KR100784442B1 - Pet-g film having incombustibility - Google Patents

Abstract

The present invention relates to a synthetic resin film having excellent flame retardancy, more specifically, a glycol-modified polyethylene terephthalate (PET-G) as the main, but is molded into a PET-G composition containing a flame retardant, lubricant and processing aids, It relates to a PET-G film having excellent flame retardancy and low smoke properties. The resin composition for molding the PET-G film according to the present invention is 20 parts by weight to 35 parts by weight of the flame retardant, 0.5 parts by weight to 5 parts by weight, 0.1 parts by weight of lubricant, based on 100 parts by weight of PET-G. To 1.5 parts by weight. Flame retardant low smoke film of the present invention has a carbonization area of less than 30 cm 2 of the standard of the thin sheet in the flame retardant (flame retardant) standard of Korea flame retardant performance (KOFEIS 1001) standard, and has an excellent smoke suppression effect. PET-G film according to the present invention is usefully used for building interior / exterior materials, flooring materials, advertising materials, vehicle / aviation interior materials, and other decorative applications.

Flame Retardant, Low Smoke, Zinc Borate, Zinc Oxide, Smoke Inhibitor, Molybdenum

Description

PITAGE FILM with flame retardant {PET-G FILM HAVING INCOMBUSTIBILITY}

The present invention relates to a synthetic resin film having excellent flame retardancy, and more particularly, molded in a flame retardant and flame retardant composition based on glycol-modified polyethylene terephthalate (PET-G), building interior / exterior materials, flooring material, advertising The present invention relates to a PET-G film usefully used for materials, vehicle / aviation interior materials, and other decorative applications.

Recently, as a large-scale fire incident occurred, attention has been focused on the flame retardancy and the amount of smoke generated in the interior / exterior materials, interior materials for vehicles / aviation, etc. socially. As a result, it is expected to strengthen the flame retardant standards for building interior materials, and to strictly comply with the smoke concentration by restricting the smoke concentration by applying fire retardancy to the flame retardant standard items in the national fire codes.

In general, films including decorative sheets used for various purposes are molded of synthetic resin, and their chemical structure is composed of combustible materials such as hydrogen and carbon. It causes many lives.

Accordingly, it is mainly used for covering wires in Korean Unexamined Patent Publication No. 2003-0040953, Korean Unexamined Patent Publication No. 2001-0061909, Japanese Unexamined Patent Publication No. 5 (1993) -170984, US Patent No. 6,492,453, US Patent No. 6,414,059, etc. Techniques for imparting flame retardancy and low smokeability to synthetic resin (polymer) compositions are described.

These prior arts mainly use a large amount of hydroxides such as magnesium hydroxide, aluminum trihydroxide, calcium hydroxide, etc. to improve the low smokeability and flame retardancy of the non-toxic synthetic resin composition for wire coating, or as a secondary flame retardant, phosphorus-based flame retardant or trioxide / antimony pentoxide I use it. The use of these has been described as being able to lower the flame retardancy and the smoke concentration compared to pure polymer materials. Hydroxide has been widely used because of the effect of delaying the initial smoke time and slowing the smoke rate by the endothermic effect of releasing water during its own pyrolysis.

In addition, smoke density inhibitors such as silicon-based inorganic powders and zinc borates are used in an auxiliary manner to improve low-foaming properties. However, the prior art including the prior art does not mention the flame propagation and the bombardment area regulated in the fire-related laws. In addition, in the film production, when an excess of an inorganic material is filled, it is difficult to disperse the inorganic material, and during the film manufacturing process, the physical properties of the resin mixture are lowered, which makes it difficult to form the film. That is, in order to obtain a flame retardant effect of a certain level, at least a certain level of flame retardant must be contained. However, when using a flame retardant of a certain level, there is a problem in processing that it is difficult to add a certain level of flame retardant to the base resin because of poor workability.

The present invention is to solve the problems of the prior art, to provide a synthetic resin film having excellent flame retardancy.

The present invention is to solve the problem that it was not possible to add a flame retardant above a certain level.

The above object of the present invention can be achieved by adding a flame retardant to glycol modified polyethylene terephthalate (PET-G), in addition to adding a processing aid at an appropriate composition ratio.

Glycol modified polyethylene terephthalate (PET-G) film having excellent flame retardancy according to the present invention contains a flame retardant, a lubricant and a processing aid.

Glycol modified polyethylene terephthalate (PET-G) film excellent in flame retardancy according to the present invention is a glycol modified polyethylene terephthalate (Glycol modified polyethylene terephthalate: PET-G) composition containing a flame retardant, lubricant and processing aid Is molded into.

Glycol modified polyethylene terephthalate (PET-G) film (hereinafter referred to as “PETG film”) having excellent flame retardancy of the present invention is mainly used for building interior / exterior materials, flooring materials, It is used as advertising materials, vehicle / aviation interior materials, and other decorative films.

The excellent flame retardancy (PET-G) film according to the present invention is a flame retardant comprising a smoke inhibitor for imparting a low smoke, flame retardant or flame retardant with a glycol-modified polyethylene terephthalate (PET-G) as a base resin The PET-G resin composition containing a lubricating agent and a processing aid at a predetermined ratio is molded into a film (or sheet).

The PET-G resin composition excellent in flame retardancy according to the present invention is to increase the amount of the flame retardant by adding a predetermined amount of the processing aid to greatly improve the workability with flame retardancy.

The resin composition for forming the PET-G film according to the present invention is 0.5 to 5 parts by weight of the processing aid, 0.1 to 1.5 parts by weight of the lubricant, based on 100 parts by weight of the PET-G film. By addition of up to 20 to 35 parts by weight of a flame retardant including a smoke suppressant It can be contained.

Glycol modified polyethylene terephthalate (PET-G) resin, which is a base resin used in the present invention, is a terephthalic acid (TPA), an ethylene glycol (Ethylene glycol: EG), and cyclohexanedimethanol: It is an amorphous resin copolymerized with CHDM) and has excellent processability, moldability and printability, no deformation due to shrinkage, excellent impact resistance, no chlorine gas generated during incineration or fire and no harmful substances such as environmental hormones. It has no properties at all and is suitable as the base resin of the flame retardant PET-G film according to the present invention.

The processing aid used in the present invention is added to compensate for the deterioration in formability due to the addition of the flame retardant.

PET-G film production according to the present invention should contain a certain amount of flame retardant to obtain a certain level of flame retardant effect. However, when a flame retardant is added in an amount exceeding a predetermined amount to obtain a certain level of flame retardant effect, the dispersion is difficult, and during the film manufacturing process, the processing properties of the resin mixture are degraded, resulting in difficulty in film formation. Accordingly, in the present invention, a processing aid is used to compensate for the deterioration of workability due to the use of a flame retardant of a predetermined level or more.

Preferred processing aids used in the present invention are a three-component copolymer resin consisting of methyl methacrylate (MMA), butyl acrylate and ethyl acrylate as an acrylic copolymer resin. As such a three-component copolymer resin, for example, an acrylic copolymer produced by LG Chemical Co., Ltd., Seoul, Korea under the trade names PA-828, 822, 910, 920, and 930 is preferable. Examples of the composition of the three-component acrylic copolymer, methyl methacrylate (MMA) 60 to 85%, butyl acrylate (5-15%), ethyl acrylate (Ethyl acrylate) 5-25% Is made of.

The amount of the processing aid used in the present invention is preferably 0.5 parts by weight to 5 parts by weight with respect to 100 parts by weight of PET-G resin. If the above range is exceeded, compatibility with PET-G resin may be deteriorated and film (sheet) surface defects may be generated. If it is less than the above range, processability is poor and roll adhesion and melt elasticity are insufficient during calendering. This is a problem.

In the present invention, the lubricant may be one or more selected from montan lubricants (Montan wax), Montan ester (Montan ester wax), and PE oxide lubricant, the composition ratio of 100 weight PET-G resin 0.1 parts by weight to 1.5 parts by weight with respect to parts are preferred. In this case, when less than 0.1 part by weight, roll adhesion and deterioration of activity may appear, and when it exceeds 1.5 parts by weight, it is difficult to form a bank of calender rolls, resulting in deterioration of film properties such as poor printability.

Flame retardant in the present invention is used in the concept including a smoke inhibitor. Smoke inhibitors, along with smoke suppression, increase the flame retardant effect. In the present invention, as a flame retardant for suppressing smoke, a compound such as a zinc compound such as zinc borate or zinc oxide, or a compound such as molybdenum compound may be used. The smoke suppressant has an average particle size distribution of 0.01 micron (μm) to 50 micron (μm) and is dispersed and blended in the gelled or molten resin at high temperature.

As the flame retardant used in the present invention, an organic halogen-based compound or a non-halogen-based compound such as a phosphorus-based compound and an inorganic compound may be used. Examples of the organic halogen-based compound include tris (tribromophenyl) triazine, decabromodiphenyl ethane, octabromodiphenyl oxide, and phenoxy termine. Itdecarbonate carbonate oligomer, tetrabromobisphenol A, hexabromocyclododecane and the like can be used, and the non-halogen based phosphorus and inorganic type, such as the phosphorus melamine phosphate, ammonium phosphate, The polyphosphate-based, red-based, etc. may be used as the antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, guanidine nitrate, and the like.

In the present invention, the flame retardant may be selected and mixed with one or two or more kinds of flame retardants including the smoke suppressant, but it is preferable to use two or more kinds including one selected from the smoke suppressant.

In the present invention, the blending amount of the flame retardant is preferably 20 to 35 parts by weight based on 100 parts by weight of the PET-G resin in order to have a flame retardancy of a predetermined level or more and at the same time the composition has good processability. If the blending amount of the flame retardant is less than the above range, the flame retardancy, flame retardancy, smoke suppression ability, etc. are not satisfied, and if it exceeds the above range, the processing and addition of processing aids, the active and melted when processing the PET-G resin composition The elasticity (melt strength) is lowered, which causes a problem that difficult to process, such as film molding.

In addition, in the present invention, an ultraviolet (UV) stabilizer, a hardness modifier, a heat stabilizer, a pigment, an inorganic filler, and the like may be further added and used to improve physical properties as necessary.

The PET-G film excellent in flame retardancy according to the present invention can be molded by a conventional calendar molding method using the PET-G composition. The processing conditions at this time are molded at a processing temperature of 160 to 210 ° C. in the 2 to 6 main calendars.

The PET-G film excellent in flame retardancy according to the present invention can be provided to various uses by forming the thickness of the 0.08mm ~ 0.5mm range.

The PET-G film having excellent flame retardancy according to the present invention may be formed on one side thereof with a printed layer of various patterns or letters and a transparent surface layer for protecting the printed layer.

In addition, the PET-G film having excellent flame retardancy according to the present invention may be provided with a printing layer and the surface layer formed on one side thereof, and an adhesive layer and a release paper layer formed on the other side thereof, such as an adhesive sheet. .

The invention is illustrated by the following examples and comparative examples.

Example 1-8

PET-G resin (Eastman copolyester cadence GS1 ~ 5) 1 kg (kg) of flame retardant, 5.2 specific gravity, 0.3 micron meter (μm) of antimony trioxide and flame retardant for smoke suppression, average particle size 2-4 Zinc microborate (μm) and Montan ester as a lubricant, and other flame retardants were mixed in the composition shown in Table 1 below to prepare a PET-G resin composition dispersed for 10 minutes at 2500 rpm / min with a homogenizer. This PET-G composition was gelled in a half-barrier mixer and processed into a film on four calender rolls. At this time, the temperature of the calendar roll was 160-210 degreeC.

 [Comparative Example 1-8]

The same composition as in Example was prepared in the same manner as in Example, but only the composition ratio was mixed and prepared in the composition shown in Table 2 below.

<Example of Raw Material Composition Unit: Gram (g)> ingredient Example One 2 3 4 5 6 7 8 PET-G Resin 1000 1000 1000 1000 1000 1000 1000 1000 Lubricant 9 9 9 9 9 9 9 9 Tris (tribromophenyl) triazine 150 150 - - - - - - Decabromodiphenyl ethane - - 150 120 - - - - Phenoxy terminated carbonate oligomer - - - - 150 200 - - Melamine polyphosphate - - 100 - - - 150 150 Ammonium polyphosphate - - - - - - 100 100 Antimony trioxide 50 70 100 50 70 70 70 70 Zinc borate - 30 - 30 - 30 - 30 Processing aid 5 40 50 10 30 25 15 10

<Example of Raw Material Composition Unit: Gram (g)> ingredient Comparative example One 2 3 4 5 6 7 8 PET-G Resin 1000 1000 1000 1000 1000 1000 1000 1000 Lubricant 9 9 9 9 9 9 9 9 Tris (tribromophenyl) triazine - 150 140 - 150 150 - - Decabromodiphenyl ethane - - - - - - - - Phenoxy terminated carbonate oligomer - - - - - - - - Melamine polyphosphate - - - 150 - - 150 150 Ammonium polyphosphate - - - 100 - - 100 100 Antimony trioxide - 50 50 80 50 50 70 70 Zinc borate - - - 30 - - - 30 Processing aid 15 - 15 10 3 55 3 55

The composition according to the Examples and Comparative Examples of the present invention to produce a film specimen (7.5 cm * 7.5 cm * 0.10 mm) according to the present invention with the same thickness at the same mixing time and temperature, flame retardancy (carbon surface area) is KOFEIS 1001 standard By the test method according to the present invention, the smoke density (value indicating light transmittance) was measured by the test method according to ISO 5659, and the results are shown in Tables 3 and 4.

division Example One 2 3 4 5 6 7 8 Flame retardant (burning area, ㎠) 27 26 28 28 29 27 30 29 Smoke density 67 64 70 66 69 65 69 69

division Comparative example One 2 3 4 5 6 7 8 Flame retardant (burning area, ㎠) Burned down 56 Impossible to process 45 Impossible to process Impossible to process Impossible to process Impossible to process Impossible to process Smoke density 95 or more - 90 - - - - -

Note 1). Flame retardancy is the carbonization area according to KOFEIS 1001 standard, indicating that the larger the value, the lower the flame retardancy,

2). Smoke density is a numerical value representing light transmittance according to ISO 5659, and the larger the value, the lower the smoke efficiency.

In the case of the composition according to the embodiment of the present invention, it can be seen that the film formability is excellent, as well as the physical properties (flame retardancy) is also excellent, in the case of the composition according to the comparative example outside the composition range of the present invention (processing film forming ), As well as the physical properties and surface of the molded film.

That is, PETG film of Comparative Example 1, which does not contain the flame retardant according to the present invention, was burned during the flame test, and the smoke density also showed a result of 95 or more.

In Comparative Example 2, in which the processing aid according to the present invention was not added, the melt strength of the resin mixture was lowered during the formation of the calendar film, resulting in adhesion to the calendar roll, and the film thickness was not uniform.

In the case of Comparative Example 3 in which the composition amount of the flame retardant was set to less than 190 grams (g) than the composition range of the present invention, and the processing aid was formulated in the composition range of the present invention, the flame retardancy and the smoke density were failed.

The composition amount of the flame retardant is 360 grams (g) more than the composition range of the present invention, and the processing aid has a large amount of the flame retardant of Comparative Example 4, which is formed in the composition range of the present invention. Adhesion occurred, and film molding was difficult, and the molded film brought a deterioration of physical properties.

In the case of Comparative Example 5 in which the composition amount of the processing aid was set to less than 3 grams (g) than the composition range of the present invention, and the flame retardant was formed in the lower limit of the present invention, film formation was difficult due to the decrease in melt strength of the workpiece.

In the case of Comparative Example 6 in which the composition amount of the processing aid was set to 55 grams (g) more than the composition range of the present invention, and the flame retardant was formed in the lower limit of the present invention, there was a problem in compatibility between the processing aid and the resin. Flow lines and undispersed particles were generated on the film surface.

In the case of Comparative Example 7 in which the composition amount of the processing aid was formed in 3 grams (g) less than the composition range of the present invention and the flame retardant was formed in the upper limit composition range of the present invention, film processing was impossible due to the decrease in melt strength during calendering. , Roll adhesion, etc.,

In the case of Comparative Example 8 in which the composition amount of the processing aid was set to 55 grams (g) higher than the composition range of the present invention and the flame retardant was formed in the upper limit of the present invention, the excessive roll strength caused the overload of the calender roll during processing. In addition, due to poor compatibility between the processing aid and PETG resin, the gelling phenomenon occurred due to undispersed raw materials on the film surface.

The low smoked film of the present invention prepared as described above has a carbonization area within 30 cm 2 of the proposed standard of the thin sheet in the KOFEIS 1001 standard in the case of flame retardancy.

In addition, the effect of suppressing the smoke density of the present invention shows an effect of suppressing the smoke of 5% or more when the zinc borate is added, and there is an effect that the deterioration of the process property and the sheet physical property accordingly does not appear.

Claims (9)

To 100 parts by weight of glycol modified polyethylene terephthalate (PET-G), it contains 20 to 35 parts by weight of flame retardant, 0.5 to 5 parts by weight of acrylic processing aid, and 0.1 to 1.5 parts by weight of montan lubricant PITAGE (PET-G) film excellent in flame retardancy to be. The method of claim 1, The acrylic processing aid is PET-G excellent flame retardancy, characterized in that the acrylic copolymer resin consisting of methyl methacrylate (MMA), butyl acrylate (butyl acrylate) and ethyl acrylate (Ethyl acrylate) ) film. The method of claim 2, The acrylic copolymer resin is a methyl methacrylate (MMA) 60 ~ 85%, butyl acrylate (butyl acrylate) 5-15% and ethyl acrylate (Ethyl acrylate) is a copolymer resin consisting of 5-25% PET-G film with excellent flame retardancy. delete The method of claim 1, The flame retardant is zinc borate (ZnBO3), zinc oxide (ZnO), molybdenum compound (Ca-Mo), tris (tribromophenyl) triazine, decabromodiphenyl ethane, Octabromodiphenyl oxide, phenoxyterminated carbonate oligomer, tetrabromobisphenolA, hexabromocyclododecane, melamine phosphate, ammonium phosphate, polyphosphate system, enemy An excellent flame retardancy (PET-G) film, characterized in that at least one selected from the group, antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide, guanidine nitrate. The method of claim 1, The Montan-based lubricant is Montan wax (Montan wax) or Montan ester (Esterified montan wax), characterized in that the excellent flame retardancy PET film (PET-G) film.  The method of claim 1, The PET-G film having excellent flame retardancy, characterized in that the thickness of the PET-G film has a thickness of 0.05mm to 0.5mm.  The method of claim 7, wherein The PET-G film has excellent flame retardancy, characterized in that the print layer and the surface layer is further formed on one side thereof (PET-G) film. The method of claim 8, The PET-G film has excellent flame retardancy, characterized in that the pressure-sensitive adhesive layer and a release paper layer is further formed on the other side of the PET-G film.