EP1044239A1 - Film polyester a turbidite reduite et depourvu de mouchetures - Google Patents

Film polyester a turbidite reduite et depourvu de mouchetures

Info

Publication number
EP1044239A1
EP1044239A1 EP98963878A EP98963878A EP1044239A1 EP 1044239 A1 EP1044239 A1 EP 1044239A1 EP 98963878 A EP98963878 A EP 98963878A EP 98963878 A EP98963878 A EP 98963878A EP 1044239 A1 EP1044239 A1 EP 1044239A1
Authority
EP
European Patent Office
Prior art keywords
film
parts per
per million
microns
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98963878A
Other languages
German (de)
English (en)
Inventor
Junaid A. Siddiqui
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Teijin Films US LP
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1044239A1 publication Critical patent/EP1044239A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention relates to polyester films.
  • this invention is related to low haze, speckle free polyester film containing calcined silicone particles and fumed silica particles.
  • Slip is critical to the processability of the film, especially thin films.
  • Slip is typically controlled by incorporating fillers to enhance surface roughness.
  • These additives include inert particles of materials such as silica, china clay, aluminum silicate, calcium phosphate, and glass. The addition of these fillers improves the winding and slitting properties of the film. However, these additives may produce haze and loss of clarity, which make the film unsuitable for certain applications, such as solar windows.
  • Siddiqui U.S. Pat. No. 5,132,356, discloses films of linear polyester containing glass spheres and fumed silica agglomerates. Addition of these materials improves the dynamic coefficient of friction and the static coefficient of the film. Although this film is suitable for solar window applications, a small amount of haze and speckle, an optical distortion of light at the film surface, is present.
  • Mills, Siddiqui, and Rakos, WO 96/01739 disclose a polymeric film consisting of a layer of polymeric material having on the surface a layer of polymeric material comprising silicone resin particles and/or calcined silicone resin particles in combination with particles of china clay.
  • the film had improved optical and handling properties, it is more expensive to manufacture than a single layer film.
  • the particles had a volume distributed median particle diameter of 1.5 to 12.5 microns. The presence of particles larger than about 7 microns can cause speckle.
  • polyester films with good slip properties and decreased haze and speckle for use in solar window applications are examples of polyester films with good slip properties and decreased haze and speckle for use in solar window applications.
  • the invention is an orientated and heat-set polyester film with good slip properties and decreased haze and speckle.
  • the film comprises: (a) about 2 parts per million to about 20 parts per million, based upon the weight of the film, of calcined silicone particles, wherein about 100 percent of the calcined silicone particles have a particle size below about 7 microns; and
  • the film has good slip properties as well as the optical properties required for solar window applications. Because the refractive index of both the fumed silica agglomerates and the calcined silicone particles is close to that of biaxially orientated polyethylene terephthalate that contains no additives, the film is very clear and has a minimum amount of haze.
  • Calcined Silicone Particles Silicone particles comprise a three-dimensional polymer chain of the formula:
  • x is a positive number greater than or equal to 1 , preferably 1 to 1.9, more preferably 1 to 1.5, and most preferably 1 to 1.2
  • R is an organic group, such as an aliphatic hydrocarbon group, e.g., methyl, ethyl, or butyl, or an aromatic hydrocarbon, e.g., phenyl, an unsaturated group, e.g., vinyl, or a mixture of two or more of these groups.
  • R is preferably a hydrocarbon group having 1 to 8, more preferably 1 to 5, carbon atoms. R is most preferably methyl. Particularly preferred silicone resin particles comprise methyl sesquioxane. Silicone particles are described in detail in WO 96/01739, mentioned above.
  • Silicone particles have a cross-linked network of siloxane linkages, comprising a mixture of the following structures:
  • Suitable silicone particles are commercially available from Toshiba Silicone Co., Ltd., Tokyo, Japan, under the name of "Tospearl" silicone resin particles. These particles have a three-dimensional network structure in which each silicon atom is bonded to one methyl group. Calcining eliminates some or all or the R group, reducing the value of x. If all of the organic group is eliminated (i.e., x is 0), the particle is converted to silica (SiU 2 ).
  • the particles are calcined at about 300°C to about 400°C for about 30 min to about 3 hr, preferably at about 300°C for about 45 min. Calcining may be carried out in air or in a suitable inert atmosphere, such as nitrogen. Elimination of some or all of the organic material during calcination reduces the weight of the particle.
  • the particles typically lose about 3% to about 5%, preferably about 2% to about 4%, of their original weight when calcined under these conditions.
  • the porosity of the calcined silicone particles enhances the adhesion of the particles to the polymer. Because the calcined silicone particles are softer (mob hardness of 3) than glass particles (moh hardness of 6), they are less prone to scratch the film during the winding and slitting operations.
  • Fumed Silica Agglomerates Fumed silica is formed when silicon tetrachloride (SiC ⁇ ) reacts in a hydrogen flame to form single, spherical droplets of silicon dioxide, which grow through collision and coalescence to form larger droplets. As the droplets cool and begin to freeze, but continue to collide, they stick together but do not coalesce, forming solid aggregates. The aggregates continue to collide to from clusters, known as agglomerates.
  • the particle size for the fumed silica particle given by the manufacturer refers to the particle size of a single cooled spherical droplet, not to the size of the agglomerate.
  • compositions comprising about 2 to about 20 parts per million, preferably about 4 to about 10 parts per million, based on the weight of the film, of calcined silicone particles.
  • About 100 percent (i.e., essentially all) of the calcined silicone particles have a particle size below about 7 microns.
  • about 100 percent of the particles have a particle size below 6 microns, more preferably below 5.5 microns.
  • about 100 percent of the calcined silicone particles have a particle size below about 6 microns, at least about 95 percent have a particle size below about 5 microns, and 50 percent have a particle size below about 2.2 microns.
  • the calcined silicone particles typically have an average particle size of about 2 to about 3 microns, preferably about 2 to about 2.4 microns, more preferably about 2.2 microns.
  • the glass particles disclosed in Siddiqui U.S. Pat. No. 5,132,356, for example, about 3% of the glass particles have a particle size above about 7 microns.
  • About 100 percent (i.e.. essentially all) of the fumed silica agglomerates are below about one micron is size.
  • the average agglomerate size is preferably about 0.10 to about 0.50 microns, more preferably about 0.25 to 0.35 microns.
  • the discrete fumed silica particles that form these agglomerates generally have a particle size of about 0.05 micron. However, these particles are typically present as agglomerates of two or more particles.
  • the concentration of fumed silica agglomerates should be adequate to help impart good winding properties to the film, but not so high that the optical properties of the film are adversely affected by excessive haze.
  • the film comprises about 20 parts per million (0.002%) to about 6000 parts per million (0.6001), preferably about 500 parts per million (0.005%) to about 3000 parts per million (0.300%), more preferably about 1000 parts per million (0.100%) to about 2000 parts per million (0.200%), even more preferably about 1400 parts per million (0.140%) to about 1800 parts per million (0.180%), based upon the weight of the film, of fumed silica agglomerates.
  • the polyester film preferably has a thickness of about 8 microns to about 75 microns, more preferably about 12 microns to about 15 microns.
  • Polyester films are well known to those skilled in the art.
  • the polymer preparation and film manufacturing processes are well known to those skilled in the art and are disclosed in many texts, such as Encyclopedia of Polymer Science and Engineering, 2nd. Ed., Vol. 12, Wiley, New York, pp. 1-313, as well as in numerous patents, such as UK Patent 838,708.
  • Polyester may be obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters with one or more glycols.
  • Preferred polyester films are those of the group consisting of polyethylene terephthalate (PET) film and polyethylene naphthanate film. These polymers are typically obtained by condensing the appropriate dicarboxylic acid or its lower alkyl diester with ethylene glycol.
  • PET polyethylene terephthalate
  • Polyethylene naphthanate is formed from 2,7-naphthalene dicarboxylic acid.
  • the most preferred polyester film is polyethylene terephthalate.
  • the calcined silicone particles and fumed silica agglomerates can be added to the polyester precursors at any point in the manufacturing process prior to extrusion of the polymer. Addition during the polymerization step is preferred.
  • the particles can be added, for example, as slurry in the glycol from which the polyester is formed, prior to commencement of the polycondensation.
  • the particles are added after formation of bishydroxyethylene terephthalate (BHET).
  • BHET bishydroxyethylene terephthalate
  • a conventional polyester polymerization catalyst is added and the polymerization carried out in the conventional manner to produce a polyester resin.
  • polyester film the polyester resin is melted and extruded as an amorphous sheet onto a polished revolving casting drum to form a cast sheet of the polymer. Thereafter, the cast sheet of polymer is heated to just above its glass transition temperature, 80°C to 100°C for polyethylene terephthalate, and is generally stretched or drawn in one or more directions.
  • the film is typically stretched in two directions, the direction of extrusion (longitudinal direction) and perpendicular to the direction of extrusion (transverse direction) to produce a biaxially orientated film.
  • the first stretching which imparts strength and toughness to the film, conventionally ranges from about 2.0 to about 4.0 times its original length.
  • Subsequent stretchings each also increase the size of the film about 2.0 to about 4.0 times.
  • the film is then heat set, generally at a temperature in the range of about 190°C to 240°C for polyethylene terephthalate, to lock in the strength, toughness, and other physical properties.
  • the film may contain any of the additives known in the art, such as dyes, pigments, lubricants, anti-oxidants, anti-blocking agents, surface active agents, slip aids, gloss improvers, ultra-violet stabilizers, viscosity modifiers, dispersion stabilizers, etc.
  • additives known in the art, such as dyes, pigments, lubricants, anti-oxidants, anti-blocking agents, surface active agents, slip aids, gloss improvers, ultra-violet stabilizers, viscosity modifiers, dispersion stabilizers, etc.
  • the additives should not greatly affect the refractive index of the film.
  • a conventional coating may be applied to the film.
  • Such coatings are customarily applied to improve the adhesive or anti-static properties of the film.
  • the composition of such coatings and the procedures for applying them are well known to those skilled in the art and are described in numerous patents and publications, such as for example, Siddiqui, U.S. Pat. No. 5,132,356, incorporated herein by reference.
  • the coating may be applied to a uniaxially orientated or to a biaxially orientated film.
  • the coating can be applied either before or after the stretching process.
  • the coating is preferably applied between the two operations, i.e. between the longitudinal and transverse stretching operations.
  • the film is stretched in the longitudinal direction over a series of rotating rollers, coated, stretched transversely in a stenter oven, and, preferably, heat set to produce the coated film.
  • the film can be metalized with, for example gold or aluminum, by techniques well known in the art.
  • the films can be used in solar window applications.
  • the film may be metalized and dyed or coated to reduce light transmission.
  • ultraviolet absorbers may be coated onto the film or incorporated into the polymer as described above.
  • a hard coating which can contain a dye and/or an ultra-violet absorber, can be applied to the outer surface of the film to improve resistance to surface scratching.
  • a pressure sensitive adhesive and a silicone-coated release liner are applied to the opposite surface for use in application of the film to glass.
  • a metalized film a laminate comprised of at least two laminated layers of polyester film is used to protect the metalized surface.
  • the laminating adhesive also can contain a dye and/or an ultra-violet absorber.
  • Tosprearl 130 Silicone resin particles mean particle size 3.0 microns, specific surface area m 2 , linseed oil absorption 75 mL/100 g
  • EXAMPLE 1 This example illustrates preparation of a filled biaxially oriented polyethylene terephthalate film containing calcined silicone particles and fumed silica agglomerates.
  • BHET polyethylene terephthalate
  • the dried chips of PET resin were extruded into a film at 285°C and then biaxially oriented by stretching in sequence in mutually perpendicular directions at draw directions of about 2.9: 1 in each direction.
  • the film was heat set at 225°C.
  • the resulting film had a thickness of 12 microns.
  • the film contained 6 ppm of calcined silicone particles and 50 ppm (0.005%) of fumed silica agglomerates.
  • this film as well as the other films described, in the Examples, can be metalized with, for example gold or aluminum, for use in solar window applications.
  • Example 2 The procedure of Example 1 was repeated except that the film contained 3 ppm of calcined silicone particles and 830 ppm (0.083%) of fumed silica agglomerates.
  • Example 4 The procedure of Example 1 was repeated except that the film contained 6 ppm of calcined silicone particles and 1250 ppm (0.125% ) of fumed silica agglomerates.

Abstract

L'invention concerne un film polyester à turbidité réduite et dépourvu de mouchetures destiné à des fenêtres solaires. Ce film comprend un mélange de particules de silicone calciné et d'agglomérats de silice sublimée, dans lequel la quasi-totalité des particules de silicone calciné ont une taille inférieure à 7 microns environ; et la quasi-totalité des agglomérats de silice sublimée ont une taille inférieure à 1 micron. Le film est très net et présente un taux de turbidité minimal.
EP98963878A 1997-12-31 1998-12-11 Film polyester a turbidite reduite et depourvu de mouchetures Withdrawn EP1044239A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7021497P 1997-12-31 1997-12-31
US70214P 1997-12-31
PCT/US1998/026429 WO1999033910A1 (fr) 1997-12-31 1998-12-11 Film polyester a turbidite reduite et depourvu de mouchetures

Publications (1)

Publication Number Publication Date
EP1044239A1 true EP1044239A1 (fr) 2000-10-18

Family

ID=22093898

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98963878A Withdrawn EP1044239A1 (fr) 1997-12-31 1998-12-11 Film polyester a turbidite reduite et depourvu de mouchetures

Country Status (6)

Country Link
EP (1) EP1044239A1 (fr)
JP (1) JP2001527147A (fr)
KR (1) KR20010033739A (fr)
CN (1) CN1283211A (fr)
AU (1) AU1911499A (fr)
WO (1) WO1999033910A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6503616B1 (en) 1999-10-25 2003-01-07 P. T. Indorama Synthetics Micronized particles
US6788182B2 (en) 2002-09-03 2004-09-07 Dupont Teijin Films U.S. Limited Partnership Metalized polyester film with heat-seal layer on opposite side for flyback transformer application
US6893476B2 (en) 2002-12-09 2005-05-17 Dupont Air Products Nanomaterials Llc Composition and associated methods for chemical mechanical planarization having high selectivity for metal removal
GB0602678D0 (en) * 2006-02-09 2006-03-22 Dupont Teijin Films Us Ltd Polyester film and manufacturing process
CN103554855B (zh) * 2013-11-08 2015-09-23 河南卓立膜材料股份有限公司 一种ttr树脂基用bopet
CN108594342B (zh) 2013-12-19 2020-09-25 康宁股份有限公司 用于显示器应用的织构化表面

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132356A (en) * 1990-11-14 1992-07-21 Ici Americas Inc. Polyester film containing minute glass spheres and fumed silica
US5459120A (en) * 1993-06-09 1995-10-17 Agfa-Gevaert, N.V. Heat-resistant layer for dye-donor element
US5626959A (en) * 1994-07-07 1997-05-06 Imperial Chemical Industries Plc Polymeric film comprising filler particles obtained by calcining precursor silicone resin particles
US5614313A (en) * 1994-07-07 1997-03-25 Imperial Chemical Industries Plc Polymeric film having a layer comprising calcined silicone particles and china clay particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9933910A1 *

Also Published As

Publication number Publication date
KR20010033739A (ko) 2001-04-25
AU1911499A (en) 1999-07-19
JP2001527147A (ja) 2001-12-25
WO1999033910A1 (fr) 1999-07-08
CN1283211A (zh) 2001-02-07

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