CN1286911C - Black lighttight type polyester film and preparation method - Google Patents

Abstract

The invention relates to a polyester film and a production method thereof, in particular to a black opaque polyester film and a production method thereof. The polyester film consists of (1) polyester chips, (2) carbon black type black Polyester masterbatch, (3) Carbon black organic dye composite black polyester masterbatch, the weight percentage content of each component is: polyester chips 65-97.9%; carbon black type black polyester masterbatch 2-20% %; carbon black organic dye composite black polyester masterbatch 0.1 to 15%; its preparation method includes the following steps: (1) polyester chips, carbon black black polyester masterbatch, carbon black organic dye composite black polyester Mix and dry the ester masterbatch; (2) Melt and extrude the dried material, and cool the melt on the casting roll to form a thick sheet; (3) Preheat the cooled thick sheet and stretch it longitudinally by 3.0 to 3.8 times; (4) After preheating the film after longitudinal stretching, stretch it transversely by 3.0 to 4.0 times; (5) heat-setting the stretched film, and winding it after cooling to obtain a black opaque polyester film, The polyester film produced by the method has uniform blackness, light-tightness, bright appearance, good thermal stability and high strength, and can be widely used in the fields of drum instruments, electronic appliances, packaging, decoration and the like.

Description

A kind of black opaque polyester film and preparation method thereof

technical field

The invention relates to a black polyester film, in particular to a black opaque polyester film and a production method thereof.

technical background

Polyester film has excellent physical and chemical properties and can be widely used in many industrial fields. In recent years, a kind of black polyester film used in the fields of drum instruments, electronic appliances, packaging and decoration has developed rapidly, and its usage is increasing. In addition to the stability characteristics, there are also requirements for the blackness and opacity of polyester films. For example, US Patent No. 4,603,073 describes a black polyester film for magnetic recording media. This film uses Black polyester masterbatch is produced by adding carbon black in the process of synthesizing polyester. Although the dispersion of carbon black particles is better, the process is complicated and the production cost is higher; U.S. Patent US5,385,768 describes a The black polyester film produced by coating the coating containing carbon black particles on the film support body, the black polyester film produced by this method has uniform blackness, but the coating process increases the production cost, and the coating is easy to use during use. Shedding occurs; U.S. Patent No. 6,436,219 describes a double-layer co-extruded black polyester film with an optical density above 2.0, one of which contains carbon black particles, and the film has good apparent quality, but the double-layer co-extrusion production process Complicated; Japanese patents JP61-237622 and JP62-122734 disclose a black polyester film containing carbon black particles and inactive particles, but the film has a certain light transmittance.

In the production of black opaque polyester film, there is a problem that carbon black particles are difficult to disperse evenly. At present, the method of mixing and extruding organic dye-type black polyester masterbatch with polyester chips is generally used to produce black light-transmitting polyester film. Film, the film has light transmission; the black polyester film produced by the coating method has the disadvantages that the black layer is easy to fall off and the production process is complicated.

Contents of the invention

The object of the present invention is to provide a black opaque polyester film, which has uniform blackness, opacity, smooth appearance, high mechanical strength and stable thermal performance.

Another object of the present invention is to provide a method for preparing the black opaque polyester film, which solves the problems of easy peeling off of the black layer of the film produced by the existing method, light transmission, uneven blackness, complex production process, etc. question.

Technical scheme of the present invention is:

A kind of black opaque polyester film is made up of (1) polyester chip, (2) carbon black type black polyester masterbatch, (3) carbon black organic dye composite type black polyester masterbatch, and its each group The weight percent content of minute is:

Polyester chip 65%～97.9%

Carbon black type black polyester masterbatch 2%～20%

Carbon black organic dye compound black polyester masterbatch 0.1%～15%

A preferred version, wherein the weight percent content of each component is:

Polyester chip 75%～96%

Carbon black type black polyester masterbatch 2%～15%

Carbon black organic dye compound black polyester masterbatch 2%～10%

A preferred scheme, wherein the polyester chips are ethylene terephthalate with an intrinsic viscosity of 0.5dL/g to 0.9dL/g, preferably ethylene terephthalate with an intrinsic viscosity of 0.6dL/g to 0.7dL/g Ethylene glycol phthalate.

A preferred scheme, wherein said carbon black type black polyester masterbatch is T1001 type black polyester masterbatch.

A preferred scheme, wherein said carbon black organic dye composite black polyester masterbatch is TBC03 type black polyester masterbatch.

Another technical scheme of the present invention is, a kind of black opaque polyester film, it is characterized in that, its preparation method comprises the following steps:

(1) polyester chips, carbon black type black polyester masterbatch, carbon black organic dye composite type black polyester masterbatch are mixed and dried;

(2) Melt and extrude the dry material, and the melt is cooled on the casting roll to form a thick sheet;

(3) After preheating the cooled thick sheet, stretch it longitudinally by 3.0 to 3.8 times;

(4) After preheating the film stretched longitudinally, stretch it transversely by 3.0 to 4.0 times;

(5) heat-setting the stretched film, winding after cooling to obtain a black opaque polyester film.

A preferred solution, wherein the drying temperature is 150°C to 180°C.

A preferred solution, wherein the melt extrusion temperature of the dried chip is 260°C to 300°C.

A preferred solution, wherein the heat setting temperature of the film is 210°C~240°C.

Polyester chips used for biaxial stretching mainly refer to the condensation products of dibasic acids and dibasic alcohols. Among them, dibasic acids can be straight-chain fatty acids, but mainly aromatic diacids, such as terephthalic acid, terephthalic acid, etc. Diacetic acid, terephthalic acid, etc.; diols are mainly aliphatic diols with 2 to 4 carbon atoms, such as ethylene glycol, propylene glycol, butanediol, etc. In addition to the above components, the polyester chip can also be a modified polyester with a small amount of isophthalic acid, phthalic acid and other substances added. The polyester chip suitable for the present invention is ethylene terephthalate, a polycondensate of terephthalic acid and ethylene glycol with an intrinsic viscosity of 0.5dL/g to 0.9dL/g, preferably with an intrinsic viscosity of 0.6dL/g to 0.7dL/g of ethylene terephthalate.

In order to endow the polyester film with blackness and opacity, carbon black type black polyester masterbatch can be added in the production. The main components of carbon black type black polyester masterbatch are polyethylene terephthalate and carbon black. The masterbatch can withstand the processing temperature of 300°C, and the particle size of carbon black particles is 10nm~500nm, preferably 15nm~ 100nm, suitable for carbon black type black polyester masterbatch of the present invention is the carbon black type black polyester masterbatch of models such as T1003, T1001 that Yinzhou Lihe Chemical Fiber Plastic Factory produces, preferred T1001 type carbon black type black polyester masterbatch .

In order to solve the disadvantages of uneven blackness and texture of the film that only adopt carbon black type black polyester masterbatch, the present invention also uses carbon black organic dye composite black polyester masterbatch, these two kinds of black polyester masterbatch The combined use of materials not only solves the light transmittance of only carbon black organic dye composite black polyester masterbatch, but also solves the uneven blackness and texture of only carbon black type black polyester masterbatch. disadvantages and make the product easy to process. The main components of carbon black organic dye composite black polyester masterbatch are polyethylene terephthalate, carbon black, quinone dyes and auxiliaries. The masterbatch can withstand the processing temperature of 300 ℃, and is suitable for the carbon black of the present invention The organic dye composite black polyester masterbatch is preferably the TBC03 carbon black organic dye composite black polyester masterbatch produced by Guangdong Caiyan Co., Ltd.

In order to control the roughness of the film and adjust the running performance of the film, an appropriate amount of additive chips containing silica, kaolin, calcium carbonate, titanium dioxide, and iron oxide fillers can be selected according to the winding situation.

The black opaque polyester film of the present invention is made up of polyester chips, carbon black type black polyester masterbatch, carbon black organic dye composite type black polyester masterbatch, and the weight percent content of each component is:

Polyester chip 65%～97.9%

Carbon black type black polyester masterbatch 2%～20%

Carbon black organic dye composite black polyester masterbatch 0.1%～15%

A preferred formulation suitable for the present invention is:

Polyester chip 75%～96%

Carbon black type black polyester masterbatch 2%～15%

Carbon black organic dye compound black polyester masterbatch 2%～10%

In order to solve the shortcomings of the existing method that the black layer of the film is easy to fall off, light transmission, uneven blackness, and complicated production process, the preparation method of the present invention comprises the following steps:

(1) polyester chips, carbon black type black polyester masterbatch, carbon black organic dye composite type black polyester masterbatch are mixed and dried;

(2) Melt and extrude the dry material, and the melt is cooled on the casting roll to form a thick sheet;

(3) After preheating the cooled thick sheet, stretch it longitudinally by 3.0 to 3.8 times;

(4) After preheating the film stretched longitudinally, stretch it transversely by 3.0 to 4.0 times;

(5) heat-setting the stretched film, winding after cooling to obtain a black opaque polyester film.

The specific preparation process of the polyester film of the present invention is: adding polyester chips, carbon black type black polyester masterbatch, carbon black organic dye compound type black polyester masterbatch into the mixer according to the ratio in the formula, mixing After uniformity, dry at 150°C-180°C; the dried slices are melted and extruded at a temperature of 260°C-300°C through an extruder, and the polyester melt flows out through a die to a casting roll at a temperature of 15°C-30°C. Cooling into a thick sheet; the thick sheet enters the longitudinal stretching machine, after being preheated by the preheating roller and heated by an infrared heater, it is stretched 3.0 to 3.8 times longitudinally at a temperature higher than the glass transition temperature of the polyester, and then cooled rapidly; The pull sheet enters the transverse stretching machine, after being preheated at 90°C to 110°C in the preheating zone, it is stretched 3.0 to 4.0 times in the transverse direction, heat-set at 210°C to 240°C, and after cooling, it is trimmed, thickness measured, Winding to obtain a black opaque polyester film. The black polyester film is opaque, uniform in blackness, small in thickness tolerance, bright in appearance, good in thermal stability, and meets use requirements in mechanical strength.

The black opaque polyester film provided by the invention can be widely used in the fields of drum instruments, electronic appliances, packaging, decoration and the like.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments.

Comparative example 1

formula:

Ethylene terephthalate 90.0kg

(IV=0.62dL/g)

T1001 10.0kg

operate:

Add 90.0kg of polyester chips and 10.0kg of black polyester masterbatch T1001 into the mixer, and after mixing evenly, crystallize and dry at 170°C; the dried chips are melted and extruded at a temperature of 275°C through an extruder, and the polyester The melt flows out of the die to the casting roller at 30°C and is rapidly cooled to form a thick sheet; the thick sheet enters the longitudinal stretching machine, and after being preheated by the preheating roller and heated by the infrared heater, it is heated at a temperature higher than the glass transition temperature of the polyester. Stretch 3.1 times longitudinally under the same conditions, and then cool rapidly; the longitudinally stretched sheet enters the transverse stretching machine, preheats at 95°C in the preheating zone, stretches 3.2 times transversely, heat sets at 230°C, and cuts after cooling. Edge, thickness measurement, central slitting, and winding to obtain a black opaque polyester film. Measure its performance (see Table 1).

Comparative example 2

formula:

Ethylene terephthalate 90.0kg

(IV=0.5dL/g)

TBC03 10.0kg

operate:

Add 90.0kg of polyester chips and 10.0kg of carbon black organic dye compound black polyester masterbatch TBC03 into the mixer, mix well, and then crystallize and dry at 180°C; the dried slices pass through the extruder at a temperature of 260°C Melt extrusion, the polyester melt flows out of the die to the casting roller at 25°C and is rapidly cooled to form a thick sheet; the thick sheet enters the longitudinal stretching machine, and after being preheated by the preheating roller and heated by the infrared heater, Stretch 3.8 times longitudinally under the glass transition temperature of polyester, and then cool rapidly; the longitudinal stretching sheet enters the transverse stretching machine, and after preheating at 90°C in the preheating zone, stretches transversely 4.0 times, and heats it at 210°C Shaping, after cooling, trimming, thickness measurement, central slitting, and winding to obtain a black opaque polyester film. Measure its performance (see Table 1).

Example 1

formula:

Ethylene terephthalate 93.9kg

(IV=0.6dL/g)

T1001 6.0kg

TBC03 0.1kg

operate:

Add 93.9kg of polyester chips, 6.0kg of black polyester masterbatch T1001, and 0.1kg of carbon black organic dye composite black polyester masterbatch TBC03 into the mixer, mix well, and crystallize and dry at 170°C; The extruder is melted and extruded at a temperature of 260°C, and the polyester melt flows out through the die to the casting roll at 30°C and is rapidly cooled to form a thick sheet; the thick sheet enters the longitudinal stretching machine, is preheated by the preheating roller, After being heated by an infrared heater, stretch 3.1 times longitudinally at a temperature higher than the glass transition temperature of the polyester, and then cool rapidly; Stretch 3.2 times, heat setting at 230°C, after cooling, cut the edge, measure the thickness, cut the center, and wind up to obtain a black opaque polyester film. Measure its performance (see Table 1).

Example 2

formula:

Ethylene terephthalate 85.9kg

(IV=0.7dL/g)

T1001 9.0kg

TBC03 5.1kg

operate:

Add 85.9kg of polyester chips, 9.0kg of black polyester masterbatch T1001, and 5.1kg of carbon black organic dye composite black polyester masterbatch TBC03 into the mixer, mix well, and crystallize and dry at 180°C; dry the slices by The extruder is melted and extruded at a temperature of 275°C, and the polyester melt flows out through the die to the casting roller at 25°C and is rapidly cooled into a thick sheet; the thick sheet enters the longitudinal stretching machine, is preheated by the preheating roller, After being heated by an infrared heater, it is stretched 3.8 times longitudinally at a temperature higher than the glass transition temperature of the polyester, and then cooled rapidly; Stretch 4.0 times, heat setting at 210°C, after cooling, cut the edge, measure the thickness, cut the center, and wind up to obtain a black opaque polyester film. Measure its performance (see Table 1).

Example 3

formula:

Ethylene terephthalate 83.0kg

(IV=0.66dL/g)

T1001 2.0kg

TBC03 15.0kg

operate:

Add 83.0kg of polyester chips, 2.0kg of black polyester masterbatch T1001, and 15.0kg of carbon black organic dye composite black polyester masterbatch TBC03 into the mixer. After mixing evenly, crystallize and dry at 150°C; dry the slices by The extruder is melted and extruded at a temperature of 300°C, and the polyester melt flows out through the die to the casting roll at 15°C and is rapidly cooled into a thick sheet; the thick sheet enters the longitudinal stretching machine, is preheated by the preheating roller, After being heated by an infrared heater, it is stretched 3.0 times longitudinally at a temperature higher than the glass transition temperature of the polyester, and then cooled rapidly; Stretch 3.3 times, heat setting at 240°C, after cooling, cut the edge, measure the thickness, cut the center, and wind up to obtain a black opaque polyester film. Measure its performance (see Table 1).

Example 4

formula:

Ethylene terephthalate 65.0kg

(IV=0.9dL/g)

T1001 20.0kg

TBC03 15.0kg

operate:

Add 65.0kg of polyester chips, 20.0kg of black polyester masterbatch T1001, and 15.0kg of carbon black organic dye composite black polyester masterbatch TBC03 into the mixer, mix well, and crystallize and dry at 160°C; dry the slices by The extruder is melted and extruded at a temperature of 260°C, and the polyester melt flows out through the die to the casting roll at 30°C and is rapidly cooled into a thick sheet; the thick sheet enters the longitudinal stretching machine, is preheated by the preheating roller, After being heated by an infrared heater, stretch 3.5 times longitudinally at a temperature higher than the glass transition temperature of the polyester, and then cool rapidly; Stretch 3.0 times, heat setting at 220°C, after cooling, cut the edge, measure the thickness, cut the center, and wind up to obtain a black opaque polyester film. Measure its performance (see Table 1).

Table I

Detection method:

Tensile strength, elongation at break:

Measured according to GB/T12683-1990.

Heat shrinkage rate:

Test according to GB/T13541-1992.

thickness:

The LG-1 vertical optical meter of Shanghai No. 2 Optical Instrument Factory was used for testing.

Blackness and opacity: visual inspection

Beneficial effect:

As can be seen from the data in the table, the present invention solves the problem of uneven dispersion of carbon black in the black polyester film, and solves the problem that the film layer of the black polyester film produced by the existing method is easy to fall off and light-transmitting. The black polyester film produced has uniform blackness, opacity, bright appearance, good thermal stability, high strength, and meets the requirements of use.

Claims (10)

1. a kind of black light-tight type polyester film, by (1) polyester chip, (2) carbon black type black polyester masterbatch, (3) carbon black organic dye composite type black polyester masterbatch is formed, its The weight percent content of each component is: Polyester chip 65%～97.9% Carbon black type black polyester masterbatch 2%～20% Carbon black organic dye composite black polyester masterbatch 0.1% to 15%. 2. black opaque polyester film according to claim 1, is characterized in that, wherein the weight percent content of each component described is: Polyester chip 75%～96% Carbon black type black polyester masterbatch 2%～15% Carbon black organic dye composite black polyester masterbatch 2% to 10%. 3. The black opaque polyester film according to claim 1 or 2, wherein said polyester chip is ethyl terephthalate with intrinsic viscosity of 0.5dL/g～0.9dL/g Glycol esters. 4. The black opaque polyester film according to claim 3, wherein said polyester chips are ethylene terephthalate whose intrinsic viscosity is 0.6dL/g～0.7dL/g ester. 5. The black opaque polyester film according to claim 1 or 2, wherein said carbon black type black polyester masterbatch is T1001 type black polyester masterbatch. 6. The black opaque polyester film according to claim 1 or 2, wherein said carbon black organic dye composite black polyester masterbatch is TBC03 type black polyester masterbatch. 7. a kind of preparation method of claim 1 or 2 described black opaque type polyester film is characterized in that, its preparation method may further comprise the steps: (1) polyester chips, carbon black type black polyester masterbatch, carbon black organic dye composite type black polyester masterbatch are mixed and dried; (2) Melt and extrude the dry material, and the melt is cooled on the casting roll to form a thick sheet; (3) After preheating the cooled thick sheet, stretch it longitudinally by 3.0 to 3.8 times; (4) After preheating the film stretched longitudinally, stretch it transversely by 3.0 to 4.0 times; (5) heat-setting the stretched film, winding after cooling to obtain a black opaque polyester film. 8 . The method for preparing a black opaque polyester film according to claim 7 , wherein the drying temperature is 150° C. to 180° C. 9 . The method for preparing a black opaque polyester film according to claim 7 , wherein the melt extrusion temperature of the dried chips is 260° C. to 300° C. 10 . The method for preparing a black opaque polyester film according to claim 7 , wherein the heat-setting temperature of the film is 210° C. to 240° C.