TWI314938B - Anti-static polyester release film - Google Patents

Description

1314938 IX. Description of the Invention: [Technical Field] The present invention relates to an antistatic polyester film, and more particularly to a polyester film formed by forming a conductive polymer on at least one side of a polyester film. The antistatic layer forms a tantalum resin layer on the upper layer of the antistatic layer to improve antistatic property and release property. [Prior Art]

With the development of industrialization, the problem of the use of synthetic resin or synthetic fiber in various fields of electrical and electrical equipment, information and communication, and general household goods is increasing. Recently, the release film with the main purpose of protecting the adhesive layer is also required to have an electrostatic function. In the past, in order to solve the problem of static electricity generated when the release film is separated from the adhesive layer, the adhesive layer is rendered antistatic. When the agent layer is given an antistatic function, there is a problem that the antistatic agent and the adhesive are poor in compatibility, and the antistatic property cannot be sufficiently exhibited. Therefore, in addition to the adhesive layer, the antistatic function is imparted to the release layer. On the other hand, the physical properties required for the above-mentioned release film electrical work m丄4 (four) film, in addition to anti-static stability, Type peeling force, solvent resistance, 矽 非 r r : type peeling force is only shown when the point of preparation is applied, but the case of the release layer is also the indicator "the peeling force at the time of peeling is good, generally '", make the self-adhesive agent layer. On the other hand, the mouth of the mouth is low with a release liner aspect. When the W contained in the release film is transferred to the adhesive layer may be ::::, the A core knife is lowered. In the process of joining I) 1314938 adhesive and release film, the solvent used for the adhesive may cause: layer separation, and the separated contact layer of the adhesive will reduce the adhesive function to make antistatic The function (four) type film is known as a method for coating a metal material such as a clock, a copper, a two-m-go, or a metal material in a stone-like composition. However, the above method is not only uneconomical, but the aforementioned Shi Xi cannot perform sufficient performance in the release liner. Further, when a composition is mixed with Shi Xi resin and an antistatic resin, nitrogen, scale, and sulfide containing fat may hinder the hardening of the crucible, which is difficult. Furthermore, when the (four) cloth is applied to the antistatic coating surface of the surfactant, the general electrostatic agent will exert an antistatic function depending on the humidity in the atmosphere, but it is caused by the anti-static ray screen & ^ Α曰The coating on the enamel coating on the enamel will reduce the antistatic function. In particular: the combination of the anti-static layer and the stone layer. - The transfer of the enamel to the adhesive surface reduces the function of the adhesive. SUMMARY OF THE INVENTION The above object of the present invention is to provide an anti-resin two film even if it is in the upper layer of the antistatic layer. The effect is not lowered and the release property is improved. For the purpose of the present invention, the film comprises: forming a polyester film comprising two: Γ-face or both sides; an antistatic coating layer; a static electricity polymer; and laminating the antistatic household 1314938: resin layer To improve the release properties. The fat and static: layer preferably comprises: a conductive polymer, a binder tree of 100 weights, and the antistatic layer is preferably: 40 to 1 〇〇 'package 3 binder resin 200 to 2000 with respect to the conductive polymer Parts by weight and parts by weight of the crosslinking agent. Bio:: The conductive polymer is preferably obtained by kneading a polyanion and a poly phenotype or a derivative thereof. It is preferable that the mixture resin contains a functional group selected from the group consisting of a 'carbonyl group, a hydroxyl group, an acrylic group, a carbamate group, a soil' amidino group, a quinone imine group, and the like. Tannic acid, maleic acid and maleic anhydride. Last month, it is preferred that the parent agent is a compound selected from the group consisting of the following: h compound: isocyanate vinegar, mercaptoimine system, serotonin β and melamine. Preferably, the antistatic layer contains from 0 to 10% by weight of the solid component. The ruthenium resin contained in the ruthenium resin layer preferably contains an alkyl group-t-oxane or an alkyl hydrazine agent. The bauxite 11-form m-form, the platinum-gold complex, and the stone-like-like coupling are preferably composed of a solid component of 5 to 5 〇. The thickness of the above-mentioned brewed film is preferably 5 to 3 〇〇 μηι. °° Anti-static poly, release film according to the invention, used in various 亍 : : : , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Defects caused by the 'anti-resin layer' anti-static work property. Wang Jian's virginity 1314938 [Embodiment] Hereinafter, the present invention will be described in detail. The antistatic polyester film of the present invention comprises: a poly layer a conductive polymer formed on one or both sides of the polyester film; and a resin layer laminated to provide physical properties. First, an antistatic layer is described. The antistatic layer of the present invention is prevented from being in the polyester. Static on the film: the electrostatic layer is: contains: conductive polymer, binder resin and cross: 曰 Further, the antistatic layer is preferably: relative to the conductive polymer (9) reset part, including binder resin 200 to 2000 parts by weight && _ parts by weight. 5 conductive materials and parent-linked agent 40 to 100 conductive layer contained in the conductive layer, in order to impart anti-static, mixed polythiophene or its derivative in polyanion Used as a thing. And two of Formula i Formula 2

An ester film; an antistatic coating comprising an antistatic layer as described above and polymerized in the presence of a polyanion. Early or mixed

[Chemical: L J

The aliphatic group of C丨·2 has, for example, a f group, and in the above formula 1, &, each represents a hydrogen group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and a specific hexapropyl group or an isopropyl group. , butyl and stupid. 1314938

In the above formula 2,! ! For 丄~4 integers. The acid precursor ion is an acidic polymer, and is a polymer carboxylic acid or a polymer m-based acid. The macromolecular acid is polyacrylic acid, polymethyl, fluorene maleic acid, etc. The polymer acid is polystyrene acid. Weight II::: The present invention uses poly(3,4·ethyl roasted dioxin). ·5: and 1 part of the ethylene-acid dispersion (molecular weight Mn=150000) 0.8% by weight of the poly-zine white water dispersion (Baytron ρ, the binder resin contained in Bayer's eight-iw electrostatic layer is water-dispersed or water-dissolved Properties: 2: Resin 'in order to achieve adhesion between the antistatic layer and the polyester film of the substrate film 200~Γ ^In the conductive polymer resin _ part by weight, add the weight of the target. If the bonding agent The content of the resin is less than 200 parts by weight, and the adhesion to the substrate may be problematic. If it exceeds 2 parts by weight, the transparency and the antistatic property may be problematic. Any one of the following groups selected from the group consisting of: a group, a thiol group, an acryl group, a urethane group, a buffer group, a carboxylic acid, a maleic acid, and a maleic anhydride. The binder may be used in the following ones: a polyacid system, a polyamino phthalic acid sap " a oxime system, a % oxygen system, a polyester system, a vinyl resin, a brewed glutinous rice. Skeletal structure, which can be combined by a copolymerization or the like 1314938 with a composite structure of a scallop, with the complex The binders to be constructed are, for example, acrylic resin grafting, acrylic resin grafted polyurethane, vinyl resin grafting, vinyl resin grafting, and the like, which are contained in the antistatic layer. The crosslinking agent is used for improving the adhesion between the coating layer of the antistatic layer and the polyester film of the substrate layer, and it is preferred to use any one of the following groups: Cyanamide, a number of bases, a melamine system, a melamine system, and a melamine compound. The crosslinking agent is added to the above-mentioned crosslinking agent 40 to 400 fish k: 'If the amount of addition is low 640 parts by weight, it is not sufficiently hard to be hardened: the current adhesion 'if it exceeds 400 parts by weight, the transparency is hindered. μ The n electric layer is diluted, and the m agent is diluted to a content of 〇5 to η with respect to the total weight component. η./秘$士随· If it is possible to dissolve the J:成=S film of the present invention, the solvent may be applied to the polyester film only for the solid content of the month, but water is preferably used. - Aspects... The above solids are:, two miles below 〇.5 4% by % Film layers to form more anti = function to show the problem of insufficient, if ...: Two

There is a problem that the transparency of the film is lowered. IJ Next, the resin layer is described. The stone layer of U-H H, the type of physical property can be: the above-mentioned antistatic layer can improve the vinyl group of the vinyl group, and the anthracene resin layer used in the present invention contains an alkane siloxane. Mixture: more burnt-based nitriding polysulfide oxy-fire, platinum complex and Shishi weight fraction 'system, cast two-burning relative to the base-burning polyoxy-oxygen 10 . Input 2~5 weight ten: "Xi oxygen burning i·5~10 parts by weight, preferably weigh the weight. Compared with the base of the base group, 10 1314938 is wrong, 4 is not 1〇~5 〇〇PPm. 0.5 to 30 parts by weight of decane coupling agent is used in combination with the ethylene-based dilute oxygen-doped dimethoate. : 矽 偶 coupling agent, using amino decane series, ethoxy oxime, and WW ^ ^Alkyl oxyalkylene-based, isocyanic acid-based decane-based, etc., using an epoxy-based decane coupling agent. The lithium resin layer of the present invention is diluted with a solvent to a side component with respect to the total weight, and then coated. It is placed on the film of poly s. If it is a moon shape, it cannot show sufficient release force, and in the case of A 10% or more, f is poor in visibility, and it will change the time and shape of the hardening. The solvent is only a soluble component. It can be applied to the antistatic layer, and the type is not limited. It can be used in any of the following groups: LV μ γ ^ , , any of the above: methyl yeast, ethanol, methyl ethyl ketone, methyl, hexane and Ethyl acetate, etc. 2 矽 使用 resin used, 彳 should be dispersed in the form of emulsion or dispersed phase can be added step by step An aqueous polymer such as an alcohol or a polyvinyl alcohol or a surfactant such as an alkylphenyl polyglycol ether. Next, a description will be given of a polyester film. The polyester hydrazine type used in the present invention is not known. As an antistatic coating I ϋ i material. The present invention is based on polyethylene terephthalate vinegar polybutylene terephthalate S, polyethylene naphthalate vinegar, etc. The polyester film of the present invention is not limited thereto. The polyester constituting the film is obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol to obtain a polystyrene. For example, there are terephthalic acid, 2,6-nine-second bio-acidacy, 'on gti ^seven>, for example, there are glycols, diethylene glycol, 1,4 - rings. Ppm 疋-methanol, etc. Representative polyesters are, for example, 11 1314938 to ethylene glycolate (PET), polyca-2,6-didecanoic acid glycol (PEN), etc. It may be a copolymer containing the third component. For the above-mentioned copolymerization of the dicarboxylic acid component, for example, isophthalic acid, phthalic acid, terephthalic acid, 2, 6 _Naphthalene dicarboxylic acid, adipic acid, sebacic acid, hydroxy retinoic acid (for example, P-hydroxybenzoic acid, etc.); diol components are, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol,丨, 4_cyclohexanedimethanol, neodecyl glycol, etc. These dicarboxylic acid components and diol components can be used together 2 or more types.

The film of the present invention is a uniaxial or biaxial alignment film which has high transparency and is excellent in both productivity and workability. The polyester film of the substrate film can be produced by a known method, melted in a vacuum, dried, extruded in an extruder, and extruded through a die (t_die) onto a sheet, and passed through a cooling roll. By electrostatic application (pinning to make a dense. In a drum, cooling and solidifying to obtain an unstretched polyester sheet. Further, by heating the roller to a glass transition temperature or higher of the polyester resin, using a roller and a roller The circumferential speed ratio difference is 25 to 45 times in the longitudinal direction, and then the film held by the jig is stretched in the lateral direction of the mechanical extension, and the inner stretch is 3. G to 7. G times. A thermosetting method can obtain a stretched alignment film. The coating method between the longitudinal stretching step and the transverse stretching step is not limited thereto, and a Meyer bar (1 bar, Γ bar) method can be used. It is preferable to print a θ type or the like, and it is preferred to introduce a polar group on the surface of the film before coating, and perform a corona discharge treatment, w „adhesiveness or coating property of the X cloth layer and the film. Electrostatic coating Wei Pan dip - into the liquid Queen's sex, affinity (wetting) k leveling (leveling), can be B , ^ isopropanol (isopropanol) and other alcohol cheeks; ethyl fibrin, third base / fibrin oxime ether; methyl ethyl ketone, acetone 12 1314938 and other ketones such as methylethanolamine and other amines / ionic / Non-^ J /JJS ν *Mountain 'Carved Ding Tu' <braj Τ王1 or more kinds of mixed use. The thickness of the polyester film is usually 5~300μηη' preferably 1〇~25〇 from m. The antistatic layer on the base film is formed by applying a coating liquid obtained by diluting a conductive polymer resin, a binder resin, and a crosslinking agent with water on at least the γ surface of the base film. The coating method of the cloth composition can be carried out using a general method such as gravure printing (inhibiting _ ^. (1) or reversing = Ve: Se roll) using a roll coating method, using a Meyer rod (four) = cloth method The coating method of the air knife (ai) and the knife is preferably applied to the coating of the second layer: the halo discharge treatment, the introduction of the polar group on the surface of the film, the surface tension is high, and the coating property of the composition is improved. The composition and the poly(tetra)lipid=layer are on the upper part of the antistatic layer on at least one side of the base film, and the product: the core layer, the enamel layer, and the layer of the lipid layer The method and the antistatic layer are followed by coating by a gravure coating method. 2: air drying?: to produce a poly(tetra) type film excellent in antistatic property. Differently, the mechanism of the antistatic agent is to use a c agent. The mechanism realizes an antistatic function, and the invention realizes an antistatic effect by using a conductive 'two: ion exchange mechanism, and the antistatic property can be maintained even in the electronic coating of the resin layer of the object. The present invention will be described in more detail below by way of examples, and the scope of the present invention is not limited to the above. 13 1314938 ' <Manufacturing Example 1 > Production of polyester film substrate 2 S has an average particle diameter Amorphous spherical oxidized oxide particles of 2.5: Q β - ethylene glycol granules (limit viscosity 1, 2 / §) 'Using a vacuum dryer, after 16 (r fully dried for 7 hours) The ΐ-type mold is adhered to the cooling drum by electrostatic application, and the 未-shaped unstretched sheet is reheated at 95 ° C. The film is stretched 3 _ 5 times in the direction of the film. -a, /, the person is subjected to corona discharge treatment on the film surface to be coated, and a polyester film is produced. <Example 1> On the surface of the & corona treatment, the conductive high knife K 曰月曰 (Bayer, Baytr〇n P; contains poly 3,4-ethylene II) Oxythiophene, weight / hydrazine and styrene polystyrene sulfonate · 8 wt% aqueous dispersion) just weight acrylonitrile-based binder resin (Japan Carbide, γ8 〇〇 3 Β) 4 〇〇 伤 环氧 环氧The combination agent (Nagase Chemtech, DENACOLEX- φ) is mixed with water to form an antistatic coating liquid. At this time, the inner portion of the oral cavity was 2.0% by weight with respect to the entire antistatic coating liquid. The antistatic coating liquid described in the above section was coated with a small film such as the above-mentioned production example using #8. After coating, the coated coating liquid was dried at a stretching range of 1 〇〇 to 13 ', and subjected to a 3.5-fold stretching in a direction perpendicular to the film direction. A biaxially stretched antistatic polyester film having a thickness of 25/xm was obtained. On the formation surface of Yuhong electrostatic layer, enamel resin (Dow Corning, SYL-• 〇 FF (g) SD 7226) 1 〇〇 part by weight of n (anch 〇 rage) additive (Dow Kang 14 1314938 Ning Company, SYL-0FF ( §) S1 9250) 1 part by weight and 1 part by weight of platinum catalyst (Dow Corning, 40 〇〇 cat) mixed with 1900 parts by weight of a dilution solvent composed of benzene and hexane, and the total solid content is diluted to 15 parts by weight. After %, it was coated using a gravure coater. After the above coating, it was dried and hardened in the range of 川5丨5〇艽 to finally obtain a polyester release film. <Example 2 > In the production stage of the antistatic layer, a conductive polymer resin (Bayer's Baytr〇n P) was used in an amount of 1 part by weight, and a urethane slag resin (large曰本墨化学, Ap_4〇F) 5 parts by weight, trimeric guanamine crosslinker (Cytec, CYMEL385) 15 parts by weight, mixed with water and diluted to a total solid content of 2 _5% by weight, except This was carried out in the same manner as in Example 1, to prepare a polyester release film. <Example 3> In the production stage of the antistatic layer, a conductive high-part 2 resin (Bayer, Baytr〇np) was used in an amount of 1 part by weight, based on the solid content, and a polyester resin (曰-成W〇) 〇 30) 40 parts by weight, epoxy crosslinking agent (Nagase chemtech △ Division, DENACOL ΕΧ-313) 1 〇〇 part by weight, mixed with water and diluted to a total solid content of 2. 5 wt% ' Otherwise, the same procedure as in the above-described Example 1 was carried out to produce a poly-δ-release film. <Comparative Example 1 > In the production stage of the antistatic layer, the conductive polymer resin was not added, and the electrostatic agent (Cytec, cystaT 6〇9) was added to the level 4: 1 〇〇 weight: carbamate s intended binder resin (Daily Ink Chemistry, Ap_4〇F) 3 〇〇 Lizhi - olamine crosslinker (Cytec, CYMEL 385) 50 weight

A polyester release film was produced in the same manner as in the above Example 1 except that the amount of the solid content was adjusted to be a weight % by mixing with water and mixing it with water. <Comparing your j 2> In the manufacturing stage of the antistatic layer, 'without adding a conductive polymer resin, and adding 4 (four) antistatic agent (Japanese fat public 51, Xianqing 264_~(10) parts by weight, acrylic resin (Japan Carbide, γ8〇〇3Β) 2 parts by weight, 50 parts by weight of an epoxy crosslinking agent (Nagase chemtech, denac〇l Εχ 313), diluted in water and diluted to a total solid content of 2.0% by weight, except In the same manner as in the above Example, the polyester release film was produced in the same manner. The biaxially stretched films produced in the above Examples 1 to 3 and Comparative Examples 2 to 2 were evaluated for physical properties by the following methods. As shown in Table 1. 1. Antistatic static sputum using antistatic measuring machine (Mitsubishi (stock); model MCP-T600), in the environment of temperature 23 ° C, humidity 50% RH, after setting the sample, according to JIS K7194 'Measure surface resistance.

UtJLj·sheng (turbid Tang (hazM placed a piece of sample sampled at 1 Ocmx 10cm vertically in a turbidity measuring machine (AUTOMATIC DIGITAL HAZEMETER, manufactured by Nippon Paint Co., Ltd.) to make the wavelength 400~700/xm The light is transmitted through the direction perpendicular to the vertically placed sample, and the displayed value is measured. At this time, the haze is calculated by the following formula: Haze (%) = (i_the amount of scattered light / the total amount of light transmitted) xl 〇〇16. 一〆1314938 3. Release peeling force After the sample is stored in the humidity of 25: (:, 65% RH for 24 hours, a standard tape (TESA7475) is attached to the coated surface of the crucible. After normal temperature (25. 〇 conditions were pressed at a load of 20 g/cm 2 for 3 minutes, the peeling force was measured at a speed of 12 in/min from 180° at a rate of 12 in/min. The unit of force is g/in, and the measured value is expressed as the average value of 5 times of measurement.

_4·Residual adhesion rate After the sample was stored at 25 ° C, 65 Q / 〇 RH humidity for 24 hours, a standard tape (Nitt〇 31B) was attached to the stone coating surface at room temperature (25C > c) The load of 20 g/cm 2 was pressurized for 24 hours. After the adhesive tape adhered to the kneading surface was recovered without contamination, the surface was adhered to a flat clean PET film, and then pressed back and forth three times with a 2 kg roller (ASTM D-1000-55T). Thereafter, a peeling force measuring device (cheminstrument Ar_i〇〇〇) was used, and 180 was used at a speed of 12 in/min. The peeling force was measured at the angle peeling. At this time, the residual adhesion rate value is calculated by the following formula. Adhesion residue ratio (%) = tape peeling force after peeling on the kneading surface / tape peeling force without contact with the kneading surface X 1 〇〇

The resistance of the film surface to the solvent was measured. In the measurement, the cotton swab was dipped with ethanol, and then the cotton swab was passed back and forth at a speed of 5 cm/sec at a speed of 5 cm while maintaining the swab angle of 45 degrees. The state of the coating surface of the film surface was evaluated on the basis of the following criteria. 〇·Antistatic properties are almost unchanged, no scratches. 17 U14938 No antistatic properties, or peeling off the coated surface.

L Table 1] Surface Electrolysis Example 2 Example 3 Comparative Example 1 Comparative Example 2 Transparency ΙΟ5 (10, 106 (104) 105 (104) 1015 (1011) ΙΟ16 (ΙΟ11) 1.35 1.13 Release release rate 1.07 1.84 2.20 Residue Adhesion rate 9.2. 11.2 9.8 11.4 10.5 Solvent resistance, M: 95 ----- 96 95 96 95 _JT〇y___ Resistance — Ο 〇〇 XX 0 〇 XX Among the surface resistance item values, the value in parentheses indicates the formation of tantalum resin Before the layer, force >I^ & the surface resistance value of any antistatic coated surface, formed by the outer table T; 5 ;; ^ surface resistance value after the grease layer. _ Solvent (T is called measurement for A Laughter, solvent resistance, and solvent resistance (MEK) are measured for solvent resistance to methyl ethyl ketone. 4 As shown in Table 1, the conventional humidity-dependent antistatic layer of Comparative Examples 1 and 2 Shi Xi is covered by the film and causes antistatic function to be reduced. When it contains conductive tree, it can combine with the physical properties and stability and is excellent in anti-JUh 疋* // month & 0 ^ The present invention is only for the above The embodiment is described in detail, but those skilled in the art should understand that it is within the technical idea of the present invention. Deformation and for a variety of modifications, of course, contain the modification and modified within the scope of the patent application., [1314938] Brief Description of the drawings The main element SIGNS LIST None

19

Claims (1)

<1314938 > Patent Application No. 095,110, 881 'Application Patent Scope Replacement This Application B: Ride: 1. An antistatic poly-strand film characterized by a ϋ·'. a oxime ester film, an antistatic coating layer formed on one or both sides of the polyester film, and a resin layer laminated on the outer side of the antistatic coating layer to improve release properties; the antistatic coating layer contains conductivity a polymer, a binder resin, and a crosslinking agent, wherein the conductive polymer is obtained by polymerizing a polyanion with a polythiophene or a polythiol derivative, and the binder resin is selected from the group consisting of a carbonyl group, a hydroxyl group, and an acrylic acid. a functional group of any one or more of the group consisting of a base group, an amino ester group, a carboxyl group, a decylamino group, a quinone imine group, a slowfeet maleic acid, and a maleic acid liver, the crosslinking agent containing a selected from the group consisting of an isocyanate group and a carbonyl group. a compound of any one or more of the group consisting of a quinone imine, an oxazoline, an epoxy, and a melamine; the lyre resin layer is an alkyl vinyl polysiloxane, an alkyl hydrogenated polyoxane, Platinum complex and decane coupling agent mixing Made. 2. The antistatic polyester release film according to item 1 of the patent application, wherein the '°H antistatic coating layer' contains a binder resin 2〇〇~2 with respect to the conductive polymer 丨〇〇 by weight. 〇〇〇 by weight and crosslinker 4〇~1〇() by weight. 3. The antistatic polyester release film of claim 1, wherein the antistatic coating has a solid content of 〇.5 to 1 () by weight 0/〇. 4. The antistatic polyester release film of claim 1, wherein the solid content of the resin layer is 〇 5 to 5 mm 〇 weight 0 / 〇. 5. In the antistatic polyester release film of claim 1 of the patent scope, in 20 1314938, the polyanion is an acidic polymer and is selected from the group consisting of polyacrylic acid, polymethacrylic acid or polymaleic acid. One or a mixture of two or more of a group consisting of a polymer sulfonic acid such as a carboxylic acid or a polystyrene sulfonic acid and a polyvinyl sulfonic acid. XI. Schema: None 21