CN102653588B - Polyester for matt film and preparation method of film thereof - Google Patents
Polyester for matt film and preparation method of film thereof Download PDFInfo
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- CN102653588B CN102653588B CN201110052079.9A CN201110052079A CN102653588B CN 102653588 B CN102653588 B CN 102653588B CN 201110052079 A CN201110052079 A CN 201110052079A CN 102653588 B CN102653588 B CN 102653588B
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Abstract
The invention discloses a polyester for a matt film and a preparation method of a film thereof. The method comprises the following steps of: firstly, dispersing an additive and a dispersant in dibasic alcohol to prepare an additive dispersion solution; then, mixing dibasic acid, the dibasic alcohol, a catalyst and the additive dispersion solution, and then carrying out esterification reaction; and finally, after the esterification reaction is finished, adding a stabilizer for carrying out polycondensation reaction. In the invention, a proper additive is selected and is added in the polymerization process for synthesizing a polyester by direct esterification to prepare a polyester for a matt film, and the polyester is dried, extruded and stretched to prepare a matt polyester film; and compared with a conventional polyester film, the matt polyester film has a better and relatively uniform matt effect.
Description
Technical field
The invention belongs to field of polymer chemical industry, be specifically related to a kind of sub-preparation method of light polyester for film and the preparation method of its film.
Background technology
Two-way stretch pet film (being called for short BOPET), has excellent physical and chemical performance, can be widely used in numerous areas.
Packaging industry has very large demand to the biaxially oriented polyester film of high transparency, high gloss all the time, because it can make surface of package have gloss and magnetism.Correspond, the sub-optical thin film of low-luster can make surface of package have more dim sense and artistry, the desire to purchase more stimulated consumer, sub-light film is except having the superior chemical physics performance of conventional polyester film, mainly also have: haze, the features such as low gloss, have and aluminize preferably and printing performance.Sub-light film is applicable to the overlay film application etc. of the printing packagings such as the making of the special high-grade label such as household electrical appliance, computer precision plant and instrument, indoor sub-light finishing material and high-grade cigarette, wine, high-grade books.
For reducing polyester film glossiness, more people is studied work, and these researchs mainly contain:
Number of patent application is the manufacture method that patent discloses a kind of transparent suboptical polyester film of 200810044519.4, and this patent adopts sub-for acrylic clear photopolymer resin and solvent, is mixed with the sub-photopolymer resin solution of acrylic clear; Again sub-for acrylic clear photopolymer resin solution is coated on polyester film through coating process, obtained transparent suboptical polyester film.This patent coating method prepares sub-optical thin film, requires higher to masking, coating apparatus.
Number of patent application is the polyester film that patent discloses a kind of at least single-face matt and the production method thereof of 200410016500.0, and this patent adopts interpolation nano silicon and micron silica to make master batch, then prepares sub-optical thin film.Wherein nano silicon is more difficult is uniformly dispersed.
Number of patent application be 200410039196.1 patent discloses light tight sub-smooth type polyester film of a kind of black and preparation method thereof, this patent polyester film is by (1) sub-light polyester slice, (2) carbon black type black polyester masterbatch, (3) the compound black polyester masterbatch composition of carbon black organic dye, this patent adopts blending method to prepare sub-optical thin film, and additive is not easily uniformly dispersed in the film.
Number of patent application be 200810015273.8 patent discloses a kind of single-face matt polyester film, this patent adopt does not prepare master batch in advance, the method adding nylon superpolymer and crystallization nucleation auxiliary agent when masking prepares sub-optical thin film.Adding crystallization nucleating agent when masking can cause film crystal unity excessive, occurs that not easily stretching and additive disperse uneven drawback.
Summary of the invention
The object of the invention is to overcome the existing deficiency preparing matt polyester film, film glossiness principle is affected by research, there is provided a kind of and the easy method of relative ease can prepare sub-light polyester and film thereof, by matt polyester film prepared by the method, compared with normal polyester film, to have preferably, comparatively uniform matt effect.
Object of the present invention can be reached by following measures:
A preparation method for sub-light polyester for film, with diprotic acid and dibasic alcohol for main raw material, adopt direct esterification to produce polyester, add applicable additive, catalyzer and stablizer when reacting, preparation process comprises esterification and polycondensation; The method specifically comprises the steps:
A, additive and dispersant are prepared additive dispersion liquid in dibasic alcohol;
B, by diprotic acid, dibasic alcohol, catalyzer and additive dispersion liquid mix after carry out esterification;
Add stablizer after C, esterification terminate, carry out polycondensation.
Wherein esterification temperature is 210 ~ 280 DEG C, and absolute pressure is 0.0 ~ 0.5MPa, and esterification time is 1 ~ 5 hour; Condensation temperature is 250 ~ 295 DEG C, polycondensation absolute pressure≤1KPa, and the reaction times is 0.5 ~ 4 hour, and through pelletizing, drying, obtained polyester slice, the limiting viscosity of gained polyester slice is 0.55 ~ 0.70dl/g.
Above-mentioned sub-light polyester for film and the diprotic acid described in preparation method of film thereof are terephthalic acid, preferred PTA or QTA, the dibasic alcohol that described dibasic alcohol (steps A and B) is EG class, concrete as ethylene glycol, the polyester obtained is the homopolymer of polyester, or multipolymer.
Catalyzer described in aforesaid method can be germanium, antimony, the compound of titanium or their organic complex, and its add-on is relative to polyester quality 0.01 ~ 0.09%.
Additive described in aforesaid method is barium sulfate.The median size of the additive be applicable to is 1.0 ~ 4.0 μm, and preferably 1.2 ~ 3.5 μm, the add-on of additive is relative to polyester quality 10 ~ 15%.
Additive described in aforesaid method, needs, first through high speed dispersion or with granulated glass sphere grinding, to make it be dispersed in EG, then join in polyester synthetic system.Grinding distribution become mass concentration be 20 ~ 60% additive dispersion liquid, preferred mass concentration 30 ~ 50%.
The additive be applicable to described in aforesaid method, in grinding distribution process, need add dispersion agent, and dispersion agent is one or both in sodium polyphosphate, potassium polyphosphate, and its add-on is relative to above-mentioned suitable additive quality 0.1% ~ 0.5%.
Described stablizer is selected from one or more in phosphoric acid, phosphorous acid, Tripyrophosphoric acid, trimethyl phosphite 99, triphenylphosphate or triethyl phosphate, and the add-on of stablizer is relative to polyester quality 0.0003 ~ 0.040%.
A preparation for sub-light polyester for film film, by above-mentioned sub-light polyester for film directly through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cooling, traction, rolling, make 20 ~ 100 μm of matt polyester films.First drying removal moisture content is carried out in polyester for film section when producing film, drying temperature 130 ~ 170 DEG C, drying mode is for bleed or hot gas flow is carried secretly; Dry slicedly obtain sheet through melt extruding again, extrusion temperature be 275 ~ 290 DEG C (also can 280 ~ 290 DEG C); The operations such as sheet drawn, sizing obtain film, and vertical La Wendu is 80 ~ 120 DEG C, and horizontal La Wendu is 80 ~ 120 DEG C, and indulge and draw multiplying power to be 3.0 ~ 4.0: 1, horizontal multiplying power of drawing is 3.0 ~ 4.0: 1.
A kind of preparation of sub-light polyester for film film, above-mentioned sub-light polyester for film also can add as master batch, light polyester for film is had to mix with super, through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cooling, traction, rolling, make 20 ~ 100 μm of matt polyester films.
Above-mentioned matt polyester film is single or multiple lift coextruded structure.In the preparation method of film, described sub-light polyester for film can be used as master batch interpolation or is directly used in prepares matt polyester film, need not add other caking inhibiters again.
In above-mentioned matt polyester film, barium sulfate content is equivalent to the 8-15% of film quality.
The present invention relates to the preparation method of a kind of sub-light polyester for film and film thereof, by selecting suitable additive, add in the polymerization process of direct esterification synthesizing polyester, obtained sub-light polyester for film, this polyester drying is extruded stretching and is made matt polyester film, compared with normal polyester film, to have preferably, comparatively uniform matt effect.Prepare 20-100 μm of film 45 degree of glossiness and be less than 30%.
Embodiment
Embodiment 1
In sand mill, add 1600ml granulated glass sphere, 750g barium sulfate, 3000g ethylene glycol, 1.13g sodium polyphosphate, grind 1 hour, prepare barium sulfate-glycolic suspension, wherein barium sulfate median size 3.5 μm.
5.0Kg PTA is added in 20L typical zolymerization reactor, 0.8KgEG, 2.0g antimony acetate, the above-mentioned barium sulfate-glycolic suspension of 3615g, 230 ~ 265 DEG C, carry out esterification under 0.2 ~ 0.3Mpa (gauge pressure), when aquifer yield reaches 1200ml, pressure release, to normal pressure, adds 1.025g triphenylphosphate, atmospheric agitation 10 minutes, intensification degree of falling is pressed onto 280 DEG C and below 100Pa, reacts 1 ~ 3 hour.React complete and extrude through Melt Pump, pelletizing, drying, obtain sub-light polyester slice.
By obtained sub-light polyester slice through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cool, make single thin film.Wherein extrusion temperature is 275 ~ 285 DEG C, and vertical La Wendu is 105 DEG C, and horizontal La Wendu is 105 DEG C, and vertical multiplying power of drawing is: 3.0: 1, and horizontal multiplying power of drawing is: 3.0: 1.
Embodiment 2
In sand mill, add 1200ml granulated glass sphere, 1500g barium sulfate, 1500g ethylene glycol, 3.0g potassium polyphosphate, grind 1.5 hours, prepare barium sulfate-glycolic suspension, wherein 500g barium sulfate median size 1.8 μm, 1000g barium sulfate median size 3.5 μm.
5.0kg PTA is added in 20L typical zolymerization reactor, 2.7kgEG, 0.93g germanium dioxide, 1720g above-mentioned barium sulfate-second two suspension, 230 ~ 265 DEG C, carry out esterification under 0.2 ~ 0.3Mpa (gauge pressure), when aquifer yield reaches 1200ml, pressure release, to normal pressure, adds 0.44g trimethyl phosphite 99, atmospheric agitation 10 minutes, intensification degree of falling is pressed onto 280 DEG C and below 100Pa, reacts 1 ~ 3 hour.React complete and extrude through Melt Pump, pelletizing, drying, obtain sub-light polyester slice.
By obtained sub-light polyester slice through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cool, make single thin film.Wherein extrusion temperature is 275 ~ 285 DEG C, and vertical La Wendu is 105 DEG C, and horizontal La Wendu is 105 DEG C, and vertical multiplying power of drawing is: 3.0: 1, and horizontal multiplying power of drawing is: 3.0: 1.
Embodiment 3
Using sub-light polyester slice obtained in embodiment 1 as two top layers, do not add the super bright PET chips of any additive as middle layer.Wherein two top layers account for 80% of film total amount, and middle layer accounts for 20% of film total amount.Cut into slices through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cool, make the three-layer co-extruded film of ABA.Wherein extrusion temperature is 275 ~ 285 DEG C, and vertical La Wendu is 115 DEG C, and horizontal La Wendu is 115 DEG C, and vertical multiplying power of drawing is: 3.6: 1, and horizontal multiplying power of drawing is: 3.6: 1.
Embodiment 4
Using sub-light polyester slice obtained in embodiment 2 as two top layers, do not add the super bright PET chips of any additive as middle layer.Wherein two top layers account for 75% of film total amount, and middle layer accounts for 25% of film total amount.Cut into slices through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cool, make the three-layer co-extruded film of ABA.Wherein extrusion temperature is 275 ~ 285 DEG C, and vertical La Wendu is 115 DEG C, and horizontal La Wendu is 115 DEG C, and vertical multiplying power of drawing is: 3.6: 1, and horizontal multiplying power of drawing is: 3.6: 1.
Reference example 1
By conventional do not add any additive superly have light polyester for film to cut into slices to cut into slices to mix according to certain proportioning with the conventional silicon dioxide polyester master batch that contains, in compound, dioxide-containing silica is 1000ppm, compound through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cooling, make single thin film.Filming technology and embodiment one, two identical.
Reference example 2
The section of light polyester for film is had to prepare the three-layer co-extruded film of ABA with conventional cutting into slices containing silicon dioxide polyester master batch conventional the super of any additive of not adding.Wherein A layer is that the super silicon dioxide polyester master batch that contains having light polyester for film to cut into slices and to commonly use is cut into slices, and wherein dioxide-containing silica is 850ppm; The ratio that A layer accounts for total amount is 18% (mass ratio), and the ratio that B layer accounts for total amount is 82% (mass ratio).Each layer mixes according to above-mentioned proportioning, compound through pre-crystallized, dry, three-layer co-extruded go out, two-way stretch in length and breadth, heat setting type, lax, cooling, make three-layer co-extruded film.Filming technology and embodiment three, four identical.
Table 1 embodiments of the invention and reference example film performance test result
| Sample number | Additive/particle diameter μm | Membrane structure | 45 degree of glossiness (%) | Mean thickness μm |
| Embodiment 1 | BaSO 4/3.5 | Individual layer | 12.1 | 69.2 |
| Embodiment 2 | BaSO 4/1.8/3.5 | Individual layer | 11.8 | 68.5 |
| Embodiment 3 | BaSO 4/3.5 | Three layers | 28.9 | 26.3 |
| Embodiment 4 | BaSO 4/1.8/3.5 | Three layers | 26.2 | 25.9 |
| Reference example 1 | SiO 2/3.2 | Individual layer | 105 | 68.2 |
| Reference example 2 | SiO 2/3.2 | Three layers | 125 | 26.3 |
Claims (6)
1. a preparation method for sub-light polyester for film, is characterized in that comprising the steps:
A, additive barium sulfate and dispersant are prepared additive dispersion liquid in dibasic alcohol;
B, by diprotic acid, dibasic alcohol, catalyzer and additive dispersion liquid mix after carry out esterification;
Add stablizer after C, esterification terminate, carry out polycondensation;
The median size of wherein said additive is 1.0 ~ 4.0 μm, and the add-on of additive barium sulfate is relative to 10 ~ 15% of polyester total mass; Described dispersion agent is one or both in sodium polyphosphate or potassium polyphosphate, and the add-on of dispersion agent is equivalent to 0.1% ~ 0.5% of additive quality.
2. the preparation method of sub-light polyester for film according to claim 1, is characterized in that the mass concentration of described additive dispersion liquid is 20 ~ 60%.
3. the preparation method of sub-light polyester for film according to claim 1, is characterized in that described dibasic alcohol is glycols dibasic alcohol; Described diprotic acid is terephthalic acid; Described catalyzer is compound containing germanium, antimony or titanium or its organic complex.
4. the preparation method of sub-light polyester for film according to claim 1, is characterized in that esterification temperature is 210 ~ 280 DEG C, and the absolute pressure of esterification is 0.0 ~ 0.5MPa, and esterification time is 1 ~ 5 hour; Condensation temperature is 250 ~ 295 DEG C, polycondensation absolute pressure≤1KPa, and the reaction times is 0.5 ~ 4 hour.
5. the preparation method of sub-light polyester for film according to claim 1, it is characterized in that one or more that described stablizer is selected from phosphoric acid, phosphorous acid, Tripyrophosphoric acid, trimethyl phosphite 99, triphenylphosphate or triethyl phosphate, the add-on of stablizer is relative to polyester quality 0.0003 ~ 0.040%.
6. the preparation method of a sub-light polyester for film film, it is characterized in that having light polyester for film to mix separately or with super sub-light polyester for film prepared by the preparation method of claim 1, through pre-crystallized, dry, extrude, in length and breadth to two-way stretch, heat setting type, lax, cooling, traction, rolling, make 20 ~ 100 μm of polyester films, wherein extrusion temperature is 275 ~ 290 DEG C, vertical La Wendu is 80 ~ 120 DEG C, horizontal La Wendu is 80 ~ 120 DEG C, indulging draws multiplying power to be 3.0 ~ 4.0:1, and horizontal multiplying power of drawing is 3.0 ~ 4.0:1; In matt polyester film, barium sulfate content is equivalent to 8 ~ 15% of film quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110052079.9A CN102653588B (en) | 2011-03-04 | 2011-03-04 | Polyester for matt film and preparation method of film thereof |
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| CN201110052079.9A CN102653588B (en) | 2011-03-04 | 2011-03-04 | Polyester for matt film and preparation method of film thereof |
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| CN102653588B true CN102653588B (en) | 2015-05-20 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102924905B (en) * | 2012-10-22 | 2016-03-02 | 佛山佛塑科技集团股份有限公司 | A kind of two-way stretch sub-light BOPA film and preparation method thereof |
| CN104108222A (en) * | 2014-06-16 | 2014-10-22 | 嘉兴鹏翔包装材料有限公司 | Production process of matte aluminum plated film |
| CN104385609A (en) * | 2014-09-30 | 2015-03-04 | 厦门海洋南方特种聚酯薄膜有限公司 | Preparation method for high-matte-degree matte polyester film |
| CN106589841B (en) * | 2015-10-14 | 2018-08-17 | 中国石化仪征化纤有限责任公司 | A kind of preparation method of highlighted polyester for film and film |
| CN105415722A (en) * | 2015-11-23 | 2016-03-23 | 安徽国泰印务有限公司 | Preparation process for matte aluminized polyester film |
| CN112646139B (en) * | 2019-10-12 | 2023-05-05 | 中国石油化工股份有限公司 | Polyester for matte film and preparation method of film of polyester |
| CN112679914B (en) * | 2019-10-17 | 2023-01-24 | 中国石油化工股份有限公司 | Polyester composition and preparation method and application thereof |
| CN111002677B (en) * | 2019-11-26 | 2020-10-30 | 杭州和顺科技股份有限公司 | Colored matte flame-retardant polyester film and preparation method thereof |
| CN113002027A (en) * | 2021-03-15 | 2021-06-22 | 江苏宗亮新材料有限公司 | Method for manufacturing matte vacuum aluminized polyester film |
| CN115594833A (en) * | 2021-07-08 | 2023-01-13 | 中国石油天然气股份有限公司（Cn） | Flame-retardant matte polyethylene glycol terephthalate composite material and preparation method thereof |
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| CN101307513A (en) * | 2008-07-08 | 2008-11-19 | 中国石化仪征化纤股份有限公司 | Low shrinkage polyester industrial filament preparation method |
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