TWI224119B - Coated film and method for preparing a coated polyester film - Google Patents

Abstract

An oriented polyester film coated on at least one surface with a coating that improves its adhesion to gelatin is disclosed. The dry coating contains one or more sulfopolyesters; one or more tetrablock copolymer resins; and one or more non-volatile polyamines. Other ingredients, such as particulate materials and surfactants, may be present in the coating. The coating is preferably applied at the interdraw stage.

Description

1224119 V. Description of the invention (1) Scope of the invention The present invention relates to polyester film. In particular, the present invention relates to an oriented film coated on at least one coated surface, which improves its adhesion to gelatin. BACKGROUND OF THE INVENTION Polymer linear polyesters have excellent stretch orientation and have proven to be particularly suitable for biaxial film orientation. These polymer films, especially polyethylene terephthalate or PET, are tough and have excellent inherent chemical and thermal properties. In addition, it has good optical transparency, toughness, and electrostatic properties, making it ideal for photographic and reproduction applications. In these applications, polymer films are laminated with a layer of gelatin. However, valuable polyester films are not quite acceptable for coatings with gelatin. Poor adhesion between hydrophobic precious polyester film and hydrophilic gelatin. Although coatings for improving the adhesion of gelatin to polyester, such as vinylidene polyester, are disclosed in US Patent No. 2,698,240, but there is still a need to improve the adhesion of gelatin to polyester. Sexual materials. SUMMARY OF THE INVENTION The present invention is a coated polyester film comprising: (a) an oriented polyester film including a first surface and a second surface, and (b) a coating on at least one surface of the film The coating comprises: (1) one or more sulfopolyesters of about 8 5% by weight to about 98% by weight; (2) one or more of about 0.5% by weight to about 5% by weight A total of four segments

Page 4 1224119 V. Description of the invention (2) polymer resin; and (3) one or more non-volatile polyamines of about 2% by weight to about 12% by weight; wherein the sulfopolyester is The weight ratio of the segment copolymer resin and the non-volatile polyamine is based on the total weight of the sulfopolyester present in the coating, the weight of the tetrablock copolymer resin, and the weight of the non-volatile polyamine; and the coating is The thickness is from about 0.05 to about 0.4 micron. In another specific embodiment, the present invention is a polyester film coating method. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester film coated on at least one coated surface, which improves the viscosity of the polyester to gelatin. The coating is preferably applied in the stretching stage of polyester. The coated polyester film of the present invention has good adhesion to a gelatin-containing layer. Polyester film Polyester film is well known to artists. Preferred polyester films are those including a polyethylene phthalate (PET) film and a polyethylene naphthalate film. The most preferred polyester film is polyethylene terephthalate. Polymer preparation and film making methods are well known to those skilled in the art and are disclosed in many literatures, such as the Encyclopedia of Polymer Science and Engineering (Encyclopedia of Polymer Science and Engineering), Second Edition, 1 2 Booklet, Wiley, New York, p. 313, and in many patents, such as British Patent No. 83 8, 708. This polymer is typically obtained by condensing an appropriate dicarboxylic acid or its lower alkyl diester with ethylene glycol. Polyethylene terephthalate

1224119 V. Description of the invention (5) When some amines are present in the coating, good wet viscosity is obtained due to diffusion and cross-linking. Although not limited to any theory, Xian believes that the highly branched polyethyleneimine, which contains primary, secondary and tertiary amine functionality, not only acts as a catalyst but also reacts with the acidic components of gelatin, such as And aspartic acid to strengthen the interface between gelatin and coating. Polyethyleneimine is available from BASF under the trade name LupasolTM Polyethyleneimine. High molecular weight non-volatile polyamines can also be used alone or in combination with other lower molecular weight polyamines to improve the adhesion of gelatin to polyester films. High molecular weight non-volatile polyamines include high molecular weight (Wn about 30,000 or more) polyethyleneimines, such as Lupa so P p polyethyleneimine and high molecular weight polyamido · polyethylene Ethyleneimine, such as LupasolTM SKA modified high molecular weight poly (ethyleneimine). The difference between polyamidopolyethyleneimine and unmodified poly (ethyleneimine) is that at least about 20-25%, preferably about 100% of the poly (ethyleneimine) is primary N-ethylamine. An amidino (NHCOCH3) group is substituted. These high molecular weight polyamines can be obtained from BASF. U.S. Patent No. 5,4 5 3,326 to the use of polyamidopolyethyleneimide and Sidd1QU1 in the coating of polyester films is incorporated herein by reference. Other components include a small amount that can be further improved: particulate material; I, external stabilizers; the coating composition may also contain other additives that have high coating practicality. Such ingredients include dyes; pH adjusters; antioxidants; 扦 4, 柷 electrostatic agents, surfactants, and the like. You can add an effective amount of fine separation from the sliding properties of 彡 ix SJL. 1 cloth polyester film. These "materials" or pigments improve the coating and also increase the surface roughness and polyester,

1224119 V. Description of the invention (6) The surface area of the film, which also improves the adhesion to the surface of the gelatin coating. Inorganic pigments include, clay, brookite, talc, carbonated, zinc oxide, titanium dioxide, barium sulfate, carbonic acid # 5, glass, and stone stone. Organic pigments include, for example, crosslinked polystyrene, crosslinked polyethylene, and crosslinked acrylic polymers and copolymers such as fine particles of crosslinked polymethyl methacrylate. For photographic and other applications that require a transparent polyester film, materials such as silica that do not affect the transparency of the polyester film should be used. Amorphous fumed silica particles of a size below micron are preferred. For applications requiring opaque films, pigments of titanium dioxide and calcium carbonate can be used. When the coating composition is coated on a polyester film, the coating may include an effective amount of one or more surfactants to disperse the improved component in the coating composition and act as a wetting agent to achieve Good wetting and even dyeing. Nonionic surfactants are preferred. If an ionic surfactant is used, the coating and composition may be cloudy. Suitable surfactants include alcohol acetates and acetosulfonyls. Acetyl sulfonyl is a preferred nonionic surfactant. The coating composition The dry coating combination should not include: (1) about 85% by weight to about 98% by weight, preferably about 90% by weight to about 95% by weight of one or more kinds of continuous polymer (2) about 0.5% to about 5% by weight, preferably about 0.8% to about 3% by weight of one or more tetrablock copolymer resins; and (3) about 2 % To about 12% by weight, preferably about 3% to about 8% by weight of one or more non-volatile polyamines. The weight percentages of sulfopolyester, tetrablock copolymer tree, and non-volatile polyamine are based on the stone yellow present in the coating.

Page 9 1224119 V. Description of the invention (7) Based on the total weight of polyester, tetrablock copolymer resin, and non-volatile polyamine. Typically from about 0.5% to about 5% by weight of the total weight of the non-volatile amine is a high molecular weight non-volatile polyamine. This layer typically contains from about 2% to about 7% by weight, and is a particulate material based on the weight of the layer. This layer typically contains from about 1% to about 5% by weight, based on the weight of the layer, as a surfactant. Manufacturing In the typical manufacturing of polyester films, polyester resins are melted and extruded to form amorphous sheets on polished rotating casting barrels to form polymer sheets. Thereafter, the polymer casting sheet is heated to a temperature just above its glass transition temperature, 80 ° C to 100 ° C for polyethylene terephthalate, and usually elongates in one or more directions or Stretch. The film is typically stretched in two directions, producing a biaxially oriented film in the extrusion direction (longitudinal direction) and the vertical extrusion direction (lateral direction). The first elongation, which makes the film tough and tough, is traditionally about 2.0 to about 4.0 times its original length. The subsequent elongation also increases the film size by about 2.0 to about 4.0 times each. Generally, it is preferred to first elongate in the longitudinal direction and then transversely. The film is then heat-set, usually for polyethylene terephthalate in a temperature range of about 190 ° C to 240 ° C to lock the length, toughness and other physical properties. The coating composition is preferably applied before the film is finally stretched. For uniaxially stretched films, the coating composition is preferably applied during the pre-stretching phase. For biaxially stretched films, the coating composition is preferably applied during the internal stretching phase, i.e. after the film is stretched in one direction, but after

Page 10 1224119 V. Description of the invention (8) Before stretching. The coating is preferably applied by the manufacturer in "1 ni 1 ne" π, so consumers get a film that can be coated with the desired layer or undercoat. The coating is "off the line" by the consumer (0ff 1 i ne) "will require consumers to have equipment to unwind the uncoated film, coat it, stretch the coated film, and then wind it up, making uncoated coating time consuming and expensive. The coating The layer composition is conveniently applied to polyester films as an aqueous dispersion. Application from aqueous media has economic benefits, avoids potential explosion and / or toxicity hazards often associated with the use of volatile organic solvents, and eliminates the common problems encountered when using organic solvents Residual odor problem. Sulfopolyesters with higher sulfonate content are usually able to dissolve in hot water alone. However, if the lutein acid polyester is not dispersed in hot water without adjuvant, the dispersion is usually This can be achieved by adding appropriate surfactants. It may be advantageous to dissolve the sulfopolyester in a small amount of organic solvent before dispersing in water. The coating composition typically includes about 4% to 12% total solids. As Familiar with this As is known, total solids means the total amount of non-volatile materials in the coating composition, even if some of these materials can be liquids that are non-volatile at room temperature. Any conventional coating method, such as spray coating, roller Wheel coating, groove coating, meniscus coating, dip coating, wire-rod coating, air knife coating, curtain coating, doctor blade coating, front and back gravure coating and similar methods, Can be used to apply the coating composition. Once the coating is dry, the coated surface is acceptable for gelatin and requires no further treatment. The coating is typically applied as a continuous coating

1224119 V. Description of Invention (9). The preferred thickness of the wet coating is about 6.5 to about 7.5 microns as measured by a wet infrared meter. After drying, the coating preferably has a thickness of about 0.05 to about 0.4 microns, preferably about 0 β 1 to about 0.2 microns, and more preferably about 0.1 2 to about (L 1 8 Micron. Optimal thickness is 0.1 to 0.17 micron. Depending on the intended application of the polyester film, the coating can be applied to one or both sides of the film. In some applications, for example, X- A radiographic recording film is a gelatin coating applied to each side of the film. If the coating is applied to only one side, a different coating can be applied to the other side. The coating composition can be like an aqueous dispersion, sufficient The concentration and amount of application to produce a coating with the desired tack properties. The coating typically contains from about 3% to about 20% total solids, preferably from about 4% to about 18% total solids. It is known that the total solids represent the total amount of non-volatile materials in the coating composition, even if some of these materials may be liquids that are non-volatile at room temperature. Industrial Applicability The coatings of the present invention improve gelatin to polymer The viscosity of ester film, especially polyethylene terephthalate film. The coated polyester film of the present invention is useful for The application of a gelatin-containing layer coated on a polyester film. In the preparation of photographic and X-ray films, a gelatin layer containing a photosensitive silver halide emulsion is coated on a polyester film. The gelatin-containing layer can be directly coated On the coating of the present invention, or a gelatin undercoat may be applied on the coating of the present invention before the additional layer is coated on the polyester film. The coating film can also be used in which it is desired to apply a gelatin-containing layer In the reprographic application of polyester film. The advantageous properties of the present invention can be observed with reference to the following example, which is

Page 12 1224119 V. Description of the invention (10) Explains but does not limit the invention. Examples

Eastek®1300 sulfopolyester (Eastman Chemical Company, Kingsport, TN)

Lupasol ™ FG Low Molecular Weight Poly (ethyleneimine) Homopolymer, 98% solids; Viscosity = 2,000 to 10,000cps; Mw = 800; Mn = 600 (BASF, Parsippany, NJ )

Lupasol ™ P high molecular weight poly (ethyleneimine) homopolymer, 50% solids; viscosity = 18,000 to 40,000 cps;

Mw = 750,000; Mn = 60,000 (BASF, Parsippany, N J)

Lupasol ™ SKA modified high molecular weight poly (ethyleneimine), about 20% solids; viscosity = 50 to 1, 0 0 0 cps;

Mw = 2,000,000 (BASF, Parsippany, NJ) OX- 5 0 Amorphous fuming stone Xixite (Degussa, Switzerland

Ridgefield Park, NJ) Renew® 6 9 0 Anaerobic alcohol_ 1 0 Non-ionic surfactant (I C I America, Wilmington, DE)

Tetronic® 90R4 is derived from a tetrafunctional block copolymer in which propylene oxide and ethylene oxide are successively added to ethylenediamine; MW = 7,240; viscosity = 3,870 cps; mp = 12 C (BASF, Parsippany, NJ)

Page 13 1224119

Example 1 Thin film This example illustrates the steps for making a sacrificial coating. Add a layer of soil, soil, and polyethylene terephthalate to Eastek® 1 3 0 0 (43 6 wells), .ir. ^ Rn »〇y- ^ · liter) to 5 5 gallons Mix the tank and begin to stir. Add deionized 4 M 7 ^ eight under stirring; ^ ^ effectively combine to make the contents of the tank to = order.

Λ 4 · Λ aS〇1TM FG (pure), 40 ml LuPasolTM L V'a o / '-' r- niC0 9〇R4 valley fluid), and i 9 male well r ⑧ / _ surname π ^ κ y Λ Open 1 ^ 11 ^ 0 690 (20% solution in water). Add deionized water to make the tank contents reach the 50 gallon mark, and stir the raw dispersion for another 15 minutes. The coating composition was 8.7% total solids. The i-layer composition is used to stretch k layers during the manufacture of polyethylene terephthalate film. The wet coating thickness, as measured by an infrared meter, was 6 · 5 to 7 · 5 microns. The dry coating thickness was 0.16 microns. The dry coating contains 87 · 8% by weight of Eastek® 13〇〇, 4.7% by weight of Lupas〇iTM FG, 12% by weight & LuPasolTM P, i · 2% by weight of Tetrode® 90R4, 3.6% weight ratio 0x-50, and 2.4% weight ratio Renex 690. t_M2 This example illustrates the steps of manufacturing a coating composition and coating a polyethylene terephthalate film. The procedure of Example 1 was repeated, except that 800 ml of triaminononane was used.

(10% solution) in place of LupasolTM and 40 ml of LupaS0: P SKA (1% solution) in place of LupasolTM P. The resulting coating composition contained 8.7 / 0 total solids.

Page 14 1224119 The resulting coating composition is used in the manufacture of polyethylene terephthalate film = inner 4 stretch coating. The thickness of the wet coating was 6,5 to 5 micrometers as measured by an infrared meter. The thickness of the dried coating was 0. 6 microns. The dry coating had a weight of 0.024 g / m2. ij > 13

In Example 5 of this Example, the steps of manufacturing a coating composition and coating a polyethylene terephthalate film are performed. The procedure of Example i was repeated, except that LupasoPiTM SKA (1% solution) was used instead of LupasoPip. The resulting coating composition contained 8.6% total solids. During the film of ethylene terephthalate, the infrared meter was 0. 16 microns. The dry

The resulting coating composition was used to make a polymeric internal stretch coating. The wet coating thickness' is 6.5 to 7.5 m. Dry coating thickness The coating weight is 0.024 g / m². This example illustrates the steps for manufacturing a coating composition and coating a polyethylene terephthalate film. Add Eastek0 (21.8 liters) to the 55-gallon mixing tank and start stirring. Add deionized water under stirring to effectively mix the tank contents to the 25-gallon mark. The following materials were added to the resulting dispersion in the given order: 400 ml of Lu ^ asoln FG (10% solution), 40 ml of LupasoiTM p (1% solution), 20¾ liters of Tetronic ⑨ 90R4, 0.73 liters χ-50 (in a 32% solution of ethylene glycol), and h9 liters of Renex @ 69〇 (a 20% solution in water). 3. Add deionized water under stirring to make the tank contents reach the 50 gallon mark and stir the resulting dispersion for an additional 15 minutes. Resulting coating composition

Page 15 1224119 V. Description of the invention (13) Contains 4.5% total solids. The dry coating contains 87.8% by weight Eastek® 1300 '4.7% by weight LupasolTM FG weight by LupasolTM P' 1.2% by weight Tetronic® 90 ° 4, 3.6% by weight OX-50, and 2.4% by weight Than Renex® 690. The resulting coating composition was used for internally stretched coatings during the manufacture of polyethylene terephthalate films. The thickness of the wet coating layer, as measured by an infrared meter, was 6 · 5 to 7 · 5 microns. The thickness of the dried coating was 0.8 μm. The dry coating weight was 0.012 g / m².

This example illustrates the steps for producing a coating composition and applying a polyethylene terephthalate film .. Add E a s t e k (8 7.2 liters) to the 5 5 life mixing tank and start to stir. Add deionized water under agitation to effectively mix the contents of the tank to the 25 gallon mark. The following materials were added to the resulting dispersion in the stated order: 16,000 ml of LupasoFM FG (10% solution), 80 ml of p (u solution), 80 ml of Tetronic @ 9〇R4, 2.92 Liters 0xρ_50 (32% solution in Eichichi), and 19 liters. Take a 69% (in 20% solution). Under stirring, Wo 4; I mark, and will produce ϋ to make the contents of the tank reach 50 plus

The compound contained 16.2% total solids. The politician was given another 15 minutes. Produced coating group The produced coating and composition are used for the inner stretch coating of polyethylene terephthalate film door. This wetness 卞 :: The amount during the thick film period is 6.5 to 7.5 micrometers and the thickness is U48 g / m2 measured by an infrared meter. The coating thickness is 0.32 micrometers. Dry coating

Page 16 1224119 V. Description of the invention (14) After describing the present invention, the following is the scope of patent application and its equivalent description. _ ilii Page 17

Claims (1)

1224119 Case No. 88112499% Year F. Amendment VI. Scope of patent application I " '! ·' | 1. A coated polyester film v: It includes ... (a)-a oriented polyS film, The film includes a first surface and a second surface, and sequentially (b) a first coating on at least one surface of the film, the coating comprising: (1) 85% by weight to 98% by weight In contrast, one or more sulfopolyesters are composed of a polyol and (i) at least one sulfonated polycarboxylic acid or its anhydride or a lower alkyl group and (ii) at least one unsulfonated polyweilic acid or its anhydride. Or derived from the reaction of lower alkyl esters; (2) one or more tetrablock copolymer resins ranging from 0.5% by weight to 5% by weight, which are sequentially added by ethylene oxide institute and then propylene oxide institute Derived from ethylenediamine; and (3) one or more non-volatile polyamines from 2% by weight to 12% by weight; ii wherein the one or more nonvolatile polyamines include 0.5% by weight to 5% by weight, based on the one or more non-volatile polyamines, high molecular weight non-volatile polyamines, of which sulfo The weight of the ester, tetrablock copolymer resin, and nonvolatile polyamine is based on one or more sulfopolyesters, one or more tetrablock copolymer resins, and one or more nonvolatiles present in the coating. The total weight of the polyamine is used as a basis; and the thickness of the coating is from 0.05 to 0.4 microns; and (c) a second coating includes a hydrophilic gelatin layer. 2. The coating film according to item 1 of the patent application scope, wherein the polyester film is selected from the group consisting of a polyethylene terephthalate film and a polyethylene naphthalate film O: \ 59 \ 59539-920305.ptc Page 19 1224119 Case No. 88112499 Amendment VI. Application for Patent Scope: Coating No. 1 of the thin film coating of the item 2 No. Fan Li specially asked the Chinese government to make the 3 The film is thin. The micro-item of the thin-coated cloth material is coated with the '-< 3 cut-off enclosing the dense range of the day 1MMJ detailed. Please specifically apply for the 114th layer of the outer root of the contract, and the item 4 of its thin-film coating. Enveloping film Fanboli ester specifically asks for ethyl phthalate to be polymerized to 5 meters of rice, and the film is coated with rice item 5 micro 2nd fanli special 1 • Medium ο is according to the root thickness 6 The layer coating film is thin and coated with a thin sheet of cloth coated with 0 meters of item C micro h 2 18th ο to Fan M, ΤΠΊ micro-specialist 12 please 0. Apply as the basis of the thickness of 7 · Among them, the film is covered with a thin cloth. The second upper surface of the surface is shown in the table. The second surface is requested. According to the table, the root is 8. The number of sulfonated species is more than or equal to 30:] heavy LL species-of. Specific gravity four or more or more or one of the ratio of ο / 5 specific gravity 9 to the amount of% specific weight 3 ° / 0 to the specific amount of weight including the percentage 〇8 layer 0 fatty amine and dagger polymer properties Gathering a total of non-embedded seed coating-No. 8 in the film and thin cloth coating No. 8 Fan Li specially requested in accordance with the root 9 Micro-divided fine seed 1 Including the outer layer 10 to 11 Item 9 No. Wei Fanli specially requested that according to the film thin film S diacetic acid phthalic acid coating on the polylayer coating to be thin Membrane 〇Thin cloth coated material is the first item in which the film is coated. 11 Fan Fan Li specially requested to apply for the root ο Middle ο for Yu Weisan and J degree thick rice micro 1 2 section • Wai ο To Fan Milli Micro-Professional 1Please apply the item in its film thin cloth to Micron Micro O: \ 59 \ 59539-920305.ptc Page 20 1224119 Case No. 88112499 Amendment VI. Patent Application Scope 1 3 According to the application, please apply for the coating film of Item 12 of Llj, where the first coating is additional Includes a surfactant. 1 4. A method for preparing a coated polyester film according to item 1 of the scope of patent application, the method comprising applying a first coating composition on the polyester film in an internal stretching stage, the composition comprising: ( 1) one or more sulfopolyesters with a weight ratio of 85% to 98% by weight, which are composed of a polyol and (i) at least one luteinized polyretic acid or anhydride or lower alkyl ester thereof and (ii ) Derived from the reaction of at least one unsulfonated polycarboxylic acid or its anhydride or a lower alkyl group; (2) one or more tetrablock copolymer resins of 0.5 to 5% by weight; It is produced by successively adding ethylene oxide and then propylene oxide to ethylenediamine; and (3) one or more nonvolatile polyamines in a weight ratio of 2% to 12% by weight; wherein one or more A variety of non-volatile polyamines include 0.5% by weight to 5% by weight. Based on the one or more non-volatile polyamines, high molecular weight non-volatile polyamines, including sulfopolyester and tetrablock The weight of the copolymer resin and non-volatile polyamine is based on one or more sulfonic acids present in the coating. A polyester, one or more tetrablock copolymer resins, and one or more non-volatile polyamines based on the total weight; and the coating composition comprises 4% by weight to 12% by weight total solids, and then coated The cloth comprises a second coating composition of a hydrophilic gelatin layer. 15. The method according to item 14 of the scope of patent application, wherein the film is a polyethylene terephthalate film. O: \ 59 \ 59539-920305.ptc Page 21