WO2009151225A2 - Laminating co-extrusion dispersion-proof film - Google Patents

Laminating co-extrusion dispersion-proof film Download PDF

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Publication number
WO2009151225A2
WO2009151225A2 PCT/KR2009/002904 KR2009002904W WO2009151225A2 WO 2009151225 A2 WO2009151225 A2 WO 2009151225A2 KR 2009002904 W KR2009002904 W KR 2009002904W WO 2009151225 A2 WO2009151225 A2 WO 2009151225A2
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WO
WIPO (PCT)
Prior art keywords
laminating
proof film
extrusion
dispersion
extrusion dispersion
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PCT/KR2009/002904
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French (fr)
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WO2009151225A3 (en
Inventor
Heyoung Suk Park
Gwan Hyung Lee
Young Deuk Kim
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Skc Co., Ltd.
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Publication of WO2009151225A2 publication Critical patent/WO2009151225A2/en
Publication of WO2009151225A3 publication Critical patent/WO2009151225A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present invention relates to a laminating co-extrusion dispersion-proof film comprising a stiff layer containing a polyester or copolyester polymer resin, and a flexible layer comprising a polybutylene terephthalate glycol copolymer containing polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated, and more particularly, to a dispersion-proof film suitable for glass for buildings or automobiles and having excellent tear resistance, high visible light transmittance (%), and low haze.
  • PTMEG polytetra methylene ether glycol
  • a film with a thickness of several hundred micrometers prepared by extruding crystal materials is attached to glass in order to prevent glass from being broken or dispersed by external impact.
  • a thick film has poor optical properties (a light transmittance ranging from 20 to 30%).
  • the film cannot be efficiently applied to exterior windows of buildings or windows of automobiles.
  • U.S. Patent No. 6,040,061 and Japanese Patent Publication No. 1998-76620 disclose methods of preventing glass from being broken or dispersed by preparing a sheet by laminating a polyethylene terephthalate layer and a counter layer comprising bisphenol A copolymer and sebacic acid, and attaching the sheet to the glass by stretching the sheet.
  • a white residue is formed in the sheet by UV rays with a lapse of time to significantly reduce the visible light transmittance, and the sheet cannot sufficiently prevent glass from being broken or dispersed at a very low temperature due to poor adhesion between the polyethylene terephthalate and the bisphenol A copolymer or sebacic acid.
  • a film is prepared using at least two layers formed of different materials via multilayer co-extrusion.
  • the film has poor optical properties such as light transmittance and haze although it has excellent tear resistance. Accordingly, there is still a need to develop a dispersion-proof film having excellent optical properties.
  • dispersion-proof film prepared by conventional co-extrusion to obtain excellent tear resistance and by introducing specific materials thereto and adjusting the compositions of the specific materials to obtain excellent optical properties.
  • a laminating co-extrusion dispersion-proof film comprising: a stiff layer containing a polyester or copolyester polymer resin; and a flexible layer comprising a polybutylene terephthalate glycol copolymer which comprises polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated.
  • PTMEG polytetra methylene ether glycol
  • the laminating co-extrusion dispersion-proof film according to the present invention has excellent tear strength which hardly change with the lapse of time, high visible light transmittance, and low haze. Thus, the laminating co-extrusion dispersion-proof film can be efficiently applied to glass of buildings and automobiles.
  • the laminating co-extrusion dispersion-proof film comprises: a stiff layer comprising a polyester or copolyester polymer resin; and a flexible layer comprising a polybutylene terephthalate glycol copolymer comprising polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated.
  • a stiff layer comprising a polyester or copolyester polymer resin
  • a flexible layer comprising a polybutylene terephthalate glycol copolymer comprising polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated.
  • PTMEG polytetra methylene ether glycol
  • the stiff layer comprises polyester or copolyester polymer resin.
  • the polymer resin may be a polyalkylene terephthalate resin, wherein alkylene of the polyalkylene may include 1 to 6 carbon atoms.
  • the polymer resin may be a polyethylene terephthalate resin, a copolymerized polyethylene terephthalate, or any mixtures of at least two of them.
  • the polymer resin may have a crystallinity of 70% or greater, preferably in the range of 75% to 95%. If the crystallinity of the polymer resin is less than 70%, impact resistance strength and tensile strength may decrease.
  • the polybutylene terephthalate glycol copolymer of the flexible layer may comprise equal to or less than 90% by weight, preferably 10 to 60% by weight, of polytetra methylene ether glycol (PTMEG) based on the total weight of the polybutylene terephthalate glycol copolymer.
  • PTMEG polytetra methylene ether glycol
  • the amount of the PTMEG is greater than 90% by weight based on the total weight of the polybutylene terephthalate glycol copolymer, thermal resistance may decrease, so that the film properties may be deteriorated during the manufacturing process and post-treatment of the film.
  • the amount of the PTMEG is less than 10% by weight based on the total weight of the polybutylene terephthalate glycol copolymer, elongation decreases, so that impact resistance strength and tear strength may decrease.
  • the flexible layer is described in more detail.
  • the flexible layer may be any polymer having an ester group in addition to the polybutylene terephthalate glycol copolymer having PTMEG.
  • the flexible layer may comprise polybutylene terephthalate glycol alone, or may further comnprise at least one selected from the group consisting of polyalkylene, polyurethane, and polyacetate.
  • alkylene of the polyalkylene may have 1 to 10 carbon atoms, preferably 2 to 4 carbon atoms.
  • the polyalkylene may be polyethylene containing 1,4-cyclohexanedimethanol (CHDM).
  • the weight ratio of the stiff layer to the flexible layer may be in the range of 5 to 40:1, (extrusion ratio, kg/hr), preferably in the range of 10 to 30:1. If the weight ratio of the stiff layer to the flexible layer is less than 5:1, light transmittance and thermal shrinkage may decrease. On the other hand, if the weight ratio of the stiff layer to the flexible layer is greater than 40:1, tear strength and elongation may decrease.
  • the dispersion-proof film according to the present invention is prepared by extrusion that is commonly used in the art.
  • materials that are used to form the layers are alternately laminated through a feedblock, and then the resultant is extruded while being passed through a co-extrusion die to form a sheet.
  • the capacity of an extruder may be controlled such that the weight ratio of the stiff layer to the flexible layer is in the range of 2 to 40:1.
  • the extruded sheet is rapidly cooled using a casting roll to obtain a solidified sheet.
  • the extruded sheet is adhered to the casting roll by applying constant voltage thereto in order to prepare a sheet having uniform thickness and smooth surface.
  • the constant voltage may be in the range of 4 to 6 kv, but is not limited thereto.
  • the sheet is sequentially elongated in longitudinal and lateral directions.
  • the elongation magnification of the sheet may be in the range of 1.5 to 5 times in both longitudinal and lateral directions. If the elongation magnification of the sheet is less than 1.5 times, the thickness of the film may not be uniform, and tensile strength may decrease. On the other hand, if the elongation magnification of the sheet is greater than 5 times, thermal shrinkage and stability during manufacturing operations may decrease.
  • the laminating co-extrusion dispersion-proof film according to the present invention comprising at least two of the stiff layers and the flexible layers alternately laminated and having a thickness of 50 ⁇ m may have: a visible light transmittance of 85% or higher, preferably in the range of 85 to 95%; a haze of 2% or less, preferably in the range of 0.2 to 1.5%; a longitudinal or lateral tear strength in the range of 0.1 to 10 kg at -10°C; and a longitudinal or lateral tear strength in the range of 0.2 to 15 kg at 40°C.
  • the thickness of the laminating co-extrusion dispersion-proof film according to the present invention may be in the range of 5 to 700 ⁇ m, preferably 10 ⁇ m to 400 ⁇ m. If the thickness of the laminating co-extrusion dispersion-proof film is less than 10 ⁇ m, sufficient dispersion-proof effects may not be obtained. On the other hand, if the thickness of the laminating co-extrusion dispersion-proof film exceeds 700 ⁇ m, improvement of the dispersion-proof effects by increasing the thickness becomes negligible, thus not being economical.
  • a polyethylene terephthalate resin having a crystallinity of 75% was dried under vacuum at 120°C for 2 hours and at 180°C for about 3 hours. Then, the polyethylene terephthalate resin was melted at 280°C and added to a feedblock using an extruder.
  • a polybutylene terephthalate glycol copolymer having 40% of PTMEG was melted at 240°C and added to the feedblock using the extruder.
  • a sheet having 13 layers was prepared using a feedblock co-extrusion at about 270°C such that the weight ratio of the polyethylene terephthalate resin and the polybutylene terephthalate glycol copolymer is 15:1.
  • the sheet was prepared on a cooling roll at 45°C by applying 5 kv of constant voltage thereto.
  • the prepared sheet was elongated by about 3.5 times in the longitudinal direction at 100°C, and coated to increase slippery properties, and elongated by about 3.5 times in the lateral direction at about 110°C to prepare a film having a thickness of 50 ⁇ m and the composition shown in Table 1 below.
  • Dispersion-proof films having a thickness of 50 ⁇ m were prepared in the same manner as in Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Example 2), 5:1 (Example 3), 10:1 (Example 4), 20:1 (Example 5), and 40:1 (Example 6).
  • a dispersion-proof film having a thickness of 50 ⁇ m was prepared in the same manner as in Example 1, except that the weight ratio of the stiff layer to the flexible layer is 15:1 since a high-density polyethylene having 10 to 70% of CHDM was used instead of the polybutylene terephthalate glycol copolymer of the flexible layer.
  • Safety films having a thickness of 50 ⁇ m were prepared in the same manner as in Comparative Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Comparative Example 2), 10:1 (Comparative Example 3), 20:1 (Comparative Example 4), and 40:1 (Comparative Example 5).
  • Films were prepared in the same manner as in Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Comparative Example 6), 10:1 (Comparative Example 7), 15:1 (Comparative Example 8), 20:1 (Comparative Example 9), and 40:1 (Comparative Example 10) using a poly methylmethacrylate (PMMA) resin instead of the polybutylene terephthalate glycol copolymer as shown in Table 1 below. Then, a single-layered safety film having a thickness of 50 ⁇ m was prepared in the same manner as in Example 1, except that only the polyethylene terephthalate resin was used and a conventional extrusion method was used (Comparative Example 11) as shown in Table 1 below.
  • PMMA poly methylmethacrylate
  • Films were cut into pieces with a width of 16 cm and a length of 17 cm. A central upper portion of the pieces was cut by 2 cm, and the degree of tearing (kg) was measured using a notch. The tear strength is measured at room temperature ranging from 20 to 25°C.
  • the dispersion-proof films prepared according to Examples 1 to 6 have better visible light transmittances and lower hazes (%) compared to the dispersion-proof films prepared according to Comparative Examples 1 to 11.
  • the dispersion-proof films prepared according to Comparative Examples 6 to 10 have high visible light transmittance, low haze, and very low tear strength at room temperature. Accordingly, it can be seen that the dispersion-proof films prepared according to the present invention have excellent tear strength.
  • the dispersion-proof film prepared according to Comparative Example 11 by a normal extrusion instead of co-extrusion only using polyethylene terephthalate has very low tear strength. Thus, laminating co-extrusion may be efficiently used to increase tear strength of the dispersion-proof films.
  • the laminating co-extrusion dispersion-proof film according to the present invention with high visible light transmittance, low haze (%), and excellent tear strength may be efficiently applied to glass for buildings and automobiles.

Abstract

Disclosed is a laminating co-extrusion dispersion-proof film, and more particularly, a laminating co-extrusion dispersion-proof film comprising: a stiff layer comprising a polyester or copolyester polymer resin; and a flexible layer comprising a polybutylene terephthalate glycol copolymer containing polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated. The laminating co-extrusion dispersion-proof film has excellent tear resistance, high visible light transmittance (%), and low haze (%). Thus, the laminating co-extrusion dispersion-proof film can be efficiently applied to glass of buildings and automobiles.

Description

LAMINATING CO-EXTRUSION DISPERSION-PROOF FILM
The present invention relates to a laminating co-extrusion dispersion-proof film comprising a stiff layer containing a polyester or copolyester polymer resin, and a flexible layer comprising a polybutylene terephthalate glycol copolymer containing polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated, and more particularly, to a dispersion-proof film suitable for glass for buildings or automobiles and having excellent tear resistance, high visible light transmittance (%), and low haze.
Recently, there have been developed a variety of films that prevent glass from being broken or dispersed due to external impact.　　For example, a film with a thickness of several hundred micrometers prepared by extruding crystal materials is attached to glass in order to prevent glass from being broken or dispersed by external impact. However, such a thick film has poor optical properties (a light transmittance ranging from 20 to 30%). Thus, the film cannot be efficiently applied to exterior windows of buildings or windows of automobiles.
U.S. Patent No. 6,040,061 and Japanese Patent Publication No. 1998-76620 disclose methods of preventing glass from being broken or dispersed by preparing a sheet by laminating a polyethylene terephthalate layer and a counter layer comprising bisphenol A copolymer and sebacic acid, and attaching the sheet to the glass by stretching the sheet. However, according to the conventional methods, a white residue is formed in the sheet by UV rays with a lapse of time to significantly reduce the visible light transmittance, and the sheet cannot sufficiently prevent glass from being broken or dispersed at a very low temperature due to poor adhesion between the polyethylene terephthalate and the bisphenol A copolymer or sebacic acid.
Recently, a film is prepared using at least two layers formed of different materials via multilayer co-extrusion. However, the film has poor optical properties such as light transmittance and haze although it has excellent tear resistance. Accordingly, there is still a need to develop a dispersion-proof film having excellent optical properties.
While searching for a method of solving problems of conventional dispersion-proof films, the present inventors found a dispersion-proof film prepared by conventional co-extrusion to obtain excellent tear resistance and by introducing specific materials thereto and adjusting the compositions of the specific materials to obtain excellent optical properties.
According to an aspect of the present invention, there is provided a laminating co-extrusion dispersion-proof film comprising: a stiff layer containing a polyester or copolyester polymer resin; and a flexible layer comprising a polybutylene terephthalate glycol copolymer which comprises polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated.
The laminating co-extrusion dispersion-proof film according to the present invention has excellent tear strength which hardly change with the lapse of time, high visible light transmittance, and low haze. Thus, the laminating co-extrusion dispersion-proof film can be efficiently applied to glass of buildings and automobiles.
Hereinafter, a laminating co-extrusion dispersion-proof film according to the present invention will be described in more detail with reference to exemplary embodiments of the invention.
The laminating co-extrusion dispersion-proof film comprises: a stiff layer comprising a polyester or copolyester polymer resin; and a flexible layer comprising a polybutylene terephthalate glycol copolymer comprising polytetra methylene ether glycol (PTMEG), wherein at least two of the stiff layers and the flexible layers are alternately laminated.
In the laminating co-extrusion dispersion-proof film, the stiff layer comprises polyester or copolyester polymer resin. The polymer resin may be a polyalkylene terephthalate resin, wherein alkylene of the polyalkylene may include 1 to 6 carbon atoms. The polymer resin may be a polyethylene terephthalate resin, a copolymerized polyethylene terephthalate, or any mixtures of at least two of them.　　The polymer resin may have a crystallinity of 70% or greater, preferably in the range of 75% to 95%.　　If the crystallinity of the polymer resin is less than 70%, impact resistance strength and tensile strength may decrease.
In addition, the polybutylene terephthalate glycol copolymer of the flexible layer may comprise equal to or less than 90% by weight, preferably 10 to 60% by weight, of polytetra methylene ether glycol (PTMEG) based on the total weight of the polybutylene terephthalate glycol copolymer.　　In this regard, if the amount of the PTMEG is greater than 90% by weight based on the total weight of the polybutylene terephthalate glycol copolymer, thermal resistance may decrease, so that the film properties may be deteriorated during the manufacturing process and post-treatment of the film. On the other hand, if the amount of the PTMEG is less than 10% by weight based on the total weight of the polybutylene terephthalate glycol copolymer, elongation decreases, so that impact resistance strength and tear strength may decrease.
The flexible layer is described in more detail. The flexible layer may be any polymer having an ester group in addition to the polybutylene terephthalate glycol copolymer having PTMEG. The flexible layer may comprise polybutylene terephthalate glycol alone, or may further comnprise at least one selected from the group consisting of polyalkylene, polyurethane, and polyacetate.
In the flexible layer, alkylene of the polyalkylene may have 1 to 10 carbon atoms, preferably 2 to 4 carbon atoms. The polyalkylene may be polyethylene containing 1,4-cyclohexanedimethanol (CHDM).
The weight ratio of the stiff layer to the flexible layer may be in the range of 5 to 40:1, (extrusion ratio, kg/hr), preferably in the range of 10 to 30:1. If the weight ratio of the stiff layer to the flexible layer is less than 5:1, light transmittance and thermal shrinkage may decrease. On the other hand, if the weight ratio of the stiff layer to the flexible layer is greater than 40:1, tear strength and elongation may decrease.
The dispersion-proof film according to the present invention is prepared by extrusion that is commonly used in the art. In particular, materials that are used to form the layers are alternately laminated through a feedblock, and then the resultant is extruded while being passed through a co-extrusion die to form a sheet. In this regard, the capacity of an extruder may be controlled such that the weight ratio of the stiff layer to the flexible layer is in the range of 2 to 40:1.　　Then, the extruded sheet is rapidly cooled using a casting roll to obtain a solidified sheet. In this regard, the extruded sheet is adhered to the casting roll by applying constant voltage thereto in order to prepare a sheet having uniform thickness and smooth surface. Here, the constant voltage may be in the range of 4 to 6 kv, but is not limited thereto.　　Then, the sheet is sequentially elongated in longitudinal and lateral directions. The elongation magnification of the sheet may be in the range of 1.5 to 5 times in both longitudinal and lateral directions. If the elongation magnification of the sheet is less than 1.5 times, the thickness of the film may not be uniform, and tensile strength may decrease. On the other hand, if the elongation magnification of the sheet is greater than 5 times, thermal shrinkage and stability during manufacturing operations may decrease.
As described above, the laminating co-extrusion dispersion-proof film according to the present invention comprising at least two of the stiff layers and the flexible layers alternately laminated and having a thickness of 50 ㎛ may have: a visible light transmittance of 85% or higher, preferably in the range of 85 to 95%; a haze of 2% or less, preferably in the range of 0.2 to 1.5%; a longitudinal or lateral tear strength in the range of 0.1 to 10 kg at -10℃; and a longitudinal or lateral tear strength in the range of 0.2 to 15 kg at 40℃.　　In addition, the thickness of the laminating co-extrusion dispersion-proof film according to the present invention may be in the range of 5 to 700 ㎛, preferably 10 ㎛ to 400 ㎛. If the thickness of the laminating co-extrusion dispersion-proof film is less than 10 ㎛, sufficient dispersion-proof effects may not be obtained. On the other hand, if the thickness of the laminating co-extrusion dispersion-proof film exceeds 700 ㎛, improvement of the dispersion-proof effects by increasing the thickness becomes negligible, thus not being economical.
Hereinafter, the present invention will be described more specifically with reference to the following examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Examples
Preparation of laminating co-extrusion dispersion-proof film
Example 1
A polyethylene terephthalate resin having a crystallinity of 75% was dried under vacuum at 120℃ for 2 hours and at 180℃ for about 3 hours. Then, the polyethylene terephthalate resin was melted at 280℃ and added to a feedblock using an extruder. A polybutylene terephthalate glycol copolymer having 40% of PTMEG was melted at 240℃ and added to the feedblock using the extruder.
A sheet having 13 layers was prepared using a feedblock co-extrusion at about 270℃ such that the weight ratio of the polyethylene terephthalate resin and the polybutylene terephthalate glycol copolymer is 15:1.　　In this regard, the sheet was prepared on a cooling roll at 45℃ by applying 5 kv of constant voltage thereto.
The prepared sheet was elongated by about 3.5 times in the longitudinal direction at 100℃, and coated to increase slippery properties, and elongated by about 3.5 times in the lateral direction at about 110℃ to prepare a film having a thickness of 50 ㎛ and the composition shown in Table 1 below.
Examples 2 to 6
Dispersion-proof films having a thickness of 50 ㎛ were prepared in the same manner as in Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Example 2), 5:1 (Example 3), 10:1 (Example 4), 20:1 (Example 5), and 40:1 (Example 6).
Comparative Example 1
A dispersion-proof film having a thickness of 50 ㎛ was prepared in the same manner as in Example 1, except that the weight ratio of the stiff layer to the flexible layer is 15:1 since a high-density polyethylene having 10 to 70% of CHDM was used instead of the polybutylene terephthalate glycol copolymer of the flexible layer.
Comparative Examples 2 to 8
Safety films (Dispersion-proof films) having a thickness of 50 ㎛ were prepared in the same manner as in Comparative Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Comparative Example 2), 10:1 (Comparative Example 3), 20:1 (Comparative Example 4), and 40:1 (Comparative Example 5).
Films were prepared in the same manner as in Example 1, except that the weight ratios of the stiff layer to the flexible layer are respectively 2:1 (Comparative Example 6), 10:1 (Comparative Example 7), 15:1 (Comparative Example 8), 20:1 (Comparative Example 9), and 40:1 (Comparative Example 10) using a poly methylmethacrylate (PMMA) resin instead of the polybutylene terephthalate glycol copolymer as shown in Table 1 below.　　Then, a single-layered safety film having a thickness of 50 ㎛ was prepared in the same manner as in Example 1, except that only the polyethylene terephthalate resin was used and a conventional extrusion method was used (Comparative Example 11) as shown in Table 1 below.
Table 1
Figure PCTKR2009002904-appb-I000001
Experimental Example
Measurement of physical properties
Physical properties of dispersion-proof films prepared according to Examples 1 to 6 and Comparative Examples 1 to 11 were measured, and the results are shown in Table 2 below.
1. Tear strength
Films were cut into pieces with a width of 16 cm and a length of 17 cm. A central upper portion of the pieces was cut by 2 cm, and the degree of tearing (kg) was measured using a notch. The tear strength is measured at room temperature ranging from 20 to 25℃.
2. Visible light transmittance
Films were cut into pieces with a width of 21.0 cm and a length of 29.7 cm. Impurities of the surface of the films were removed, and visible light transmittance (%) was measured using a XL211 haze meter manufactured by Gardener [ASTM D 1003 MODE].
3. Haze
Films were cut into pieces with a width of 21.0 cm and a length of 29.7 cm. Impurities of the surface of the films were removed, and haze (%) was measured using a XL211 haze meter manufactured by Gardener [ASTM D 1003 MODE].
(*Transmittance and Haze values are simultaneously generated from the XL211 haze meter.)
Table 2
Figure PCTKR2009002904-appb-I000002
Referring to Examples 1 to 6 and Comparative Examples 1 to 11, the dispersion-proof films prepared according to Examples 1 to 6 have better visible light transmittances and lower hazes (%) compared to the dispersion-proof films prepared according to Comparative Examples 1 to 11. In particular, the dispersion-proof films prepared according to Comparative Examples 6 to 10 have high visible light transmittance, low haze, and very low tear strength at room temperature. Accordingly, it can be seen that the dispersion-proof films prepared according to the present invention have excellent tear strength.　　In particular, the dispersion-proof film prepared according to Comparative Example 11 by a normal extrusion instead of co-extrusion only using polyethylene terephthalate has very low tear strength. Thus, laminating co-extrusion may be efficiently used to increase tear strength of the dispersion-proof films.
Thus, the laminating co-extrusion dispersion-proof film according to the present invention with high visible light transmittance, low haze (%), and excellent tear strength may be efficiently applied to glass for buildings and automobiles.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims (9)

  1. A laminating co-extrusion dispersion-proof film comprising:
    a stiff layer comprising a polyester or copolyester polymer resin; and
    a flexible layer comprising a polybutylene terephthalate glycol copolymer comprising polytetra methylene ether glycol (PTMEG),
    wherein at least two of the stiff layers and the flexible layers are alternately laminated.
  2. The laminating co-extrusion dispersion-proof film of claim 1, wherein the polymer resin of the stiff layer is a polyalkylene terephthalate resin, wherein alkylene of the polyalkylene has 1 to 6 carbon atoms.
  3. The laminating co-extrusion dispersion-proof film of claim 1, wherein crystallinity of the polymer resin is in the range of 75% to 95%.
  4. The laminating co-extrusion dispersion-proof film of claim 1, wherein the polybutylene terephthalate glycol copolymer of the flexible layer comprises 10 to 60% by weight of PTMEG.
  5. The laminating co-extrusion dispersion-proof film of claim 1, wherein the weight ratio of the stiff layer to the flexible layer is in the range of 2 to 40:1 (extrusion ratio, kg/hr).
  6. The laminating co-extrusion dispersion-proof film of claim 1 or 5, having both of longitudinal and lateral tear strengths of 2.0 kg or greater at a temperature ranging from -10 to 40℃.
  7. The laminating co-extrusion dispersion-proof film of claim 1 or 5, elongated by 1.5 to 5.0 times in longitudinal and lateral directions after extrusion.
  8. The laminating co-extrusion dispersion-proof film of claim 1 or 5, having a thickness ranging from 5 to 700 ㎛.
  9. The laminating co-extrusion dispersion-proof film of claim 1 or 5, having a visible light transmittance ranging from 85% to 95%, a haze ranging from 0.2 to 1.5%, a tear strength ranging from 0.1 to 10 kg at -10℃, and a tear strength ranging from 0.5 to 15 kg at 40℃.
PCT/KR2009/002904 2008-06-09 2009-06-01 Laminating co-extrusion dispersion-proof film WO2009151225A2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10272639B2 (en) 2015-03-23 2019-04-30 Emd Millipore Corporation Abrasion resistant film for biocontainers

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JPS54152084A (en) * 1978-05-22 1979-11-29 Teijin Ltd Polyester laminated film
JP3112603B2 (en) * 1993-06-28 2000-11-27 株式会社サンエー化研 Polyester sheet for thermoforming
JP2000233481A (en) 1999-02-17 2000-08-29 Mitsubishi Polyester Film Copp Laminated polyester film
JP2001158071A (en) 1999-12-02 2001-06-12 Mitsubishi Engineering Plastics Corp Laminated polyester film
JP2006007423A (en) 2004-06-22 2006-01-12 Mitsubishi Polyester Film Copp Polyester film for back-grinding tape
JP2006027044A (en) * 2004-07-15 2006-02-02 Teijin Dupont Films Japan Ltd Multilayered film for use in heat-shrinkable packaging

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10272639B2 (en) 2015-03-23 2019-04-30 Emd Millipore Corporation Abrasion resistant film for biocontainers
US10675836B2 (en) 2015-03-23 2020-06-09 Emd Millipore Corporation Abrasion resistant film for biocontainers
US11110684B2 (en) 2015-03-23 2021-09-07 Emd Millipore Corporation Abrasion resistant film for biocontainers

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