TWI357433B - Anti-fouling thin film - Google Patents

Description

1357433 IX. Description of the Invention: [Technical Field] The present invention relates to an antifouling film, and more particularly to an antifouling film which can simultaneously have good stain resistance and ink marking property. [Prior Art] The liquid crystal display device is mainly an optical device in which a backlight module, a polarizing plate, a glass substrate, a liquid crystal layer, and a color filter are combined. The polarizing plate converts the polarized light into a polarized light, and the liquid crystal display uses the polarized light and the twisting characteristics of the liquid crystal molecules to control the passage of light. In the process of fabricating the liquid crystal panel, the upper and lower polarizing plates must be used, and the upper and lower polarizing plates must be disposed at a specific direction angle according to the polarization direction thereof, so that the polarized light generated by the first polarizing plate can pass through the liquid crystal layer. By changing the polarization direction of the liquid crystal molecules under the electric field and no electric field, the polarization direction is changed by the second month polarizing plate to be in a bright state or shielded by the second polarizing plate to exhibit a dark state, thereby displaying subtitles or patterns. . Therefore, in order to conveniently and correctly put the upper and lower polarizing plates into the liquid crystal display panel module, generally, the printing action is first performed before the installation, that is, the direction of the polarized light is marked on the polarizing plate with the ink. 1 is a schematic view showing the basic structure of a general polarizing plate, mainly by attaching a protective film 20 to a polarizing layer 10 to form a polarizing plate 100, wherein the function of the protective film is to ensure that the polarizing plate is not damaged or contaminated. The polarizing layer 10 includes a polarizing group 1 1 ' such as Poly Vinyl Alcohol (PVA); a protective body 2 such as a triacetate cellulose (TAC) film; H8452.doc and a pressure-sensitive adhesive layer 13 (Pre The Sensitive Adhesives (PSA), the pressure-sensitive adhesive layer 13 can be attached to the panel 3〇. The protective film 2 includes a pressure-sensitive adhesive layer 21, a substrate 22, and an anti-staining layer 23, and the direction of the polarized light of the polarizing plate is marked with ink above the anti-staining layer. Generally, the common source of dyeing mainly includes the fingerprint contamination during the storage period, the cleaning of the natural environment in the cutting and module assembly, or the fingerprint pollution during the manual operation. Other major pollution sources are also due to the pressure-sensitive adhesive layer 13 or 21 During the cutting process, the adhesive of the cutting line of the towel is adhered to the residual layer 23 caused by the anti-fouling layer 23 on the surface of the protective film. At this time, an organic solvent is used to clean the surface of the protective film, so the surface of the protective film is In addition to the excellent anti-fouling properties, the anti-fouling layer 23 also has good chemical resistance to prevent the anti-fouling layer 23 from being damaged by the organic solvent. As described above, since the polarizing plate must be borrowed The ink is sun-marked on the anti-fouling layer 23 of the surface of the protective film, so that the anti-staining layer η on the surface of the protective film must be easily inked, and the ink-marked ink mark must not be easily removed during wiping or other cleaning processes. In addition, the desired characteristics and the anti-fouling properties of the film are contradictory. Therefore, how to make the anti-fouling layer 23 on the surface of the protective film have antifouling property and good ink marking property has become an urgent market. Want to solve In addition, when the protective film is assembled in the liquid crystal display device 4, it is easy to generate static electricity. In addition to the contamination caused by the easy adsorption of dust, the component is also susceptible to electrostatic damage, so antistatic property is also one of the important functions of the protective film. In the past, many discussions have been made on how to improve the anti-staining property or antistatic property on the surface of the protective film, such as adding a surfactant or a hydrophilic polymer electric preventive agent, kneading a conductive filler such as carbon black, metal powder, or low use. U 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A rubbing layer and an adhesive layer, and an antistatic effect is obtained by adding a surfactant static antistatic agent. The Republic of China Patent No. M291540 discloses a protective film comprising a substrate, a scratch-resistant anti-glare layer, and anti-fouling. Layer and adhesive layer, the anti-fouling layer has a large contact angle to water (between 90 and 120 degrees), so it can achieve anti-fouling effect by surface water repellency. Republic of China Patent No. 520448 A protective film comprising a comb-type polymer coating coated on a side of a substrate via a layer of the antistatic agent; the branching portion of the comb-type graft polymer is disclosed It is made of polyfluorene, so it has water repellency and can achieve the effect that the contaminant is not easily adhered. However, in order not to hinder the function of the antistatic agent layer located in the lower layer, the coating amount of the comb-type graft polymer is limited. That is, no more than 1 〇mg/m2. A protective film is disclosed in the Republic of China Patent Publication No. 200413790, and an antistatic layer containing tin oxide and a hardened resin layer as a scratch resistant layer are sequentially disposed on the surface thereof. The scratch-resistant layer can be added with a non-reactive polyoxyl resin to make the surface less susceptible to staining or easy to decontaminate even when stained, so it can be both resistant and antistatic. The above documents disclose anti-staining or prevention. Static electricity 'or a protective film that can simultaneously prevent static electricity and stains, but does not disclose a protective film that has good ink marking properties. In view of the foregoing problems, the present invention is based on the anti-fouling film, and provides a anti-fouling film with good anti-fouling property, chemical resistance and antistatic property by the special microstructure of the polymer in the anti-fouling layer formulation. The anti-fouling film is also 118452.doc 1357433, which can achieve the balance of physical properties of both anti-staining and ink marking. SUMMARY OF THE INVENTION The inventors of the present invention have addressed the shortcomings of the prior art, and have extensively studied (4) using acrylic acid as the main bond, and the side chain contains a gas-carbon segment and a gas-fired apron An acid comb-like graft copolymer that reduces the surface tension of the coating. When forming a film, the fluorocarbon segment or the siloxane segment of the side chain of the copolymer is arranged in a comb-like graft shape, which can remove the contaminants and achieve the anti-staining effect, and can allow the smaller ink molecules to enter the comb type. The grafting structure achieves a sagittal effect, so it can have both good antifouling properties and ink marking properties. Accordingly, it is a primary object of the present invention to provide an antifouling film comprising a substrate having at least one side coated with a coating composition as an antifouling layer, wherein the coating composition comprises a polyfluorofluorene acrylic acid system The comb-type graft copolymer 'the coating composition can provide a solid content of the anti-fouling layer of from 1 mg/m2 to 500 mg/m2, preferably from 75 mg/m2 to 45〇mg/m2. [Embodiment] The substrate used in the antifouling film of the present invention may be any one known to those skilled in the art to which the present invention pertains, such as glass or plastic. The above plastic substrate is not particularly limited, and is, for example but not limited to, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate ( P〇lyethylene naphthalate, PEN); p〇iyacrylate resin, such as polymethyl methacrylate (PMMA); polyimide resin; polycycloolefin resin Polycycloolefin resin), polycarbonate resin (p〇iyCarb〇nate 118452.doc 1357433 resin) 'p〇iyUrethane resin; triacetate cellulose (TAC); or a mixture thereof . Preferred is polyethylene terephthalate, polydecyl acrylate "polycycloolefin resin", cellulose diacetate or a mixture thereof, more preferably polyethylene terephthalate. The thickness of the substrate will generally depend on the desired product desired, preferably between about 16 microns (μm) and about 50 microns. The present invention employs a coating composition comprising a polyfluorofluorene-acrylic acid-based comb-like graft copolymer to be applied to a substrate to form an anti-staining layer. As shown in FIG. 2, the copolymer is mainly composed of an acrylic resin 6 〇, and the side chain contains a fluorocarbon segment and a siloxane segment 70, which can reduce the surface tension of the antifouling layer, and when forming a film, the side chain The fluorocarbon and xenon fired sections are arranged in a comb-like graft shape. Because of the comb-type graft structure, the macromolecular contamination 40 (micron order) can be excluded from the structure to achieve the antifouling effect, so that the smaller one is The ink molecule 5 〇 (nano grade) enters the comb-type graft structure to achieve the sacrificial effect, so it can have good antifouling properties and ink marking properties. The polyfluorofluorene-acrylic comb-like graft copolymer is polymerized from the following monomers: (1) an acrylic monomer; (2) a tertiary carboxylate monomer; (3) a fluorinated acrylic Monomer; and (4) siloxane monomer. The above acrylic monomer has the following formula: R1 CH2=C-COOR2 118452.doc -10- 1357433 wherein R1 is halogen, hydrazine, CH3 'C2H5; and R2 is Η, CH3, C2H5, C3H7, C4H9, C6Hu, C2H4〇H, C3H6OH or the following groups: Eight CH2—CH-CH2 ο Preferred acrylic monomers are acrylic acid, mercaptoacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, Butyl acrylate, 2-ethylidene acrylate, 2-ethylidene acrylate, 2-hydroxypropyl methacrylate or 2-hexyl hexyl acrylate or mixtures thereof. The amount of the acrylic monomer used is from 20 to 80% by weight based on the total monomer amount, preferably from 30 to 70% by weight. The present invention utilizes a tertiary carboxylic acid ester to further provide compatibility, so that a fluorine-containing coating film excellent in compatibility can be effectively solved for long-term coating film deterioration and stain resistance reduction. The tertiary acid retardate of the present invention for forming a polymer has the following formula: R3 RC-COOR6 R4 wherein R, R. and R each independently represent a linear or branched alkyl chain: CmH2m+ 1 'where the claws ^ to. An integer of R6 is selected from the group consisting of CH=CH2' CH~bH2, CH plant, H2C=0-CH2 and H2C=£^H2. The preferred tertiary (4) is selected from the group consisting of saturated tribasic acid B (four), full 118452.doc

A group consisting of 1357433 and a tertiary carboxylic acid vinyl ester and a saturated tertiary hydrazine carboxylate. The amount of the tertiary carboxylic acid ester is from 5 to 50% by weight, preferably from 5 to 30% by weight, based on the total amount of the monomers. The above fluorinated acrylic acid single system constitutes a fluorocarbon segment of a side bond segment of the copolymer, and has the following formula:

RfCH2CH20(0)CC(R)=CH2 wherein R/ is a linear or branched perfluorinated alkyl group: CnF2n+1, where n=an integer from 2 to 20, and R is Η, CH3, C2H5 or C3H7. Preferred fluorinated acrylic monomers are n=2 to 20 mercaptopropionic acid fully vaporized leuco vinegar or mixtures thereof, more preferably n-6 to 14 mercapto acrylate perfluoroalkane A base ester or a mixture thereof. According to the present invention, the fluorinated acrylic monomer is used in an amount of 1 to 2% by weight, preferably 2 to 5 % by weight based on the total amount of the monomers. The above-mentioned siloxane single crystal system constitutes the oxirane segment of the side chain of the copolymer, and has the following formula:

Me

Me O-Si-R8 I n Me

Me R—Si—I Me Ο-Si—wherein 'R7 and R8 are each independently H, CH3, CH2 = CH, NH2, NH2-C3H6, 0H-C2H40C3H6, CH=CCH3-C00H, CH=CH-COOH or Ci ^CHOtOCsHe, where n = 10 to 25 〇. According to the present invention, the amount of the siloxane monomer is from 1 to 20% by weight, based on the total amount of the monomers, preferably from 1 to 5% by weight. The copolymer of the present invention may be added with one or more vinyl monomers, such as phenethyl H8452.doc 1357433 dilute, ethylene acetophenone hexyl hexyl sulphate, 4 • oxybutyl b-butyl ether, n-butyl The amount of the vinyl monomer used in the base, the isobutyl ethane group (10), the n-propyl ethoxylate or the isopropyl vinyl ether or a mixture thereof is 5.40% by weight based on the total monomer amount. It is preferably 525 % by weight. The polyfluorohydrogenate in the coating composition of the present invention has an average molecular weight of about 10 coffee to 5 〇, and the content is 2 based on the total weight of the solid content of the coating composition. ^% by weight ' is preferably 3〇6〇% by weight.

The coating composition used in the present invention may optionally contain - or a plurality of additives known to those skilled in the art, such as, but not limited to, antistatic agents, crosslinking agents, levelers, dispersants or stabilizers. Wait. Preferably, the coating composition of the present invention further comprises an antistatic agent and/or a crosslinking agent.

During the processing or manufacturing of resin materials, static electricity is generated when the resin material rubs against itself or other materials, and the free dust in the air is collected on the surface. 'The expensive electronic components are destroyed' or even igniting flammable gases or The powder causes fire, so it is necessary to add an antistatic agent. The coating composition of the present invention may contain one or more antistatic agents as needed. In addition to providing antistatic function, the antistatic agent used in the present invention may also provide a fireproofing agent. The surface wettability of the nano-scale ink molecules is improved, so that it is easy to adsorb on the surface of the anti-staining layer, and the sacrificial effect of the ink is greatly improved. According to the present invention, preferred antistatic agents are, for example, polyols, quaternary amine compounds, Organic salt or a mixture thereof "When present, the antistatic agent content of the coating composition of the present invention is 2〇~75 weight 118452.doc 13 &lt;sx 1357433 compared to the total weight of the solid content of the coating composition Preferably, it is 30 to 50% by weight. The coating composition of the present invention may optionally contain one or more crosslinking agents, and the crosslinking agent used in the present invention is the present invention. It is well known in the art that a person skilled in the art can make a chemical bond between a molecule and a molecule to form a crosslinking. There is no particular limitation on the crosslinking agent which can be used in the coating composition of the present invention. Those skilled in the art are well known to those skilled in the art 'e.g., polyisocyanate, alkylated melamine-formaldehyde resin or mixtures thereof' are preferably polyisocyanates. When used in the present invention, the polyisocyanate may be blocked ( B1〇cked) or Unbl〇cked, the polyisocyanate usable in the present invention is an aliphatic polyisocyanate or an aromatic polyisocyanate or a mixture thereof. Non-limiting examples of aliphatic polyisocyanates include cyclohexane diisocyanate. a dimer of a dimer or an adduct thereof, a dimer of a mercapto hexane diisocyanate, a trimer or an adduct thereof, a dimer of % hexane bis <methyl isocyanate, a trimer or an adduct thereof or a dimer, a trimer or an adduct thereof of isophorone diisocyanate. Non-limiting examples of aromatic polyisocyanates include toluene dimer a dimer, a dimer or an adduct thereof, a dimer of dinonyl diisocyanate, a dimer or an adduct thereof, or a dimer or trimer of diphenylmethane diisocyanate or Adducts. The alkylated melamine·furfuryls of the present invention may be methylated, ethylated, propylated or butylated melamine formaldehyde, non-limiting examples of which include six Melamine, melamine tree, hexa-ethyl acetal, melamine resin, tetradecyl furfural, diamine melamine resin, tetramethylammonium hydride, melamine resin, melamine resin Base Formaldehyde>: <propyl valeraldehyde> melamine tree, &lt;S)·H8452.doc 1357433 or a mixture thereof. When present, the content of the cross-linking agent in the coating composition of the present invention is the total solid content of the coating composition. The weight of the coating is from 5 to 60% by weight, preferably from 10 to 20% by weight. The coating composition of the present invention can be prepared by any of the means well known to those skilled in the art. For example, the various monomers for preparing the polyfluorofluorene-acrylic comb-type graft copolymer of the present invention are first mixed with a suitable solvent, and the mixture is reacted at an appropriate temperature and reaction time. Then, other additives (such as an antistatic agent and a crosslinking agent) are added, and after the kneading process, the coating composition of the present invention is obtained. The preparation method of the antifouling film of the present invention is not particularly limited. For example, it can be produced by a coating method comprising the following steps: (I) a polyfluorofluorene-acrylic comb-like graft copolymer and an anti-electrode The composition of the coating obtained by blending the components may be added with other conventional additives as needed and diluted with a solvent to prepare a coating liquid; (II) coating the coating liquid on the base by a bar coating rod The surface of the material to form an anti-fouling layer; (III) feeding the coated substrate to a dryer, heating at a suitable temperature for a few minutes, evaporating the solvent' and performing a thermal curing polymerization. The solvent system described in the above step (I) is not particularly limited and may be, for example, a benzene, a cool or a ketone or a mixture thereof. Non-limiting examples of benzene-based solvents include benzene, o-xylene, m-dioxene, p-nonylbenzene, tridecyl styrene or styrene or mixtures thereof. Non-limiting examples of ester solvents include, for example, B 118452 .doc •15· 1357433 Butyl Acetate, Carbon Brewing _ Feeding—Ethylene Bracelet, Review KA r »匕基乙,~_. Ethyl citrate, acetic acid acetoxy ethoxylate, ethoxyacetate: Ethyl formate, methyl acetate, a mixture thereof. Non-limiting or early methyl propylene glycol or hexyl isobutyl ketone or its present compound. Examples include propylene steel, methyl ethyl. Between anti-fouling and anti-fouling meters, it is preferably 〇.〇75 μm. It should be between Q.01 μm to 〇·5 μ.\± , A * s^ t , · 45 μm, and has good Antistatic

« 109 to 10 ΙοΩ / mouth. To 10 (mouth/square), preferably side, advance, application of mobile phone, "the exemplified by the adhesive layer is well known, the two liquids one of the invention anti-(four) material is required to be relative to the anti-fouling layer Another 乂 ^ 3 # layer. The anti-fouling film of the invention can be used as a protective film on the surface of any suitable material, such as a glass of a building or a car, a computer case or a display screen, etc., and is particularly suitable for liquid crystal display elements such as the 'anti-fouling film of the present invention can be adhered| The layer is attached to at least one surface of the liquid crystal display polarizing plate (sheet) to protect the contact member, or to be attached to the surface of other materials by a layer. The adhesives which can be used to form the above-mentioned adhesives are of ordinary skill in the art to which the present invention pertains, but are not limited to two-component adhesives such as acrylic and isocyanate type adhesives. The antifouling film of the invention has an antistatic agent added to the anti-staining layer and comprises a copolymer of a comb-like graft shape. Therefore, when used in a liquid crystal display, it has good stain resistance and ink marking property, in addition to It has chemical resistance and antistatic properties. Further, when the antifouling film of the present invention is attached to other optical films (for example, a polarizing plate for a liquid crystal display), the surface is flat without warping, and therefore, the optical properties thereof are prevented from being affected.

118452.doc 16· C.S 1357433 The following examples are intended to be illustrative of the invention and are not intended to limit the scope of the invention. Modifications and variations that may be readily made by those skilled in the art are included within the scope of the disclosure of the present disclosure and the scope of the appended claims. EXAMPLES [Example 1] 1 part by weight of a polyfluorofluorene-acrylic comb-type graft copolymer [E-4263 'Eternal Company} (about 55% solid content) was obtained, and the main chain portion of the copolymer was Acrylic polymer, the branched portion is composed of 2% fluorinated acrylic monomer and 3/ί; oxa sulphur monomer. The molecular weight is 20000~30000, and 0.3 parts by weight of isocyanate crosslinker is added [Desmodur 339〇, Bayer Company (solids about 75〇/〇), followed by 3 parts by weight of quaternary fine salt antistatic agent [GMB-36M-AS, Marubishi oil Chem. Co

Ltd] (solid content about 2 〇〇 / 0) to form a coating composition, and finally diluted with a solvent such as propylene glycol, ethyl acetate or toluene to obtain a solid content of about 2.5 ° /. A coating with a viscosity of less than 10 cps. After standing and defoaming, the prepared coating was coated on a polyethylene terephthalate film (T100G-38 'Mitsubishi Chem. Co.) by a bar coating rod (thickness: 38 μm) ) — The wet film thickness of the side surface was about 5 μm, and after drying at 120 ° C for 2 minutes, the solvent was evaporated to obtain an anti-fouling layer having a solid content of about 120 mg/m 2 . On the other side of the above PET film, a polyacrylic acid-based adhesive [E7713 'Eternal Co., Ltd.] was applied by a bar coating bar, and the wet film thickness was about 90 μm and was 12 Å. (: The solvent was evaporated by drying for 2 minutes to obtain a pressure-sensitive adhesive layer having a solid content of about 23 g/m 2 .

U8452.doc &lt;S-I 1357433 film' total film thickness is about 60 μηη, and a 25 μm or 38 μηη release film can be attached to the surface of the pressure-sensitive adhesive layer to protect the pressure resistance. Click on the layer. The characteristic test described below was carried out using this antifouling film. [Example 2] An antifouling film was prepared using the coating composition and method of Example 1, except that the solid content of the antifouling layer was changed to 75 mg/m2. [Example 3] An antifouling film was prepared using the coating composition and method of Example 1, except that the solid content of the antifouling layer was changed to 15 mg/m2. [Example 4] An antifouling film was prepared using the coating composition and method of Example 1, but the solid content of the antifouling layer was changed to 450 mg/m2. [Example 5] A stain-resistant film was prepared using the coating composition and method of Example 1, except that the proportion of the fluorinated acrylic monomer in the comb-shaped graft copolymer was changed to 15%. [Example 6] A stain-resistant film was prepared using the coating composition and method of Example 1, except that the proportion of the siloxane monomer in the comb-shaped graft copolymer was changed to 15%. [Comparative Example 1] An antifouling film was prepared using the coating composition and method of Example 1, except that the solid content of the antifouling layer was changed to 5 mg/m2. [Comparative Example 2] An antifouling film was prepared using the coating composition and method of Example 1, except that the solid content of the antifouling layer was changed to 550 mg/m2. 118452.doc 1357433 [Comparative Example 3] A stain-resistant film was prepared using the coating composition and method of Example 1, except that the proportion of the fluorinated acrylic monomer of the comb-shaped graft copolymer was changed to 25%. [Comparative Example 4] A stain-resistant film was prepared using the coating composition and method of Example 1, except that the proportion of the siloxane monomer of the comb-shaped graft copolymer was changed to 25 Å/〇. [Comparative Example 5]

The antifouling film was prepared using the coating composition and method of Example 1, but no antistatic agent was added. [Comparative Example 6] The antifouling film was prepared using the coating composition and method of Example 1, but the comb-shaped graft copolymer (Changxing Chemical Co., Ltd.) was changed to an acrylic resin as a main chain, and the side chain contained Shi Xi Oxygen-fired section but does not contain the gas-carbon segment of the polyoxo- 1 propylene polymer [E-42 1 3, Eternal Company]. Detection method

The recording surface impedance test uses an impedance measuring instrument [MCP_HT45〇, Mitsubishi Chemical Corporation], and measures the impedance value (Ω/α) of the surface of the sample to be tested after charging for 30 seconds with the volt volt voltage. The test results are shown in Table 1 below. . Haze and total light penetration measurement test using turbidity meter [NDH_2000, Japan Electro-Color Industry according to still 7361 standard method] measuring the total light penetration of the sample to be tested: Kang standard method to measure the sample to be tested Fog: As shown in the following list 1.侍,,,口果118452.doc CS》. -19· 1357433 Dynamic contact angle (DCA) test using dynamic contact angle measuring instrument [Gl0, KRUSS company], the sample to be tested is placed on the measuring platform, without tilt In the case of the curve, water is dripped on the surface, and then the lens is displayed on the computer and the contact angle value is calculated. The test results are shown in Table 1 below. Solvent resistance test, soil J J π scatter waste cloth

After soaking the roll with a specific solvent, rub it back and forth 1 () times on the surface of the sample to be tested at (4) 0 peach I. Observing the surface with almost no change is ο, and if there is a white mist, the result of the test is as shown in the following list. Ink marking test using oily singular pen, after a number of traces on the surface of the surface, using Nitto's two gongs ^ ° after sticking 'instant tear tape, observe the degree of surface ink removal, if the ink is still Remaining in its table'

Using the friction tester [TABER5750 X, the test results are shown below. ",," the removed person used the tensile machine for the adhesion evaluation test [AR1000 'All-China sample attached to the steel plate' test environment is as follows:,: use, 60%, let stand for at least half an hour, according to JIS2n C ' relative The rate of sufficiency is 3 〇 (Wmin, the standard method of measurement is performed, and the drawing is shown. The results are as follows) 118452.doc -20- 1357433 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Surface impedance (0/□) 1.38χ109 3.46x109 2.57χ109 3.15X109 4.24x109 3.46x109 DCA(°) 93.1 91.7 89.2 94.6 94.5 94.2 Penetration (%) 91.25 91.88 92.01 91.87 92.13 92.46 Haze (%) 4.12 4.30 4.07 3.95 4.06 4.19 Solvent Resistance (EtOH) 〇〇〇〇〇〇 Solvent Resistance (EA) 〇〇〇〇〇〇 Ink Marking 〇〇〇〇〇〇 Pressure Sensitive Adhesive Layer Adhesion (g/25mm ) 9.65 9.70 9.72 9.61 9.66 9.68

Table 1 (continued) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Surface Impedance (Ω/d) 2.69x109 3.21x10'° 2.57x109 3.15X109 &gt; 1013 3.46X109 DCA(°) 83.1 98.0 97.2 96.6 93.9 94.2 Penetration (%) 92.11 92.13 92.77 92.51 92.11 91.88 Haze (%) 3.72 4.11 4.22 3.99 3.72 4.30 Solvent (EtOH) X 溶剂Solvent Solvent (EA) X 〇〇〇 〇〇Ink Marking 〇XXXXX Pressure-sensitive adhesive layer adhesion (g/25mm) 9.73 9.66 9.65 9.72 9.69 9.64 From the results of Examples 1 to 6, it is known that the antifouling film of the present invention contains polyfluorinated due to the anti-fouling layer. A phthalic acid acrylic comb-like copolymer and an antistatic agent having good optical properties, antistatic properties, solvent resistance, and ink marking properties. In Comparative Example 1, the solid content of the antifouling layer was less than 10 mg/m2, and the resistance was poor. The chemical solvent resistance was poor, and the dynamic contact angle value was low, indicating that the antifouling ability was insufficient. Comparative Example 2 'The solids coating amount of the anti-staining layer exceeds 5 〇〇mg/m2, and the stain resistance and the chemical solvent property are excellent, but the ink marking property is too strong, so the ink marking property is poor; Since the thickness of the anti-fouling layer is too thick to hinder the antistatic function, the antistatic property is also poor. In Comparative Example 3 and Comparative Example 4, the proportion of the fluorinated acrylic monomer in the copolymer or the proportion of the siloxane monomer was too high, the surface energy was largely lowered, and the stain resistance was improved, but the ink marking property was poor. In Comparative Example 5, the antistatic agent was not added, and the formed antifouling layer was inferior in ink marking property except that the resistance portion exceeded the measurement range. Comparative Example 1 and Comparative Example 6, Example 1 used a polyfluorofluorene alkene-based comb-type graft copolymer, and Comparative Example 6 used a polyoxypropylene-acrylic acid-based polymer. The results obtained by observing the antifouling films obtained in Example 1 and Comparative Example 6 by atomic force were as shown in Figs. 3 and 4, respectively. As can be seen from FIG. 4, the surface of the anti-deficient film of Comparative Example 6 has a micro-scaled or block-like structure, and although the anti-fouling ability can achieve the desired effect, the nano-sized ink molecules cannot enter the comb-type structure. The labeling property is not good; as can be seen from Fig. 3, the protruding or block structure of the surface of the antifouling film of the embodiment is nanometer, which allows the ink molecules to enter the comb structure, so that not only has good stain resistance but also good ink. Marked. The above results confirmed that the antifouling film according to the present invention is excellent in antistatic property, excellent in antifouling ability, and can simultaneously satisfy ink marking property and chemical resistance. [Simple description of the diagram] 118452.doc •22- UD/433 Figure 1 is a simplified schematic diagram of the structure of the polarizing plate. Fig. 2 is a schematic illustration of a polyfluorinated acrylic comb type copolymer. Fig. 3 is an atomic force micrograph of an antifouling film containing a polyfluorofluorene-acrylic comb-like graft copolymer. Fig. 4 is an atomic force microscopic mirror image of an antifouling film containing a polyoxo acrylate polymer.

[Main component symbol description] 100 Polarizing plate 10 Polarizing layer 11 Polarizing substrate 12 Protective body 13 Pressure-sensitive adhesive layer 20 Protective film 21 Pressure-sensitive adhesive layer

22 Substrate 23 Antifouling layer .3 0 Panel 40 Contaminants 50 Ink molecules 60 Acrylic resin backbone 70 Side chains containing fluorocarbon or decane segments 118452.doc •23·

Claims (1)

1357433 at the time of the announcement and April of the year) Patent Application No. 096111954, the scope of the patent application is replaced by the scope of the patent application: 1. An anti-fouling film comprising: a substrate having at least one side coated with a coating composition as an anti-fouling layer, wherein The coating composition comprises a polyfluorinated amphetamine-based comb-like graft copolymer, which is polymerized from the following monomers: (1) an acrylic monomer; (2) a tertiary carboxylic acid ester single (3) fluorinated acrylic monomer; and (4) siloxane monomer; wherein the amount of acrylic monomer is 2 〇 to 80 weight 1 based on the total monomer amount; tertiary carboxylic acid ester The amount of the monomer is 5 to 50% by weight based on the total monomer amount; and the amount of the fluorinated acrylic monomer is 1 to 20 by weight based on the total monomer. /. The amount of the cerium oxide monomer is from 1 to 20% by weight based on the total monomer: and the coating composition provides a solid content of the antifouling layer of from 10 mg/m2 to 500 mg/m2. 2. The antifouling film according to claim 1, wherein the copolymer is mainly composed of an acrylic resin and the side chain contains a fluorocarbon segment and a decane segment. 3. The antifouling film of claim 1, wherein the coating composition further comprises an antistatic agent, wherein the antistatic agent is present in an amount of from 20 to 75% by weight based on the total weight of the solids of the coating composition. 4. The antifouling film of claim 3, wherein the antistatic agent comprises a polyol, a quaternary amine compound, an organic salt or a mixture thereof. 5. The antifouling film of claim 1, wherein the coating composition further comprises 118452-1000427.doc 1357433 crosslinking agent, wherein the crosslinking agent content is 5 to 60 based on the total weight of the solids of the coating composition. weight%. 6. The antifouling film of claim 5 wherein the crosslinking agent is selected from the group consisting of one or more polyisocyanuric acid, alkylated melamine-formaldehyde resins, and mixtures thereof. 7. The antifouling film according to claim 1, wherein the substrate is selected from the group consisting of polyester resin, polyacrylate resin, polyimine resin, polycycloolefin resin, polycarbonate resin, polyamine hydrazine A group consisting of an acid ester resin, cellulose triacetate, and a mixture thereof. 8. The antifouling film of claim 1 further comprising an adhesive layer on the substrate opposite the anti-staining layer. 9. The antifouling film of claim 8, wherein the adhesive layer is a two-component adhesive composed of acrylic and isocyanate. An anti-fouling film of claim 8, which is attached to at least one surface of the liquid crystal display element via the adhesive layer. The antifouling film of claim 8, wherein the liquid crystal display element is a liquid crystal display polarizer. 12. The antifouling film according to claim 8, wherein the antifouling film is used as a protective film for a liquid crystal display. The antifouling film comprises a polyester resin substrate, and the substrate is coated with a coating composition as an antifouling layer, and the surface resistivity of the antifouling layer is 10 to 10] 2 Ω/□, The coating composition comprises a polyfluorofluorene-acrylic comb-like graft copolymer and an antistatic agent, which is polymerized from the following monomers: ^8452-1000427 d〇c 1357433 (1) Acrylic sheet (2) a tertiary carboxylic acid ester monomer; (3) a fluorinated acrylic monomer; and (4) a siloxane monomer; wherein the amount of the acrylic monomer is based on the total monomer amount 20 to 8 重量% by weight; the amount of the tertiary carboxylic acid ester monomer, based on the total monomer amount, is 5 to 50% by weight; the amount of the fluorinated acrylic monomer, based on the total monomer amount To 20% by weight; the amount of the siloxane monomer is 1 to 20% by weight based on the total monomer; the antistatic agent is 20 to 75% by weight based on the total weight of the solids of the coating composition. And the coating composition provides a solid content of the anti-fouling layer of from 1 mg/m2 to 500 mg/m2. 14. The antifouling film of claim 13, wherein the antistatic agent comprises a polyol, a quaternary amine compound, an organic salt, and mixtures thereof. 15. The antifouling film of claim 3, wherein the copolymer is present in an amount of 2 〇 7 〇 0 〇 based on the total weight of the solids of the coating composition. 16. The antifouling film of claim 13, wherein the coating composition further comprises a crosslinking agent, wherein the crosslinking agent is present in an amount of from 5 to 60% by weight based on the total weight of the solids of the coating composition. 17. The antifouling film of claim 16, wherein the crosslinking agent is selected from the group consisting of one or more guanidinium isocyanates, alkylated melamine-formaldehyde resins, and mixtures thereof. 118452-1000427.doc 1357433 Patent Application No. 096111954 • .,· Chinese Graphic Replacement Page (July, 1996) Preparation for July γ曰:. 118452-960704.doc