JP6171343B2 - Release film - Google Patents

Description

  The present invention relates to a release film having a very low amount of polyester oligomer precipitation and a low surface resistivity, and is suitable for applications that protect various adhesives and dislike oligomer precipitation and foreign matter inclusion. For example, for manufacturing capacitive touch panels, etc., for various applications to be bonded via an adhesive layer, for manufacturing LCD components such as polarizing plates and retardation plates used in liquid crystal displays (hereinafter abbreviated as LCD) In addition to manufacturing various display components such as plasma display panel (hereinafter abbreviated as PDP) component manufacturing, organic electroluminescence (hereinafter abbreviated as organic EL) component manufacturing, various adhesive layer protection applications It is related with the release film suitable for.

  Conventionally, a release film based on a polyester film is used for manufacturing a capacitive touch panel, etc., for various purposes to be bonded via an adhesive layer, LCD polarizing plate, retardation plate manufacturing, PDP component It is used for various optical applications such as for manufacturing, for manufacturing organic EL components, for manufacturing various display components. As problems in using the release film, after application of the pressure-sensitive adhesive layer, deterioration of the inspection property of the polarizing plate for LCD due to oligomer precipitation and decrease in visibility of the pressure-sensitive adhesive layer are problems. Another problem is that foreign matter is transferred to the pressure-sensitive adhesive layer due to the inclusion of foreign matter due to charging of the release film.

  In recent years, with the advancement of IT (Information Technology) field, the quality of the release film used when manufacturing display members such as LCD, PDP, organic EL, etc., as well as the protection of the adhesive layer, the polyester oligomer from the release film Various problems associated with deposition and charging are becoming apparent.

  In particular, there is an increasing demand for quality in the application of pressure-sensitive adhesive sheets for surface bonding between objects. Various pressure-sensitive adhesive sheets are known, and a substrate-less double-sided pressure-sensitive adhesive sheet is known as one of the pressure-sensitive adhesive sheets. The substrate-less double-sided PSA sheet consists of a laminate structure in which a light release film with a relatively low peel strength and a heavy release film with a relatively high peel strength are laminated on both sides of the adhesive layer. After the removal, the double-sided pressure-sensitive adhesive sheet becomes only the pressure-sensitive adhesive layer having no supporting substrate.

  As a method of using the substrate-less double-sided pressure-sensitive adhesive sheet, first, the light release film is peeled off, and one surface of the exposed pressure-sensitive adhesive layer is adhered to the object surface of the other side to be bonded, and after the adhesion, the heavy release film is further peeled off, A processing step in which the other surface of the exposed pressure-sensitive adhesive layer is bonded to a different object surface, whereby the objects are surface-bonded is exemplified.

  In recent years, the substrate-less double-sided pressure-sensitive adhesive sheet has attracted attention because of its good workability, and its applications are expanding. It is also used for members for various optical applications such as mobile phones. In particular, a capacitive touch panel is rapidly expanding its application as an information terminal by a multi-touch operation in which a screen operation is performed with two fingers. Since the capacitive touch panel tends to have a thicker printing step than the resistive film method, a proposal has been made to eliminate the printing step by thickening the adhesive layer. When the pressure-sensitive adhesive layer is made thick, when the release film is peeled off, a part of the pressure-sensitive adhesive layer adheres to the release film, or bubbles are mixed into the part of the pressure-sensitive adhesive layer transferred to the release film. There is a case. Therefore, when using a substrateless double-sided pressure-sensitive adhesive sheet for optical applications, not only the substrateless double-sided pressure-sensitive adhesive sheet but also the release film to be combined is more stringent than before, and a release film with higher quality is required. The situation is needed.

  On the other hand, when using a release film, peeling electrification may occur when it is peeled off from the pressure-sensitive adhesive layer, and as a result, defects such as product defects due to adhesion or entrapment of foreign substances etc. occur at the processing site. There was a case. Therefore, it is not always sufficient to take antistatic measures by handling facilities in the manufacturing process, and there is a strong demand for antistatic treatment from the release film itself.

  As described above, when using a substrate-less double-sided PSA sheet in a release film, not only the substrate-less double-sided PSA sheet, but also the release film to be combined requires a more stringent quality than before. It is in.

  Conventionally, a method in which a coating film and a release layer are sequentially provided and a polythiophene conductive resin is contained in the coating layer is known (Patent Document 3). However, in the said method, since there is no oligomer sealing performance, an oligomer will precipitate.

  Conventionally, a method is known in which a release film is provided with a release layer, and the release layer contains a polythiophene conductive resin and an addition-type silicone resin (Patent Document 2). However, the above-described method has a problem in that since the curing is performed in the state of coexisting with polythiophene that inhibits the curing of the addition type silicone resin, the curing is insufficient and the adhesion of the coating film deteriorates with time.

JP 2008-156452 A Special table 2009-533256 direction JP 2011-201118 A JP 2011-189589 A JP 2011-245739 A JP 2011-224896 A JP 2011-224904 A JP2012-25030A JP 2012-184327 A JP 2012-207166 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is that the amount of oligomer precipitation of polyester is extremely low, the surface specific resistance is low, and for the protection of various adhesives, oligomer precipitation and foreign matter entrainment Suitable for applications to be disliked, for example, for the production of capacitive touch panels, etc. Various applications to be bonded via an adhesive layer, polarizing plates and retardation plates used for liquid crystal displays (hereinafter abbreviated as LCD) In addition to manufacturing various display components such as LCD component manufacturing, etc., plasma display panel (hereinafter abbreviated as PDP) component manufacturing, organic electroluminescence (hereinafter abbreviated as organic EL) component manufacturing, etc. Another object of the present invention is to provide a release film suitable for protecting various adhesive layers.

  As a result of intensive investigations in view of the above-mentioned actual situation, the present inventor has found that the above-mentioned problems can be easily solved by a release film having a specific configuration, and has completed the present invention.

That is, the gist of the present invention is a release film in which a coating layer and a release layer are sequentially provided on one side of a polyester film stretched at least in a uniaxial direction, and the coating layer contains an organic compound containing a metal element. The organic compound containing at least one kind and an organosilicon compound and containing the metal element is 5 to 15 wt% titanium compound, 5 to 15 wt% aluminum compound and / or zirconium compound, and the release layer Contains a π-conjugated conductive polymer resin and a silicone resin, the release layer has a surface resistivity (R) of 1 × 10 ¹² Ω or less, and the film is heated at 180 ° C. for 10 minutes. The amount of polyester oligomer on the surface of the mold layer is 1.0 mg / m ² or less.

  According to the release film of the present invention, it is possible to provide a release film having a polyester oligomer precipitation amount as low as possible and having a low surface resistivity, for example, for producing a capacitive touch panel. For various optical applications, such as various types of bonding, LCD polarizing plate, retardation plate manufacturing, PDP component manufacturing, organic EL component manufacturing, display component manufacturing, etc. A type film is provided, and its industrial value is high.

  The polyester film constituting the release film in the present invention may have a single-layer structure or a laminated structure. For example, the polyester film may have a four-layer or a three-layer structure as long as the gist of the present invention is not exceeded other than the two-layer or three-layer structure. It may be a multilayer having more than that, and is not particularly limited.

  The polyester used for the polyester film in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Representative polyester includes polyethylene terephthalate (PET) and the like. On the other hand, examples of the dicarboxylic acid component of the copolyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and oxycarboxylic acid (eg, P-oxybenzoic acid). 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1, 4- cyclohexane dimethanol, neopentyl glycol, is mentioned. In any case, the polyester referred to in the present invention refers to a polyester that is usually 60 mol% or more, preferably 80 mol% or more of polyethylene terephthalate or the like which is an ethylene terephthalate unit.

  In the present invention, it is preferable to blend particles in the polyester layer mainly for the purpose of imparting slipperiness. The kind of the particle to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness. Specific examples thereof include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and phosphoric acid. Examples of the particles include magnesium, kaolin, aluminum oxide, and titanium oxide. Further, the heat-resistant organic particles described in JP-B-59-5216, JP-A-59-217755 and the like may be used. Examples of other heat-resistant organic particles include thermosetting urea resins, thermosetting phenol resins, thermosetting epoxy resins, benzoguanamine resins, and the like. Furthermore, precipitated particles obtained by precipitating and finely dispersing a part of a metal compound such as a catalyst during the polyester production process can also be used.

  On the other hand, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction | limiting in particular also about the hardness, specific gravity, a color, etc. These series of particles may be used in combination of two or more as required.

  Moreover, the average particle diameter of the particle | grains to be used is 0.01-3 micrometers normally, Preferably it is the range of 0.01-1 micrometer. When the average particle diameter is less than 0.01 μm, the particles are likely to aggregate and dispersibility may be insufficient. On the other hand, when the average particle diameter exceeds 3 μm, the surface roughness of the film becomes too rough and There may be a problem when a release layer is applied in the process.

  Furthermore, the particle content in the polyester layer is usually in the range of 0.001 to 5% by weight, preferably 0.005 to 3% by weight. When the particle content is less than 0.001% by weight, the slipperiness of the film may be insufficient. On the other hand, when the content exceeds 5% by weight, the transparency of the film is insufficient. There is.

  The method for adding particles to the polyester layer is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester constituting each layer, but the polycondensation reaction may proceed preferably after the esterification stage or after the transesterification reaction.

  Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyester raw material, or a blending of dried particles and a polyester raw material using a kneading extruder. It is done by methods.

  In addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, and the like can be added to the polyester film in the present invention as necessary.

  Although the thickness of the polyester film which comprises the release film of this invention will not be specifically limited if it is a range which can be formed into a film, Usually, 5-250 micrometers, Preferably it is the range of 5-188 micrometers.

In the release film of the present invention, the amount of polyester oligomer on the film surface after heating at 180 ° C. for 10 minutes is 2.0 mg / m ² or less. The amount of oligomer after heating is determined by washing the surface of the release film at 180 ° C. for 10 minutes with 4 ml of DMF (dimethylformamide), and determining the amount of oligomer in the DMF by liquid chromatography. The value can be measured as the film surface oligomer amount (mg / m ² ) divided by the film area contacted with DMF.

  In addition, in order to reduce OL after a heating, the method of reducing the oligomer amount in polyester by solid-phase polymerization of polyester, the method of providing the coating layer which prevents precipitation of an oligomer, etc. are mentioned. In particular, in the present invention, it is effective to provide the coating layer with a function of preventing oligomer precipitation. Various methods can be used to prevent oligomer precipitation. For example, there is a method of containing an organic compound containing aluminum in the coating layer, but the method is not limited thereto.

  Next, although the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all.

  First, a method of using the polyester raw material described above and cooling and solidifying a molten sheet extruded from a die with a cooling roll to obtain an unstretched sheet is preferable. In this case, in order to improve the flatness of the sheet, it is necessary to improve the adhesion between the sheet and the rotary cooling drum, and an electrostatic application adhesion method and / or a liquid application adhesion method are preferably employed. Next, the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Subsequently, the extending | stretching temperature orthogonal to the 1st step | paragraph extending | stretching direction is 70-170 degreeC normally, and a draw ratio is 3.0-7 times normally, Preferably it is 3.5-6 times. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film. In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.

  The simultaneous biaxial stretching method can also be adopted for the production of the polyester film in the present invention. The simultaneous biaxial stretching method is a method in which the unstretched sheet is usually stretched and oriented in the machine direction and the width direction at 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is as follows: The area magnification is 4 to 50 times, preferably 7 to 35 times, and more preferably 10 to 25 times. Subsequently, heat treatment is performed at a temperature of 170 to 250 ° C. under tension or under relaxation within 30% to obtain a stretched oriented film. With respect to the simultaneous biaxial stretching apparatus that employs the above-described stretching method, conventionally known stretching methods such as a screw method, a pantograph method, and a linear drive method can be employed.

  Furthermore, a so-called coating stretching method (in-line coating) in which the film surface is treated during the above-described polyester film stretching step can be applied. When a coating layer is provided on a polyester film by a coating stretching method, coating can be performed simultaneously with stretching and the thickness of the coating layer can be reduced according to the stretching ratio, producing a film suitable as a polyester film. it can.

  Next, formation of the coating layer which comprises the release film in this invention is demonstrated. Regarding the coating layer, the above-described coating stretching method (in-line coating) may be used, so-called off-line coating that is applied outside the system on a once produced film may be employed, and any method may be employed. .

  Next, formation of the coating layer in the present invention will be described. The coating layer constituting the release film of the present invention contains an organosilicon compound in order to improve the oligomer precipitation preventing property and to improve the coating film adhesion between the release layer and the polyester film over time. It is preferable to use an organosilicon compound represented by the following general formula (1).

Si (X) _d (Y) _e (R ¹ ) _f (1)
[In the above formula, X is an organic group having at least one selected from an epoxy group, a mercapto group, a (meth) acryloyl group, an alkenyl group, a haloalkyl group and an amino group, R ¹ is a monovalent hydrocarbon group, and 1 to 10 carbon atoms, Y is a hydrolyzable group, d is an integer of 1 or 2, e is an integer of 2 or 3, f is an integer of 0 or 1, and d + e + f = 4 ]

  The organosilicon compound represented by the general formula (1) has two hydrolyzable groups Y (D unit source) or three (T unit) capable of forming a siloxane bond by hydrolysis / condensation reaction. Source) can be used.

In the general formula (1), the monovalent hydrocarbon group R ¹ has ¹ to 10 carbon atoms, and a methyl group, an ethyl group, or a propyl group is particularly preferable.

  In the general formula (1), as the hydrolyzable group Y, conventionally known ones can be used, and the following can be exemplified. Methoxy group, ethoxy group, butoxy group, isopropenoxy group, acetoxy group, butanoxime group, amino group and the like. These hydrolyzable groups may be used alone or in combination. The application of a methoxy group or an ethoxy group is particularly preferable because it can impart good storage stability to the coating material and has suitable hydrolyzability.

  In the present invention, specific examples of the organosilicon compound contained in the coating layer include vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 5-hexenyltri Methoxysilane, p-styryltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, 2- (3,4-epoxycyclohexyl) ethyl It can be exemplified trimethoxy silane.

  In the present invention, a metal element selected from aluminum, titanium and zirconium is used to improve the oligomer precipitation preventing property of the release film and to improve the adhesion of the release layer and the polyester film over time. It is an essential requirement that at least one kind of organic compound containing is contained in the coating layer.

  Specific examples of the organic compound having an aluminum element include aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum di- Illustrative examples include iso-propoxide-monomethyl acetoacetate and aluminum tris (ethyl acetoacetate).

  The amount of the aluminum compound contained in the coating layer is usually 0.001 to 70% by weight, preferably 5 to 35% by weight, and more preferably 5 to 15% by weight. When the amount of the aluminum compound is 0.001% by weight or less, the curing reaction of the coating layer does not proceed rapidly, and the coating film adhesion on the release surface after forming the release layer on the coating layer is deteriorated. Sometimes. Further, when the amount of the aluminum compound is 70% by weight or more, the aluminum compound remaining in the coating layer does not participate in the curing reaction of the coating layer and prevents the release layer from being cured, and the coating film adheres to the release surface. Sexuality may worsen.

  Specific examples of the organic compound having a titanium element include, for example, titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, Examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethylacetoacetate.

  The amount of the titanium compound contained in the coating layer is usually 0.001 to 70% by weight, preferably 5 to 30% by weight, and more preferably 5 to 15% by weight. When the amount of the titanium compound is 0.001% by weight or less, the curing reaction of the coating layer does not proceed rapidly, and the coating film adhesion on the release surface after forming the release layer on the coating layer is deteriorated. Sometimes. Further, when the amount of the titanium compound is 70% by weight or more, the titanium compound remaining in the coating layer does not participate in the curing reaction of the coating layer and prevents the release layer from being cured, and the coating film adheres to the release surface. Sexuality may worsen.

  Specific examples of the organic compound having a zirconium element include, for example, zirconium acetate, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and the like.

  The amount of the zirconium compound contained in the coating layer is usually 0.001 to 70% by weight, preferably 5 to 30% by weight, and more preferably 5 to 15% by weight. When the amount of the zirconium compound is 0.001% by weight or less, the curing reaction of the coating layer does not proceed rapidly, and the coating film adhesion of the release surface after forming the release layer on the coating layer is deteriorated. Sometimes. Further, when the amount of the zirconium compound is 70% by weight or more, the zirconium compound remaining in the coating layer does not participate in the curing reaction of the coating layer and prevents the release layer from being cured, and the coating surface adheres to the release surface. Sexuality may worsen.

  Among them, an organic compound having a chelate structure is preferable with respect to an organic compound containing a metal element selected from aluminum and zirconium, particularly in that the ability to prevent oligomer precipitation is good. It is also described in detail in the “Crosslinking agent handbook” (Yamashita Shinzo, Kaneko East Assistant Editor, Taiseisha 1990 edition).

  It is preferable that at least one organic compound containing a metal element selected from aluminum, titanium, and zirconium is contained in the coating layer from the viewpoint of good oligomer precipitation preventing performance.

  Further, inorganic particles may be contained for the purpose of improving the adhesion and slipperiness of the coating layer, and specific examples include silica, alumina, kaolin, calcium carbonate, titanium oxide, barium salt and the like.

  Moreover, an antifoamer, a coating property improving agent, a thickener, an organic lubricant, organic polymer particles, an antioxidant, a UV absorber foaming agent, a dye, and the like may be contained as necessary.

  In the range not exceeding the gist of the present invention, only one type of organic solvent may be used for the purpose of improving dispersibility, improving film forming property, etc., and two or more types may be used as appropriate.

The coating amount of the coating layer provided on the polyester film constituting the release film of the present invention (after drying) typically, 0.005~1g / ^{m 2,} the range preferably from 0.005 to 0.5 / ^{m 2} It is. When the coating amount (after drying) is less than 0.005 g / m ² , the uniformity of coating thickness may be insufficient, and the amount of oligomer deposited from the coating layer surface may increase after heat treatment. . On the other hand, when the coating is applied in excess of 1 g / m ² , problems such as a decrease in slipperiness may occur.

  In the present invention, as a method for providing the coating layer, a conventionally known coating method such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating or the like can be used. As for the coating method, there is a description example in “Coating method” published by Yoji Harasaki in 1979.

  In the present invention, the curing conditions for forming the coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, usually at 60 to 200 ° C. for 3 to 40 seconds. The heat treatment is preferably performed at 80 to 180 ° C. for 3 to 40 seconds as a guide. Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed.

Next, formation of the release layer in the present invention will be described.
The release layer constituting the release film in the present invention refers to a layer having releasability and antistatic performance. Specifically, the peeling force (F) between the acrylic adhesive tape and the release layer is It is preferably 5 to 500 mN / cm for the purpose of the present invention. The surface resistivity (R) of the release layer is preferably 1 × 10 ¹² or less, and more preferably 1 × 10 ⁹ or less from the viewpoint of foreign matter entrainment. The release layer constituting the release film in the present invention may be provided on the polyester film in the film production process such as the above-described coating stretching method (inline coating), and is applied outside the system on the once produced film. So-called off-line coating may be employed, and any method may be employed. The coating stretching method (in-line coating) is not limited to the following, but for example, in sequential biaxial stretching, the first stage of stretching may be completed and the coating treatment may be performed before the second stage of stretching. it can. When a release layer is provided on a polyester film by a coating and stretching method, the film can be applied simultaneously with stretching, and the thickness of the release layer can be reduced according to the stretching ratio. Can be manufactured.

  In addition, the release layer constituting the release film in the present invention must contain a silicone resin in order to improve the release property, and a curable silicone resin is preferable as the silicone resin. A type having a curable silicone resin as a main component may be used, or a silicone-modified resin by graft polymerization with an organic resin such as an acrylic resin, a urethane resin, an epoxy resin, or an alkyd resin may be used.

  As the type of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, and a solventless type can be used. Specific examples include KS-774, KS-775, KS-778, KS-779H, KS-847H, KS-856, X-62-2422, X-62-2461, X manufactured by Shin-Etsu Chemical Co., Ltd. -62-1387, KNS-3051, X-62-1496, KNS320A, KNS316, X-62-1574A / B, X-62-7052, X-62-7028A / B, X-62-7619, X-62 -7213, SRX357, SRX211, SD7220, LTC750A, LTC760A, SP7259, BY24-468C, SP7248S, BY24-458DKQ3-202, DKQ3-203, DKQ3-205, DKQ3-210, manufactured by Toray Dow Corning Co., Ltd. , Momentive Performance Materials YSR-3022, TPR-6700, TPR-6720, TPR-6721, TPR6500, TPR6501, UV9300, UV9425, XS56-A2775, XS56-A2982, UV9430, TPR6600, TPR6604, TPR6605, manufactured by Toray Dow Corning Co., Ltd. Illustrated. Further, a release control agent may be used in combination to adjust the release property of the release layer.

  Specific examples of the release control agent include KS3800 manufactured by Shin-Etsu Chemical Co., Ltd., SD7292, Toray Dow Corning, BY24-4980, and the like.

  Examples of the silicone-modified resin include silicone-modified urethane resin, silicone-modified polyester, silicone-modified polycarbonate, silicone-modified polyimide, and silicone-modified acrylic resin.

  The silicone-modified urethane resin uses a silicone-modified polyol obtained by reacting a polysiloxane and a polyol and / or a silicone-modified isocyanate obtained by reacting an organosilicon compound and an isocyanate as a raw material for the urethane resin. It was obtained. That is, the silicone-modified urethane resin is obtained by a combination of a silicone-modified polyol and an isocyanate, a polyol and a silicone-modified isocyanate, or a silicone-modified polyol and a silicone-modified isocyanate. The silicone-modified urethane resin can also be obtained by addition reaction of a urethane resin having an isocyanate at the terminal and a polysiloxane having a hydroxyl group.

  Here, examples of the polysiloxane used for the silicone modification include a modified silicone oil whose terminal or both ends are active hydrogen and whose main chain is polydimethylsiloxane.

  Polyols are aliphatic, alicyclic, and aliphatic aromatic polyhydric alcohols, specifically, ethylene glycol, diethylene glycol, propylene glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, etc. Is mentioned. In addition, hydrocarbon groups having an oxirane group with these polyhydric alcohols as initiators, that is, polymer (polyether) polyols modified with ethylene oxide, propylene oxide, etc., and oxirane groups with alkylamines and alkanolamines as initiators. Examples thereof include amyl polymer polyols modified with hydrocarbons, epoxy resins containing oxirane groups, and polymer polyols obtained by ring opening of epoxidized oil with water or alkanolamine. In addition, a lactone polyol obtained by ring-opening polymerization reaction of ε-caprolactone lactone using the above alcohol as an initiator, the above polyhydric alcohol and one or more polycarboxylic acids such as oxalic acid, succinic acid, Glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid or polyester polyols obtained by reacting with these acid anhydrides, known oils, castor Examples thereof include alkyd polyols synthesized by transesterification with polyhydric alcohol or esterification with polybasic acid using oil or various fatty acids. As the polyol, any type of polyol preferably has two or more hydroxyl groups in the molecule.

  Examples of the isocyanate include aliphatic, alicyclic and aliphatic aromatic polyisocyanates. Aliphatic polyisocyanates include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl. Examples include caproate (lysine isocyanate). Alicyclic polyisocyanates include 1,3- or 1,4-diisocyanate cyclohexane, 1,3- or 1,4-bis (isocyanate methyl) cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, isopropylidyl-bis (4-cyclohexyl isocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), norbornene diisocyanate and the like. Examples of the aliphatic aromatic group include xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-bis (isocyanatomethyl) diphenylmethane, and the like. In addition, examples of the isocyanate include an addition reaction compound of the diisocyanate and a polyol, a trimer compound having a diisocyanate and a buret or isocyanurate ring structure, and a multimeric compound.

  A solvent can be used when reacting a polyol and isocyanate. As the solvent, thinner, ethyl acetate or the like can be used. The polyol and the isocyanate are preferably reacted so that the NCO / OH ratio is 0.5 to 1.5. In addition, a catalyst, a pigment, and other additives are appropriately blended in one or both of the polyol and the isocyanate as necessary.

  Examples of the catalyst include organic metal compounds, and organic tin compounds and organic titanium compounds are particularly preferable. Examples of the organic tin compound and the organic titanium compound include dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, and tetraisopropyl titanate. Particularly preferred are dibutyltin dilaurate and dibutyltin diacetate.

  The silicone-modified polyester is obtained by bonding a polysiloxane and a polyester component to each other. The form of the silicone-modified resin may be any of a graft bond type or a block bond type. Examples of the graft bond type production method include a method of reacting a polysiloxane having a hydroxyl group added to a side chain with a polyester having an isocyanate group or a carboxyl group at the terminal. Moreover, as a manufacturing method of a block bond type, the method etc. which superpose | polymerize polyester and the polysiloxane which added the radical initiator to both ends are mentioned, for example.

  Examples of the polysiloxane include polydimethylsiloxane having an epoxy group, an amino group, or a hydroxyl group at the terminal or both terminals.

  Examples of the acid component constituting the polyester include terephthalic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, adipic acid, and sebacic acid. , Dodecanedicarboxylic acid, succinic acid, 5-sodium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, trimellitic acid, trimesic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, monopotassium trimellitic acid And polyvalent carboxylic acids. Examples of the hydroxy compound component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, p -Xylylene glycol, ethylene oxide adduct of bisphenol A, diethylene glycol, triethylene glycol, polyethylene oxide glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, dimethylolpropanoic acid Examples thereof include polyvalent hydroxy compounds such as potassium. The polyester may be a self-crosslinking type having a functional group in the molecule, or may be crosslinked using a curing agent such as a melamine resin or an epoxy resin.

  The silicone-modified polycarbonate is produced using polysiloxane, bisphenols and a carbonate-forming compound as raw materials.

  Examples of the polysiloxane include reactive polydimethylsiloxane containing a phenol group at one end or both ends.

  Examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, Examples include 1,1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) ether. These bisphenols may be used alone or in combination of two or more.

  Examples of the carbonate forming compound include bisaryl carbonates such as phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

  As a method for producing the silicone-modified polycarbonate, a phosgene method in which a bisphenol and phosgene are directly reacted, a transesterification method in which a bisphenol and a bisaryl carbonate are transesterified, and the like can be employed.

  In the phosgene method, polysiloxane and bisphenols are reacted with phosgene in the presence of an acid binder and a solvent. Examples of the acid binder include alkali metal hydroxides such as pyridine, sodium hydroxide, and potassium hydroxide. As the solvent, for example, methylene chloride, chloroform, chlorobenzene, xylene and the like are used. In addition, a catalyst such as a tertiary amine catalyst such as triethylamine is added to promote the condensation reaction. The reaction temperature is preferably 0 to 150 ° C, more preferably 5 to 40 ° C. The reaction time is appropriately selected depending on the reaction temperature, but it is preferably 5 minutes to 10 hours, more preferably 10 minutes to 2 hours. During the reaction, it is preferable to maintain the pH of the reaction system at 10 or more.

  In the transesterification method, polysiloxane and bisphenols and bisaryl carbonate are mixed and reacted under reduced pressure. The reaction temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. The degree of vacuum is preferably 1 mmHg or less in order to remove phenols produced by the transesterification reaction out of the system. The reaction time is appropriately selected depending on the reaction temperature, the degree of reduced pressure, etc., but is preferably about 1 to 6 hours. The reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon, and the reaction may be performed by adding an antioxidant or a branching agent.

  The silicone-modified polyimide resin is obtained by reacting polysiloxane with tetracarboxylic dianhydride to obtain a polyamic acid intermediate, and then dehydrating and ring-closing the intermediate.

  Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydrides such as biphenyltetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and the like. And cycloaliphatic tetracarboxylic dianhydrides such as cyclopentane tetracarboxylic dianhydride and cyclohexane tetracarboxylic dianhydride.

  Examples of the polysiloxane include polydimethylsiloxane containing an amino group at one end or both ends.

  As a method for synthesizing a polyamic acid intermediate by reacting polysiloxane and tetracarboxylic dianhydride, a solution polymerization method is usually desirable. Solvents used in the solution polymerization method include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidinone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Examples include sulfone, hexamethylphosphoramide, and butyl lactone. The reaction temperature for producing the polyamic acid intermediate is preferably in the range of -20 to 150 ° C, more preferably -5 to 100 ° C. Furthermore, in order to convert the polyamic acid intermediate to polyimide, a method of dehydrating and ring-closing by heating is employed. 140-400 degreeC is preferable and the heating temperature in that case has more preferable 150-250 degreeC. The reaction time in this dehydration ring closure is preferably from 30 seconds to 10 hours, more preferably from 5 minutes to 5 hours, although it depends on the reaction temperature.

  The silicone-modified acrylic resin is a modified acrylic resin having a polysiloxane portion and a polymer portion of an acrylic monomer. The form of the silicone-modified acrylic resin may be a block polymer or a graft polymer. The silicone-modified acrylic resin is obtained by copolymerization of siloxane, an acrylic monomer, and, if necessary, a vinyl monomer other than the acrylic monomer. Copolymerization can be performed, for example, by living polymerization or radical polymerization.

  Examples of siloxane include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxymethyldimethoxysilane, γ- (meth) acryloxymethyldi Examples thereof include ethoxysilane, one-end methacryl-modified polydimethylsiloxane, and both-end methacryl-modified polydimethylsiloxane.

  Examples of acrylic monomers include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl acryl. (Meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) ) Acrylate, lauryl (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxypolyethylene glycol # 1000 (meth) acrylate, methoxypolyethylene Ethylene glycol # 2000 (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxy Butylacrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, (meth) acrylamide, methyl (meth) acrylamide , Ethyl (meth) acrylamide, propyl (meth) acrylamide, isopropyl (meth) acrylamide, butyl (meth) acrylamide, diacetone (meth) acrylamide, etc. .

  Examples of vinyl monomers other than acrylic monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, and vinyl chloride. , Vinyl fluoride, vinylidene fluoride, allyl glycidyl ether, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, allylphenol glycidyl ether, 3-allyl-1 , 4-dihydroxymethylbenzene diglycidyl ether and the like.

  The silicone-modified acrylic resin can be produced by solution polymerization. Solvents used in this solution polymerization include alcohol solvents such as ethanol, isopropanol, butanol and isobutanol, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, Methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl diethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, octane, Examples include aliphatic hydrocarbons such as decane, petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. The reaction temperature for solution polymerization is preferably 50 to 150 ° C., and the reaction time is preferably 3 to 12 hours.

  In the polymerization, a polymerization initiator is usually used. As the polymerization initiator, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2 ′ -Water-soluble azo polymerization initiators such as azobis [2-methyl-N- (2-hydroxyethyl) propionamide], oil-soluble polymerization initiation of benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, azobisisobutylnitrile, etc. And polymer azo polymerization initiators such as a polydimethylsiloxane unit-containing polymer azo polymerization initiator and a polyethylene glycol unit-containing polymer azo polymerization initiator.

  In addition, the release layer constituting the release film in the present invention is required to contain a π-conjugated conductive polymer resin in the release layer in order to improve antistatic performance. . The π-conjugated conductive polymer is not particularly limited as long as the main chain is a conductive organic polymer having a π-conjugated system. For example, polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylene. , Polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of stability in air, polypyrroles, polythiophenes and polyanilines are preferred. From the viewpoint of silicone curing inhibition, polythiophenes are more preferable.

  Specific examples of the π-conjugated conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole) , Poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3 -Hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-methyl) -4-hexyloxypyrrole), poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexyl) Thiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) , Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutyl) Thiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3 -Ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3-methyl-4-methoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-methyl-4-ethoxy) Thiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline , Poly (2-methylaniline), poly (3-isobutyla) Phosphorus), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.

  Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity can be obtained. However, in order to further increase the conductivity, an alkyl group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, etc. It is preferable to introduce a functional group into the π-conjugated conductive polymer.

  The dopant may be donor-type or acceptor-type as long as the oxidation-reduction potential of the conjugated electron can be changed in doping / dedoping the π-conjugated conductive polymer. Among these dopants, acceptor inorganic acids, organic acids, and polyanions are preferred because of their particularly high doping effects. Further, among these, polyanions are more preferable because solubility in a solvent can be increased simultaneously with doping.

  Examples of the donor dopant include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, and the like. A quaternary amine compound etc. are mentioned.

  As the acceptor dopant, for example, a halogen compound, Lewis acid, proton acid, organic cyano compound, organometallic compound, fullerene, hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, sulfonated fullerene, or the like can be used. Furthermore, examples of the halogen compound include chlorine (Cl2), bromine (Br2), iodine (I2), iodine chloride (ICl), iodine bromide (IBr), and iodine fluoride (IF). Examples of the Lewis acid include PF5, AsF5, SbF5, BF5, BCl5, BBr5, and SO3. As the organic cyano compound, a compound containing two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

  Examples of the protonic acid include inorganic acids and organic acids. Furthermore, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borohydrofluoric acid, hydrofluoric acid, and perchloric acid. Examples of organic acids include organic carboxylic acids, phenols, and organic sulfonic acids.

  As the organic carboxylic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more carboxyl groups can be used. For example, formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitroacetic acid, And triphenylacetic acid.

  As the organic sulfonic acid, aliphatic, aromatic, cycloaliphatic or the like containing one or more sulfo groups, or a polymer containing sulfo groups can be used.

  As one containing one sulfo group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1 -Nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfone Acid, trifluoroethanesulfonic acid, colistin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol- 7-sulfonic acid, 3-aminopropanesulfone N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hex Tylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methyl Benzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4 -Acetamide-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, 4 -Amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1- Examples include sulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, anthraquinone sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of those containing two or more sulfo groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, and toluenedisulfonic acid. , Xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, dimethylbenzene disulfonic acid, diethylbenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 3,4-dihydroxy-1,3 Benzene disulfonic acid, naphthalene disulfonic acid, methyl naphthalene disulfonic acid, ethyl naphthalene disulfonic acid, pentadecyl naphthalene disulfonic acid, 3-amino-5-hydroxy-2,7-naphthalene disulfonic acid, 1- Cetamide-8-hydroxy-3,6-naphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-1,5-naphthalenedisulfonic acid, 8-Amino-1-naphthol-3,6-disulfonic acid, 4-amino-5-naphthol-2,7-disulfonic acid, 4-acetamido-4'-isothio-cyanotostilbene-2,2'-disulfonic acid 4-acetamido-4′-isothiocyanatostilbene-2,2′-disulfonic acid, 4-acetamido-4′-maleimidylstilbene-2,2′-disulfonic acid, naphthalenetrisulfonic acid, dinaphthylmethanedisulfone An acid, anthraquinone disulfonic acid, anthracene sulfonic acid, etc. are mentioned. These metal salts can also be used.

  Examples of the polyanion include a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, and a substituted or unsubstituted polyester having an anionic group. Examples thereof include a polymer composed only of a structural unit and a polymer composed of a structural unit having an anionic group and a structural unit not having an anionic group.

  A polyalkylene is a polymer whose main chain is composed of repeating methylenes. Polyalkenylene is a polymer composed of structural units containing one unsaturated double bond (vinyl group) in the main chain. As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′-[4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride And polyimides from acid anhydrides such as oxydiamine, paraphenylenediamine, metaphenylenediamine, benzophenonediamine and the like. Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like. Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  When the polyanion has a substituent, examples of the substituent include an alkyl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, and an alkoxyl group. In view of solubility in an organic solvent, heat resistance, and the like, an alkyl group, a hydroxyl group, a phenol group, and an ester group are preferable.

  Examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. It is done. Examples of the hydroxyl group include a hydroxyl group bonded directly or via another functional group to the main chain of the polyanion. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. Hydroxyl groups are substituted at the ends or in these functional groups. Examples of the amino group include an amino group bonded to the main chain of the polyanion directly or via another functional group. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The amino group is substituted at the end or in these functional groups. Examples of the phenol group include a phenol group bonded to the main chain of the polyanion directly or via another functional group. Examples of the other functional group include an alkyl group having 1 to 7 carbon atoms and an alkyl group having 2 to 7 carbon atoms. An alkenyl group, an amide group, an imide group, etc. are mentioned. The phenol group is substituted at the end or in these functional groups.

  Examples of the polyalkylene having a substituent include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene and the like. it can. Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-propyl-2-pentenylene, 4- Tyl-2-pentenylene, 4-hexyl-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy- Examples thereof include polymers containing one or more structural units selected from 2-pentenylene, hexenylene and the like.

Examples of the anion group of the _{^{polyanion, -O-SO 3 - X +}} , -SO 3 - X +, -COO - X + (. X + is the hydrogen ion in each of the formulas, represents an alkali metal ion), and the like. That is, the polyanion is a polymer acid containing a sulfo group and / or a carboxyl group. Among these, from the viewpoint of doping effects on the π-conjugated conductive _{^{polymer, -SO 3 - X +, -COO}} - X + are preferable. Moreover, it is preferable that this anion group is arrange | positioned in the principal chain of a polyanion adjacently or at regular intervals.

  Among the polyanions, polyisoprene sulfonic acid, a copolymer containing polyisoprene sulfonic acid, a polysulfoethyl methacrylate, a copolymer containing polysulfoethyl methacrylate, and poly (4-sulfone) are preferable in view of solvent solubility and conductivity. Butyl methacrylate), copolymers containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzene sulfonic acid, copolymers containing polymethallyloxybenzene sulfonic acid, polystyrene sulfonic acid, copolymer containing polystyrene sulfonic acid A coalescence or the like is preferable.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  The content of the dopant is preferably in the range of 0.5 to 50 mol, and more preferably in the range of 1 to 20 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the content of the dopant is less than 0.5 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. On the other hand, when the dopant content is more than 50 mol, the content of the π-conjugated conductive polymer is reduced, and it is difficult to obtain sufficient conductivity. In particular, when the dopant is a polyanion, the content of the polyanion is preferably in the range of 0.1 to 10 mol, and in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. It is more preferable. When the polyanion content is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are lowered, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content is more than 10 mol, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

  Further, the curable silicone resin and the π-conjugated conductive polymer resin contained in the release layer constituting the release film in the present invention may be mixed at the time of compounding the compounding liquid, or those previously compounded May be used.

  Further, the curable silicone resin contained in the release layer constituting the release film in the present invention is preferably a silicone-modified resin from the viewpoint of the effect of inhibition of curing by the π-conjugated conductive polymer resin. .

  In the present invention, conventionally known coating methods such as reverse gravure coating, direct gravure coating, roll coating, die coating, bar coating, curtain coating and the like can be used as a method for providing a release layer on the polyester film. Regarding the coating method, there is a description example in “Coating method” published by Yasuharu Harasaki in 1979.

In the present invention, the curing conditions for forming the release layer on the polyester film are not particularly limited, and when providing the release layer by off-line coating, usually at 120 to 200 ° C. for 3 to 40 seconds, The heat treatment is preferably performed at 100 to 180 ° C. for 3 to 40 seconds as a guide. Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed. In addition, a conventionally well-known apparatus and energy source can be used as an energy source for hardening by active energy ray irradiation. The coating amount of the release layer from the viewpoint of coating property, usually 0.005 g / ^{m 2} or more, preferably 0.01 g / ^{m 2} or more. If the coating amount is less than 0.005 g / m ² , the coating property may be less stable and it may be difficult to obtain a uniform coating film.

  The polyester film constituting the release film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  In the present invention, when a release layer is provided on the coating layer, the film may be temporarily wound after the coating layer is provided, and the release layer may be provided again. In addition, after the coating layer is provided, the release layer is continuously released. A mold layer may be provided on the coating layer, and any method may be adopted.

After the release film of the present invention is heat-treated (180 ° C., 10 minutes), the amount (OL) of the polyester extracted from the release layer surface with dimethylformamide is preferably 2.0 mg / m ² or less. More preferably, it is 1.0 mg / m ² or less. When the OL exceeds 2.0 mg / m ² , for example, when the liquid crystal component is manufactured, the adhesive layer is used for protecting the adhesive layer, the transparency of the adhesive is lowered, the adhesive strength of the adhesive layer is reduced, or optical evaluation is performed. There may be problems such as causing trouble in the accompanying inspection process.

  In the release film of the present invention, the value measured by the FP (Fundamental Parameter Method) method using a fluorescent X-ray measuring device as the amount of aluminum element contained in the coating layer is 0 because the OL satisfies the above range. It is preferably 0.01 kcps or more, more preferably 0.5 kcps or more, and particularly preferably 0.8 kcps or more. If the amount of aluminum element is less than 0.01 kcps, the desired oligomer sealing performance may not be obtained. The titanium element amount is preferably 0.05 kcps or more, more preferably 0.1 kcps or more. When the amount of titanium element is less than 0.05 kcps, the desired oligomer sealing performance may not be obtained. The zirconium amount is preferably 0.001 kcps or more, more preferably 0.02 kcps or more, and particularly preferably 0.04 or more. When the amount of zirconium element is less than 0.001 kcps, the desired oligomer sealing performance may not be obtained.

  In the present invention, “oligomer” is defined as a cyclic trimer among low molecular weight polyesters that crystallize after heat treatment and precipitate on the film surface.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measuring method used in the present invention is as follows.

(1) Measurement of intrinsic viscosity of polyester 1 g of polyester from which other polymer components and pigments incompatible with polyester have been removed are precisely weighed, and 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) is added. It was dissolved and measured at 30 ° C.

(2) Measurement of average particle diameter (d ₅₀ : μm) Integration (weight basis) 50% in equivalent spherical distribution measured using centrifugal sedimentation type particle size distribution measuring device (SA-CP3 type manufactured by Shimadzu Corporation) Was the average particle size.

(3) Surface specific resistance value Based on the method of the following (3-1), the surface specific resistance value of the film application layer was measured. In the method of (3-1), since the surface specific resistance value higher than 1 × 10 ⁸ Ω cannot be measured, the method of (3-2) was used for the sample that could not be measured in (3-1).
(3-1) Low resistivity meter manufactured by Mitsubishi Chemical Co., Ltd .: Loresta GP MCP-T600 was used, the sample was conditioned for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, and then the surface resistivity was measured.
(3-2) Using a high resistance measuring instrument made by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B, measuring the surface resistivity after conditioning the sample for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH did.
Thereafter, the peeling condition was determined according to the following criteria.
<Criteria>
○: Surface resistivity is 1 × 10 ¹² Ω or less (practical level)
X: Surface resistivity exceeds 1 × 10 ¹² Ω (practically problematic level)

(4) Measurement of polyester oligomer amount (OL) extracted from release layer surface of release film An unheat-treated release film is heated in air at 180 ° C. for 10 minutes in advance. After that, the heat-treated film is brought into close contact with the inner surface of a box having a top and width of 10 cm and a height of 3 cm, and the box shape is obtained. When the coating layer is provided, the coating layer surface is set to the inside. Next, 4 ml of DMF (dimethylformamide) is placed in the box prepared by the above method and left for 3 minutes, and then DMF is recovered. The recovered DMF was supplied to liquid chromatography (manufactured by Shimadzu Corporation: LC-7A) to determine the amount of oligomer in DMF, and this value was divided by the film area in contact with DMF to obtain the amount of film surface oligomer (mg / M ² ).

  The amount of oligomer in DMF was determined from the peak area ratio between the standard sample peak area and the measured sample peak area (absolute calibration curve method). The standard sample was prepared by accurately weighing the oligomer (cyclic trimer) collected in advance and dissolving it in DMF accurately measured. The concentration of the standard sample is preferably in the range of 0.001 to 0.01 mg / ml.

The conditions for the liquid chromatograph were as follows.
Mobile phase A: Acetonitrile Mobile phase B: 2% acetic acid aqueous solution Column: “MCI GEL ODS 1HU” manufactured by Mitsubishi Chemical Corporation
Column temperature: 40 ° C
Flow rate: 1 ml / min Detection wavelength: 254 nm
Thereafter, the peeling condition was determined according to the following criteria.
<Criteria>
○: Surface oligomer amount (OL) is 2.0 mg / m2 or less (a level that causes no problem in practical use)
X: Surface oligomer amount (OL) exceeds 2.0 mg / m2 (practically problematic level)

(5) Element amount measurement from release surface side of release film Fluorescent X-ray measurement device (Shimadzu Corporation model “XRF-1500” from the surface provided with a release layer of a sample sample in advance. ) Was used to measure the element amount under the measurement conditions shown in the following table by the FP (Fundamental Parameter Method) method.

(6) Peeling force (F) measurement of release film Affixed with one side of a double-sided adhesive tape (Nitto Denko “No. 502”) on the surface of the release layer of the sample film, then cut into a size of 50 mm × 300 mm Measure the peel force after standing at room temperature for 1 hour. For the peeling force, a tensile tester (“Intesco model 2001 type” manufactured by Intesco Co., Ltd.) was used, and 180 ° peeling was performed under a tensile speed of 300 mm / min.
Thereafter, the peeling condition was determined according to the following criteria.
<Criteria>
○: There is no catching at the time of peeling (practically no problem level)
X: There is a catch at the time of peeling (practically problematic level)

(7) Initial evaluation of coating film adhesion of release film (practical property substitution evaluation)
The release surface of the sample film immediately after coating was rubbed 5 times with a tentacle, and the degree of release of the release layer was determined according to the following criteria.
<Criteria>
○: No dropout of the coating film (practical level)
Δ: The coating film turns white but does not fall off (practical level)
×: Detachment of the coating film was confirmed (practically difficult level)

(8) Evaluation after release film adhesion test for release film (practical property substitution evaluation)
The sample film was left in a constant temperature and humidity chamber at 80 ° C. and 90% RH for 2 weeks, and then the sample film was taken out. By rubbing 5 times with a tentacle, the degree of removal of the release layer was determined according to the following criteria.
<Criteria>
A: The coating film does not come off at all, and there is no difference in the peel strength between the rubbed part and the non-rubbed part (practical level).
○: The coating film was not removed at all, and the rubbed part was slightly heavier than the non-rubbed part (practical level)
Δ: The coating film became white, but did not fall off, and the rubbed part was heavier than the non-rubbed part (practical level)
×: Detachment of the coating film was confirmed (practically difficult level)

(9) Number of foreign bodies visually observed under crossed Nicols (practical property substitution evaluation)
An acrylic pressure-sensitive adhesive composition having the following composition was applied to the release film, followed by heat treatment at 100 ° C. for 5 minutes to obtain a pressure-sensitive adhesive layer having a thickness (after drying) of 150 μm. Thereafter, the release film and the adhesive layer bonded product were heat-treated at 150 ° C. for 90 minutes, and then the release film was peeled off, the adhesive layer was sandwiched between polarizing plates, and the number of foreign matters was visually confirmed under crossed Nicols. The evaluation was made based on the detection status of foreign matter.
<Acrylic adhesive composition>
(Monomer composition)
2-ethylhexyl acrylate 70% by weight
2-methoxyethyl acrylate 29% by weight
4-hydroxybutyl acrylate 1% by weight
0.1 part of Nippon Polyurethane Coronate L was added to 100 parts by weight of the monomer composition to obtain an acrylic pressure-sensitive adhesive layer forming composition.
"Criteria"
○: No foreign matter is visually detected, and the quality is sufficient for optical applications. Δ: Foreign matter is detected visually, but there is no problem in practical use. ×: Many foreign matters are detected visually, optical. Unsuitable for use, limited use

(10) Foreign matter inspection The base material-less double-sided pressure-sensitive adhesive sheet provided with release films on both sides was observed and evaluated based on the foreign matter detection status.
○: No foreign matter is detected, and the quality is sufficient for optical use. △: Foreign matter is detected, but there is no practical problem. ×: Many foreign matters are detected, which is inappropriate for optical use. Limited use

(11) Comprehensive evaluation Using the release films produced in the examples and comparative examples, the surface resistivity, surface oligomer amount, release force (F), initial evaluation of release film adhesion, release film adhesion For each evaluation item of the evaluation after the acceleration test, the visual inspection property evaluation under crossed Nicols, and the foreign matter inspection, comprehensive evaluation was performed according to the following criteria.
(Criteria)
○: Surface specific resistance value of release film, surface oligomer amount, peeling force (F), initial evaluation of coating film adhesion, evaluation after coating film adhesion promotion test, visual inspection evaluation under crossed Nicols, foreign substance inspection Everything is better than ○
Δ: surface specific resistance value of release film, surface oligomer amount, peel force (F), initial evaluation of coating film adhesion, evaluation after coating film adhesion promotion test, evaluation of visual inspection property under crossed Nicols, inspection of foreign matter Among them, at least one is △ (level that may cause problems in practice)
X: Surface resistivity value of release film, surface oligomer amount, peel force (F), initial evaluation of coating film adhesion, evaluation after coating film adhesion promotion test, evaluation of visual inspection property under crossed Nicols, foreign substance inspection Among them, at least one is x (a level that is problematic in practice)

The polyester used in the examples and comparative examples was prepared as follows.
<Manufacture of polyester>
Production Example 1 (Polyethylene terephthalate A1)
100 parts of dimethyl terephthalate, 60 parts of ethylene glycol and 0.09 part of magnesium acetate tetrahydrate are placed in a reactor, the temperature is raised by heating, methanol is distilled off, transesterification is performed, and 4 hours are required from the start of the reaction. The temperature was raised to 230 ° C. to substantially complete the transesterification reaction. Next, 0.04 part of ethylene glycol slurry ethyl acid phosphate, 0.03 part of antimony trioxide and 0.01 part of silica particles having an average particle diameter of 1.5 μm were added, and then the temperature was 280 ° C. and the pressure was increased in 100 minutes. The pressure reached 15 mmHg, and the pressure was gradually reduced thereafter to finally reach 0.3 mmHg. After 4 hours, the system was returned to atmospheric pressure to obtain polyethylene terephthalate A1 having an intrinsic viscosity of 0.61.

Reference example 1:
The polyethylene terephthalate A1 produced in Production Example 1 was dried at 180 ° C. for 4 hours in an inert gas atmosphere, melted at 290 ° C. by a melt extruder, extruded from a die, and the surface temperature was adjusted to 40 using an electrostatic application adhesion method. The sheet was cooled and solidified on a cooling roll set to ° C. to obtain an unstretched sheet. First, the obtained unstretched sheet was stretched 3.6 times in the MD direction at 95 ° C., led to a tenter, and sequentially biaxially stretched 4.3 times in the TD direction. Thereafter, it was heat-fixed at 230 ° C. for 3 seconds to obtain a PET film having a thickness of 38 μm. Next, the following coating agent was applied by a reverse gravure coating method so that the coating amount (after drying) was 0.05 g / m ^2, and then heat-treated at 120 ° C. for 30 seconds. Examples of compounds constituting the coating layer are as follows.

(Example compounds)
-Organic compound having an aluminum element: (A1)
Aluminum tris (ethyl acetoacetate)
・ Organic compound containing titanium element: (A2)
Organic compound containing titanium tetraacetylacetonate / zirconium element: (A3)
Zirconium tetraacetylacetonate / organosilicon compound: (B1)
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane

<< Coating composition >>
Organic compound having aluminum element (A1): 10% by weight
Organosilicon compound (B1): 90% by weight
The coating agent was diluted with a toluene / MEK mixed solvent (mixing ratio was 1: 4) to obtain 4% by weight.

Thereafter, a release agent having the following release agent composition was coated on the coating layer by a reverse gravure coating method so that the coating amount (after drying) was 0.1 g / m ² and heat-treated at 150 ° C. for 30 seconds. A release film was obtained later.
<< Releasing Agent Composition >> Compound Example Curable Silicone Resin (a1): (KS847H: manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone-modified acrylic resin and polythiophene-containing conductive polymer resin mixture (b1): (SAS-F06H04C: manufactured by Shin-Etsu Polymer)
Polythiophene-containing conductive polymer resin (c1): (AS-D09E: manufactured by Shin-Etsu Polymer)
Curing agent (d1) (PL-50T: manufactured by Shin-Etsu Chemical Co., Ltd.)
(Mixing conditions)
a1: 0% by weight
b1: 100% by weight
c1: 0% by weight
d1: 0% by weight
The release agent was diluted with a 1: 1 solvent of MEK and butanol to prepare a coating solution having a concentration of 2% by weight.

Examples 5, 8, 9, Reference Examples 2-4, 6 , 7, 10-12 and Comparative Examples 1-6:
In Reference Example 1, the coating agent composition was changed to the coating agent composition shown in Table 2 below, and the release agent composition was manufactured in the same manner as Reference Example 1 except that the release agent composition was changed to the release agent composition shown in Table 3 below. A release film was obtained. Tables 4 and 5 show the properties of the release films obtained in the above Examples and Comparative Examples.

  According to the release film of the present invention, it is possible to provide a release film having a polyester oligomer precipitation amount as low as possible and having a low surface resistivity, for example, for producing a capacitive touch panel. For various optical applications, such as various types of bonding, LCD polarizing plate, retardation plate manufacturing, PDP component manufacturing, organic EL component manufacturing, display component manufacturing, etc. A type film is provided, and its industrial value is high.

Claims (2)

A release film in which a coating layer and a release layer are sequentially provided on one side of a polyester film stretched at least in a uniaxial direction, and the coating layer includes two or more organic compounds containing a metal element, an organosilicon compound, and The organic compound containing the metal element contains 5 to 15% by weight of a titanium compound, 5 to 15% by weight of an aluminum compound and / or a zirconium compound,
The release layer contains a π-conjugated conductive polymer resin and a silicone resin, the release layer has a surface resistivity (R) of 1 × 10 ¹² Ω or less, and the film is heated at 180 ° C. for 10 minutes. A release film characterized in that the amount of the polyester oligomer on the surface of the release layer after the treatment is 1.0 mg / m ² or less.
2. The release film according to claim 1, wherein the π-conjugated conductive polymer resin contains an organic compound containing sulfur.