: described in the step (a) in the diprotic acid, with the diprotic acid of 0.01～5 mass parts wherein replace with the m-phthalic acid, phthalic acid, hexanodioic acid, sebacic acid, 4,4 of 0.01～5 mass parts '-any one or two kinds of above mixtures in the biphenyl dicarboxylic acid.

3. press the manufacture method of the described solar cell backboard polyester for film of claim 1 film, it is characterized in that: described in the step (a) in the dibasic alcohol, the dibasic alcohol of 0.01～5 mass parts is wherein replaced with 1 of 0.01～5 mass parts, ammediol, 1,4-butyleneglycol, 1,4-cyclohexanedimethanol, 1, any one or two kinds of above mixtures in 6-hexylene glycol, glycol ether, neopentyl glycol, the polyalkylene glycol.

4. press the manufacture method of the described solar cell backboard polyester for film of claim 1 film, it is characterized in that: the polyvalent alcohol of high side chain described in the step (a) is glycerol, the tetramethylol methane, 1 that contains 3 and above activity hydroxy, any one or two kinds of above mixtures in 3,5 phloroglucitols.

5. press the manufacture method of the described solar cell backboard polyester for film of claim 1 film, it is characterized in that: containing 16 carbon and above containing diene or triethenoid fatty acid is along 9 in described polyenoid higher fatty acid of step (b) or the alcohol, along 12, along the 15-punicic acid, along 6, along 9, along the 12-punicic acid or along 9, along the 12-octadecadienoic acid.

6. press the manufacture method of the described solar cell backboard polyester for film of claim 1 film, it is characterized in that: contain 16 carbon in described polyenoid higher fatty acid of step (b) or the alcohol and above contain diene or the triolefin Fatty Alcohol(C12-C14 and C12-C18) is along 9, along 12-18 carbon dienols or along 9, along 12, along the 15-octadecatrienol.