JP2017110032A - Laminate polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate polyester film which is a protective film having high transparency and capable of being used for a glass, a steel sheet or the like used in mainly out door, such as for automobile, for advertising display, for solar light electric conversion, for road related members such as a traffic sign or a noise barrier, capable of omitting an operation of washing which has been conducted conventionally by prevention of adhesion of water droplet marks or dirt, pollen, sand dust, bird dung or the like, having no need for a water treatment after washing, contributing to environmental load reduction and capable of coated film deterioration prevention of various targets to be protected due to effects of acidic rain and scratch prevention to various target to be protected by scattering stones or the like.SOLUTION: There is provided a laminate polyester film having a release layer on one surface of a polyester film and an adhesive layer on another surface and having internal haze of a film at laminate state of the release layer and the polyester film of 1.0% or less.SELECTED DRAWING: None

Description

  The present invention relates to a laminated polyester film, and more specifically, protection for glass, steel plates, etc. used mainly outdoors, such as for automobiles, signboards, solar power generation, road-related members such as road signs and sound insulation walls. Prevention of adhesion of water marks and dirt, pollen, sand dust, bird dung, etc., prevention of coating film deterioration of various protection objects due to acid rain, prevention of scratches on various protection objects such as stepping stones, etc. The present invention relates to a highly transparent laminated polyester film having the following performance.

  Conventionally, polyester films, especially polyethylene terephthalate films and polyethylene naphthalate films, have excellent mechanical properties, heat resistance, and chemical resistance. Magnetic tape, ferromagnetic thin film tape, photographic film, packaging film, electronic Films for parts, electrical insulation films, metal laminate films, films to be attached to glass surfaces such as glass displays, protective films for liquid crystal display (LCD) components, optical films such as LCD backlight units, ITO for touch panels, etc. It is used in various applications such as anti-fouling / explosion-proof / scattering film for PDP filter, etc.

  Polyester films used in a wide range of applications are used as protective films for automobiles, signboards, solar power generation, road-related materials such as road signs and sound insulation walls, mainly for glass and steel sheets used outdoors. I can expect that. The reason for this is that glass, steel plates, etc. that are currently used outdoors need to be cleaned regularly due to water droplet traces, dirt, pollen, sand dust, bird dung, etc., but in recent years they have been used for cleaning. There are problems with the environmental impact of water treatment, coating film deterioration problems of various objects to be protected due to the effects of acid rain, and problems with scratches on various objects to be protected due to stepping stones in the environment of use. Because.

  Among these, the most serious problem is the adhesion of dirt, which is caused by the fact that water droplets containing dust in the atmosphere adhere to various objects to be protected, the moisture is not evaporated, and the various kinds of dust are protected. Since it occurs when the object remains, countermeasures are required.

  In addition, market needs include various types of protection objects such as, for example, the paint color of automobile bodies, the paint color and display content of signboards, and so on, and the power generation efficiency of solar power generation is reduced. In the case of using it for the purpose of preventing deterioration, a more transparent film is required.

  Conventionally, polyolefin films that have been used as various protective films are inferior in mechanical strength, heat resistance, etc., and therefore are not sufficiently effective in preventing deterioration with time and scratching. Also, due to inferior transparency, when observing an object to be protected with a protective film attached, a sufficient field of view cannot be secured, and it is necessary to peel off the protective film when performing inspections, etc. Yes, it is inconvenient.

JP 2007-270005 A

  The present invention has been made in view of the above-mentioned circumstances, and the problem to be solved is such as glass, steel plate, etc. mainly used outdoors such as automobiles, signboards, solar power generation, road-related members such as road signs and sound insulation walls, etc. Used for protective films, etc. It has high transparency, has excellent water repellency and rigidity, and is excellent in preventing water droplets and dirt, coating film deterioration due to acid rain, and scratches due to stepping stones. The object is to provide a laminated polyester film.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the above problems can be easily solved by a laminated polyester film having a specific configuration, and have completed the present invention.

  That is, the gist of the present invention is a laminated polyester film having a release layer on one surface of the polyester film and an adhesive layer on the other surface, and a laminated state film of the release layer and the polyester film. It exists in the laminated polyester film characterized by internal haze being 1.0% or less.

  According to the laminated polyester film of the present invention, as various protective films, it has excellent water repellency and rigidity, good water droplet traces and dirt adhesion prevention, paint film deterioration prevention due to acid rain, scratching prevention due to stepping stones, etc. A highly transparent film can be provided, and its industrial value is high.

  The polyester film constituting the laminated polyester film in the present invention may have a single layer structure or a multilayer structure, and may have four or more layers as long as it does not exceed the gist of the present invention other than a two-layer or three-layer structure. It may be a multilayer, and is not particularly limited. It is preferable to have a multi-layer structure of two or more layers and to give each layer a characteristic so as to achieve multiple functions.

  The polyester used for the polyester film refers to one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol etc. are mentioned.

  Representative polyesters include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), polybutylene terephthalate, and the like. Such a polyester may be a homopolymer that is not copolymerized, 20 mol% or less of the dicarboxylic acid component is a dicarboxylic acid component other than the main component, and / or 20 mol% or less of the diol component is other than the main component. It may be a copolyester that is a diol component. Moreover, those mixtures may be sufficient.

  Polyester is a conventionally known method, for example, a method of directly obtaining a low polymerization degree polyester by reaction of a dicarboxylic acid and a diol, or a reaction after reacting a lower alkyl ester of a dicarboxylic acid and a diol with a conventionally known transesterification catalyst. It can be obtained by a method in which a polymerization reaction is carried out in the presence of a catalyst. As the polymerization catalyst, a known catalyst such as an antimony compound, a germanium compound, or a titanium compound may be used. Preferably, the amount of antimony compound is zero or the amount of antimony is reduced to 100 ppm or less as antimony to further reduce film dullness. preferable.

  Further, when a titanium compound is used as a catalyst, the amount of metal remaining in the film is small, which is preferable from the viewpoint of transparency of the film and reduction in the generation of foreign matter. ) Is also an advantage.

  The intrinsic viscosity (IV) of the polyester is preferably 0.63 dl / g or more, more preferably 0.65 dl / g or more, further preferably 0.67 dl / g or more, particularly preferably 0.70 dl / g or more. Is to use polyester. By setting the intrinsic viscosity of polyester to 0.63 dl / g or higher, good long-term durability and hydrolysis resistance after wet heat treatment when assuming protective films used for glass, steel plates, etc. used outdoors Can be obtained. On the other hand, although there is no upper limit of the intrinsic viscosity of polyester, it is preferably 0.95 dl / g from the viewpoint of the efficiency of the polycondensation reaction and the prevention of pressure increase in the melt extrusion process.

  The terminal carboxyl group amount (AV) of the polyester is preferably 40 equivalent / t or less, more preferably 30 equivalent / t or less, and still more preferably 26 equivalent / t or less. In particular, in applications that strongly require durable hydrolysis resistance, it is preferably further reduced, and the range is preferably 20 equivalents / t or less, more preferably 15 equivalents / t or less, and even more preferably 10 equivalents / t. Polyester in the range of t or less, particularly preferably 8 equivalents / t or less is used. By setting the terminal carboxyl group amount of the polyester to 40 equivalent / t or less, a polyester film having good long-term durability and hydrolysis resistance after wet heat treatment can be obtained. On the other hand, there is no lower limit of the amount of terminal carboxyl groups of the polyester, but it is preferably 1 equivalent / t from the viewpoints of the efficiency of the polycondensation reaction, thermal decomposition in the melt extrusion process, and the like.

  In the polyester layer in the present invention, particles may be blended mainly for the purpose of imparting slipperiness to such an extent that the transparency is not impaired. 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 thereof include inorganic particles such as magnesium silicon oxide, kaolin, aluminum oxide, and titanium oxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenol resin, epoxy resin, and benzoguanamine resin. 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. Of these, silica particles and calcium carbonate particles are preferable because they are particularly effective in a small amount.

  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 becomes like this. Preferably it is 5 micrometers or less, More preferably, it is 0.1-3.0 micrometers, More preferably, it is the range of 0.2-2.5 micrometers. When the average particle size is less than 0.1 μm, the particles are likely to aggregate and dispersibility may be insufficient, and the particles may be added to form a surface roughness for the purpose of providing easy slip to the film. In the case of blending, it is necessary to increase the blending amount. As a result, the haze of the film is increased and the transparency may be deteriorated. On the other hand, when the thickness exceeds 5 μm, the surface roughness of the film becomes too rough and the transparency becomes inferior, so that it may be unsuitable for use as a protective film for glass, steel plates and the like.

  Furthermore, the particle content in the polyester is preferably 5% by weight or less, more preferably 0.0003 to 1.0% by weight, and still more preferably 0.0005 to 0.5%, based on the total polyester constituting the film. It is in the range of wt%. When there are no particles or when there are few, the transparency of the film will be high and a good film will be obtained, but the slipperiness may be insufficient, so by including particles in the release layer or adhesive layer In some cases, it is necessary to improve the slipping property. Also, if the particle content is high, the haze becomes high and lacks transparency, so that, for example, when various inspections or the like cannot reveal defects such as foreign matters, or when the protective film is removed, It may be necessary to observe

  The method for adding particles to the polyester 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, 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, heat stabilizers, lubricants, antistatic agents, fluorescent whitening agents, dyes, pigments and the like can be added to the polyester film as necessary. . Further, depending on the purpose such as prevention of coating film deterioration of the body of a protective film substrate, glass, steel plate or the like which is protected by ultraviolet rays, an ultraviolet absorber, particularly a benzoxazinone-based ultraviolet absorber may be contained.

  From the viewpoint of use as a protective film, the thickness of the polyester film of the present invention is preferably in the range of 1 to 350 μm, more preferably 5 to 200 μm, and still more preferably 10 to 100 μm.

  In addition, the polyester film can be formed into a laminated structure by using various conventionally known methods such as a co-extrusion method. In this case, the outermost layer thickness is a thickness on one side only, preferably 2 μm or more, more preferably 3 μm. It is preferable that the thickness is 1/8 or less of the total thickness. By using it in the above range, for example, it is possible to form a polyester film layer containing particles only on the surface layer, to express sufficient slipperiness, and to avoid a decrease in transparency due to the particles.

  In the laminated polyester film of the present invention, there is no adhesive layer, that is, a polyester film having a release layer (a film in a laminated state of a release layer and a polyester film: hereinafter abbreviated as a release layer-laminated polyester film). The internal haze is 1.0% or less, preferably 0.8% or less, more preferably 0.6% or less, and still more preferably 0.4% or less. When the internal haze exceeds 1.0%, it is sufficiently transparent when used for applications having excellent transparency, for example, for applications that place importance on transparency in protective films such as glass and steel sheets used outdoors. Does not have sex.

  In the present invention, the release layer laminated polyester film has a film longitudinal direction (MD) of preferably 1.0% or less, more preferably 0.8% or less, and still more preferably with respect to the heat shrinkage rate at 95 ° C. for 30 minutes. The range is 0.5% or less, particularly preferably 0.4 or less. The film width direction (TD) is preferably 1.0% or less, more preferably 0.7% or less, still more preferably 0.4% or less, and particularly preferably 0.3% or less. Further, the lower limit of the heat shrinkage rate is not particularly limited, but both MD and TD are preferably 0.0%. When used in the above range, when the film longitudinal direction (MD) is larger than 0.6% and the film width direction (TD) is larger than 0.4%, it is used outdoors by bonding to glass or steel plate. , It can suppress the generation of wrinkles due to the loss of dimensional stability, can reduce the occurrence of defects that peel off from the part to be protected, and can maintain and improve the performance as a protective film .

  In the laminated polyester film of the present invention, the water droplet contact angle on the surface of the polyester film on which the release layer is formed is preferably 70 degrees or more, more preferably 80 degrees or more, still more preferably 90 degrees or more, and particularly preferably 100 degrees. It is the above range. By setting the water droplet contact angle in the above range, water repellency is increased, and when used as a protective film, traces of water droplets and dirt are less likely to remain on the protective film, and transparency is easily maintained.

  In the present invention, the release layer-laminated polyester film is a color reflection method when a plurality of sheets are overlapped so that the total thickness at the time of measurement is between 900 μm and 1100 μm and is closest to 1000 μm. The y value is preferably 0.3240 or less More preferably, it is 0.3235 or less, More preferably, it is 0.3230 or less, Especially preferably, it is the range of 0.3225 or less. By using in the above range, when the color reflection method y value exceeds 0.3240, the yellowness of the film can be suppressed, and when used as a protective film for steel plate, various protected objects to be protected The paint color of the paint is neutral without being yellowish, and the appearance visibility level of various protected objects is good. In addition, in solar power generation, it is possible to prevent the power generation efficiency from being lowered.

  In order to obtain a film having such a color tone, the catalyst and auxiliary agent for producing the raw material polyester are selected, the amount of the catalyst is reduced as much as possible, and the temperature of the polyester becomes higher than necessary during polymerization and film formation. In addition, it is possible to adopt a method such as preventing the melting time from becoming longer or reducing the amount of the recyclable raw material.

  Hereinafter, although the manufacturing method of the polyester film of this invention is demonstrated concretely, as long as the summary of this invention is satisfied, this invention is not specifically limited to the following illustrations. In general, first, a dried or undried polyester chip is fed to a melt extrusion apparatus by a known method, and heated to a temperature equal to or higher than the melting point of each polymer to be melted. Next, the molten polymer is extruded from a die and rapidly cooled and solidified on a rotary cooling drum so that the temperature is equal to or lower than the glass transition temperature to obtain a substantially amorphous unoriented sheet. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed.

  It is preferable from the viewpoint of the strength of the film that the sheet obtained as described above is stretched in a biaxial direction to form a film. Specifically describing the stretching conditions, the unstretched sheet is preferably stretched 2.0 to 4.5 times at 70 to 145 ° C. in the longitudinal direction to form a longitudinally uniaxially stretched film, and then 90 to 90 in the lateral direction. It is preferable to perform 3.0 to 6.5 times stretching at 160 ° C. to obtain a biaxially stretched film, and to perform heat treatment (heat setting) at 210 to 260 ° C. for 10 to 600 seconds. A method of relaxing 1 to 10% in the longitudinal direction and / or the transverse direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet is preferable.

  In particular, when used in applications where the heat shrinkage rate is desired to be kept small, the above heat treatment temperature is preferably 215 to 250 ° C, more preferably 220 to 245 ° C, and further preferably 230 to 245 ° C. By setting the temperature range, it is possible to suppress the heat shrinkage as much as possible.

  In particular, the film of the present invention is considered for use as a protective film for automobiles, signboards, solar power generation, road-related members such as road signs and sound insulation walls, mainly used outdoors, glass, steel plates, etc. In this case, the protective film on the side that protects the object to be protected is also excellent in preventing contamination and adhesion due to water droplets, acid rain, etc. It has been found preferable.

  For example, if the protective film remains contaminated with water droplets, the visibility of the protected object including the protective film will deteriorate, making it difficult to grasp the current state of the protected object and inspecting foreign objects, etc. It is necessary to peel off and perform observation and inspection. If the protective film is peeled off, depending on the type of adhesive layer, the adhesive strength will be reduced or the adhesive strength will be lost, it will not be possible to reattach, and the film will not function sufficiently as a protective film. There is a disadvantage of being wasted. Even if a highly transparent protective film is used, if the film is contaminated, the transparency becomes worse and the purpose cannot be achieved.

  As a result of various studies to improve the functions of these protective films, avoid deterioration of visibility due to contamination and adhesion due to external factors such as acid rain, and maintain transparency, the release layer is adhered. It has been found that it can be improved by providing it on the side of the polyester film opposite to the layer. This is because the release layer that is located on the side opposite to the object to be protected and is exposed to various external environments has high water repellency.

  Further, the role of the release layer contributes not only to the effect of protecting various objects to be protected and the prevention of contamination of the protective film, but also to improving the handleability of the laminated polyester film of the present invention. For example, when the film of the present invention is stacked on a single sheet or wound in a roll shape, the release layer is prevented from sticking to the adhesive layer on the back side, ease of peeling, or improving slipperiness. Thus, there are effects such as making the film easier to manufacture, improving the handleability, and improving the processability of the adhesive layer on the film.

  Examples of the method for forming the release layer include methods such as coating, transfer, and lamination. In view of the ease of forming the release layer, it is preferable to form the release layer by coating.

  As a method by coating, it may be provided by in-line coating performed in the film production process, or may be provided by off-line coating in which the film once produced is coated outside the system. More preferably, it is formed by in-line coating.

  Specifically, the in-line coating is a method in which coating is performed at an arbitrary stage from melt extrusion of a resin forming a film to heat setting after stretching and winding. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and mold release layer formation can be performed at the same time, so there is an advantage in manufacturing cost. In addition, in order to perform stretching after coating, the thickness of the mold release layer can be changed depending on the stretch ratio. The thin film coating can be performed more easily than the offline coating.

  Further, by providing a release layer on the film before stretching, the release layer can be stretched together with the base film, whereby the release layer can be firmly adhered to the base film. Furthermore, in the production of a biaxially stretched polyester film, the film can be restrained in the longitudinal and lateral directions by stretching while gripping the film end with a clip, etc. High temperature can be applied while maintaining the properties.

  Therefore, since the heat treatment performed after coating can be performed at a high temperature that cannot be achieved by other methods, the film forming property of the release layer is improved, and the release layer and the base film are more firmly adhered to each other. In addition, a strong release layer can be obtained. In particular, it is very effective for reacting a cross-linking agent and expressing stable water repellency.

  In order to form a release layer, it is necessary to contain a release agent. There is no restriction | limiting in particular as a mold release agent, It is possible to use a conventionally well-known mold release agent, For example, a long chain alkyl group containing compound, a fluorine compound, a silicone compound, wax etc. are mentioned. Of these, long-chain alkyl compounds and fluorine compounds are preferred from the viewpoint of low contamination in terms of transfer to the other party to be protected and excellent water repellency, especially emphasizing prevention of sticking to the adhesive layer on the back side. If desired, silicone compounds are preferred. Also, wax is effective for improving the surface decontamination property. These release agents may be used alone or in combination.

  The long-chain alkyl group-containing compound is a compound having a linear or branched alkyl group having usually 6 or more, preferably 8 or more, and more preferably 12 or more carbon atoms. Examples of the alkyl group include hexyl group, octyl group, decyl group, lauryl group, octadecyl group, and behenyl group. Examples of the compound having an alkyl group include various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. . In view of heat resistance and contamination, a polymer compound is preferable. Further, from the viewpoint of effectively obtaining releasability, a polymer compound having a long-chain alkyl group in the side chain is more preferable.

  The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group capable of reacting with the reactive group. Examples of the reactive group include a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Examples of the compound having such a reactive group include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, a reactive group-containing polyester resin, and a reactive group-containing poly (meth) acrylic resin. Among these, polyvinyl alcohol is preferable in view of releasability and ease of handling.

  Examples of the compound having an alkyl group capable of reacting with the reactive group include, for example, long-chain alkyl group-containing isocyanates such as hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate, hexyl chloride, and octyl chloride. Long chain alkyl group-containing acid chlorides such as decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride, long chain alkyl group-containing amines, and long chain alkyl group-containing alcohols. Among these, long chain alkyl group-containing isocyanates are preferable, and octadecyl isocyanate is particularly preferable in consideration of releasability and ease of handling.

  In addition, a polymer compound having a long-chain alkyl group in the side chain can also be obtained by copolymerization of a long-chain alkyl (meth) acrylate polymer or a long-chain alkyl (meth) acrylate and another vinyl group-containing monomer. . Examples of the long-chain alkyl (meth) acrylate include hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate. It is done.

  The fluorine compound is a compound containing a fluorine atom in the compound. Organic fluorine compounds are preferably used in terms of the appearance of coating by in-line coating, and examples thereof include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorobenzene. . From the viewpoint of releasability, a compound having a perfluoroalkyl group is preferable. Furthermore, the compound containing the long-chain alkyl compound which is mentioned later can also be used for a fluorine compound.

  Examples of the compound having a perfluoroalkyl group include perfluoroalkyl (meth) acrylate, perfluoroalkylmethyl (meth) acrylate, 2-perfluoroalkylethyl (meth) acrylate, and 3-perfluoroalkylpropyl (meth) acrylate. Perfluoroalkyl group-containing (meth) acrylates such as 3-perfluoroalkyl-1-methylpropyl (meth) acrylate and 3-perfluoroalkyl-2-propenyl (meth) acrylate, and polymers thereof, and perfluoroalkylmethyl vinyl ether 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl Perfluoroalkyl group-containing vinyl ether and polymers thereof such as ether, and the like. In view of heat resistance and contamination, a polymer is preferable. The polymer may be a single compound or a polymer of multiple compounds. From the viewpoint of releasability, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Further, it may be a polymer with a compound containing a long-chain alkyl compound as described later. Moreover, it is also preferable that it is a polymer with vinyl chloride from a viewpoint of adhesiveness with a base material.

  The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include alkyl silicones such as dimethyl silicone and diethyl silicone, phenyl silicones having a phenyl group, and methyl phenyl silicone. Silicones having various functional groups can also be used, such as ether groups, hydroxyl groups, amino groups, epoxy groups, carboxylic acid groups, halogen groups such as fluorine, perfluoroalkyl groups, various alkyl groups, and various types. Examples thereof include hydrocarbon groups such as aromatic groups. As other functional groups, silicones having vinyl groups and hydrogen silicones in which hydrogen atoms are directly bonded to silicon atoms are also common, and both are used in combination to form silicones (addition reaction between vinyl groups and hydrogen silane). It can also be used.

  Moreover, it is also possible to use modified silicones such as acrylic graft silicone, silicone graft acrylic, amino-modified silicone, and perfluoroalkyl-modified silicone as the silicone compound. In view of heat resistance and contamination, it is preferable to use a curable silicone resin. As the type of curable type, any of the curing reaction types such as a condensation type, an addition type, and an active energy ray curable type can be used. Among these, a condensation type silicone compound is preferred from the viewpoint that there is little back surface transfer when it is formed into a roll.

  In the case of using a silicone compound, a polyether group-containing silicone compound is preferable from the viewpoint of less back transfer, good dispersibility in an aqueous solvent and high suitability for in-line coating. The polyether group may be present in the side chain or terminal of the silicone or may be present in the main chain. From the viewpoint of dispersibility in an aqueous solvent, it is preferably present in the side chain or terminal.

  A conventionally well-known structure can be used for a polyether group. From the viewpoint of the dispersibility of the aqueous solvent, an aliphatic polyether group is preferable to an aromatic polyether group, and an alkyl polyether group is preferable among the aliphatic polyether groups. Further, from the viewpoint of synthesis due to steric hindrance, a linear alkyl polyether group is preferable to a branched alkyl polyether group, and among them, a polyether group composed of linear alkyl having 8 or less carbon atoms is preferable. Further, when the developing solvent is water, a polyethylene glycol group or a polypropylene glycol group is preferable in consideration of dispersibility in water, and a polyethylene glycol group is particularly optimal.

  The number of ether bonds of the polyether group is usually in the range of 1-30, preferably in the range of 2-20, more preferably 3 from the viewpoint of improving the dispersibility in an aqueous solvent and the durability of the release layer. The range is -15. When there are few ether bonds, dispersibility will worsen, and conversely too much, durability and mold release performance will worsen.

  When the polyether group has a side chain or a terminal of the silicone, the terminal of the polyether group is not particularly limited, and is a hydroxyl group, an amino group, a thiol group, a hydrocarbon group such as an alkyl group or a phenyl group, a carboxylic acid group, Various functional groups such as a sulfonic acid group, an aldehyde group, and an acetal group can be used. Among these, considering the dispersibility in water and the crosslinkability for improving the strength of the release layer, a hydroxyl group, an amino group, a carboxylic acid group, and a sulfonic acid group are preferable, and a hydroxyl group is particularly optimal.

  The polyether group content of the polyether group-containing silicone is preferably in the range of 0.001 to 0.30, more preferably 0.01 to 0.20 in terms of a molar ratio, where the siloxane bond of the silicone is 1. %, More preferably 0.03 to 0.15%, particularly preferably 0.05 to 0.12%. By using it within this range, the dispersibility in water, the durability of the release layer and the good release properties can be maintained.

  The molecular weight of the polyether group-containing silicone is preferably not so large in consideration of dispersibility in an aqueous solvent, and is preferably large in consideration of the durability and release performance of the release layer. It is required to balance these characteristics, and the number average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 3000 to 30000, and still more preferably in the range of 5000 to 10,000.

  Further, considering the time-dependent change and release performance of the release layer and the contamination of various processes, it is preferable that the low molecular component (number average molecular weight is 500 or less) of silicone is as small as possible. The ratio of the whole compound is preferably 15% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. In addition, when using condensation type silicone, vinyl group (vinyl silane) bonded to silicon, hydrogen group (hydrogen silane), if left unreacted in the release layer, will cause various performance changes over time, The content of the functional group in the silicone is preferably 0.1 mol% or less, and more preferably not contained.

  Since polyether group-containing silicone is difficult to apply alone, it is preferable to use it dispersed in water. Various conventionally known dispersants can be used for dispersion, and examples thereof include anionic dispersants, nonionic dispersants, cationic dispersants, and amphoteric dispersants. Among these, when considering the dispersibility of the polyether group-containing silicone and the compatibility with polymers other than the polyether group-containing silicone that can be used for forming the release layer, anionic dispersants and nonionic dispersants are used. preferable. Moreover, it is also possible to use a fluorine compound for these dispersing agents.

  Anionic dispersants include sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyalkylene alkenyl. Sulfonates such as ether ammonium sulfate, sulfate esters, carboxylates such as sodium laurate and potassium oleate, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates Examples thereof include phosphates such as salts. Among these, a sulfonate system is preferable from the viewpoint of good dispersibility.

  Nonionic dispersants include, for example, ether type compounds in which alkylene oxides such as ethylene oxide and propylene oxide are added to compounds having hydroxyl groups such as higher alcohols and alkylphenols, and polyhydric alcohols such as glycerin and saccharides and ester bonds. Examples include an ester type, an ester / ether type in which an alkylene oxide is added to a fatty acid or a polyhydric alcohol fatty acid ester, and an amide type in which a hydrophobic group and a hydrophilic group are connected via an amide bond. Among these, an ether type is preferable in consideration of solubility in water and stability, and a type to which ethylene oxide is added is more preferable in consideration of handleability.

  Although it depends on the molecular weight and structure of the polyether group-containing silicone to be used and depends on the type of the dispersant to be used, it cannot be said unconditionally. As a weight ratio, it is preferably 0.01 to 0.5, more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.3.

  The wax is a wax selected from natural waxes, synthetic waxes, and blended waxes thereof. Natural waxes are plant waxes, animal waxes, mineral waxes, and petroleum waxes. Examples of plant waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil and the like. Animal waxes include beeswax, lanolin, whale wax and the like. Examples of the mineral wax include montan wax, ozokerite, and ceresin. Examples of petroleum wax include paraffin wax, microcrystalline wax, and petrolatum. Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imides, esters, ketones, and the like. Examples of synthetic hydrocarbons include Fischer-Tropsch wax (also known as sazol wax) and polyethylene wax, and other low molecular weight polymers (specifically, polymers having a number average molecular weight of 500 to 20000). The following polymers are also exemplified: polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol block or graft conjugate, and the like. Examples of the modified wax include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. The derivative herein is a compound obtained by any of purification, oxidation, esterification, saponification treatment, or a combination thereof. Hydrogenated waxes include hardened castor oil and hardened castor oil derivatives.

  Among these, synthetic waxes are preferable from the viewpoint of stable characteristics, among which polyethylene wax is more preferable, and oxidized polyethylene wax is more preferable. The number average molecular weight of the synthetic wax is preferably in the range of 500 to 30000, more preferably 1000 to 15000, and still more preferably 2000 to 8000, from the viewpoints of stability of properties such as blocking and handleability.

  In forming the release layer, it is also preferable to use various crosslinking agents in combination in order to strengthen the release layer and to stabilize performance such as water repellency.

  As the crosslinking agent, conventionally known materials can be used, and examples thereof include melamine compounds, epoxy compounds, oxazoline compounds, isocyanate compounds, carbodiimide compounds, silane coupling compounds, hydrazide compounds, and aziridine compounds. Among them, melamine compounds, epoxy compounds, isocyanate compounds, oxazoline compounds, carbodiimide compounds, and silane coupling compounds are preferable, and from the viewpoint that the water repellency can be appropriately maintained and the release layer can be strengthened. Compounds, oxazoline compounds and isocyanate compounds are preferred, and melamine compounds are particularly preferred. These crosslinking agents may be used alone or in combination of two or more.

  The melamine compound is a compound having a melamine skeleton in the compound. For example, an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used. As alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Moreover, as a melamine compound, either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used. In view of reactivity with various compounds, it is preferable that the melamine compound contains a hydroxyl group. Further, a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.

  The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, As the alkyl group, unsaturated amides such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); vinyl acetate Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride And α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene, and the like, and one or more of these monomers can be used.

  The amount of the oxazoline group of the oxazoline compound is preferably in the range of 0.5 to 10 mmol / g, more preferably 1 to 9 mmol / g, still more preferably 3 to 8 mmol / g, and particularly preferably 4 to 6 mmol / g. Use in the above range makes it easy to adjust the water repellency.

  The isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

  When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl isobutanoyl acetate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan, dodecyl mercaptan, ε-caprolactam, δ-valerolactam, etc. Lactam compounds, amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, Examples include oxime compounds such as maldehyde, acetoald oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more. Among these, an isocyanate compound blocked with an active methylene compound is preferable from the viewpoint that it is particularly effective for reducing the migration of the adhesive layer to the adherend.

  The isocyanate compound may be used alone, or may be used as a mixture or bond with various polymers. In the sense of improving the dispersibility and crosslinkability of the isocyanate compound, it is preferable to use a mixture or a bond with a polyester resin or a urethane resin.

  The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and the like hydroxyl groups and amino groups, There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Examples of the polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

  Among the above, polyether epoxy compounds are preferable from the viewpoint that various properties are good. The amount of the epoxy group is preferably a polyepoxy compound that is trifunctional or more polyfunctional than bifunctional.

  The carbodiimide compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule. For better strength of the release layer, a polycarbodiimide compound having two or more in the molecule is more preferable.

  The carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used. The diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

  Furthermore, in order not to lose the effect of the present invention, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound, adding a surfactant, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, You may add and use hydrophilic monomers, such as a hydroxyalkyl sulfonate.

  A silane coupling compound is an organosilicon compound having an organic functional group and a hydrolysis group such as an alkoxy group in one molecule. For example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4- Epoxy group) epoxy group-containing compounds such as ethyltrimethoxysilane, vinyl group-containing compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, styryl group-containing compounds such as p-styryltrimethoxysilane and p-styryltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, etc. (Meth) acrylic group-containing compound, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-triethoxysilyl-N -Amino group-containing compounds such as (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, tris (trimethoxysilylpropyl) Isocyanurate, tris (triethoxysilylpropyl) Examples include isocyanurate group-containing compounds such as cyanurate, mercapto group-containing compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. It is done.

  Among the above compounds, from the viewpoint of the strength of the release layer, an epoxy group-containing silane coupling compound, a double bond-containing silane coupling compound such as a vinyl group or (meth) acryl group, and an amino group-containing silane coupling compound are more preferable. .

  These cross-linking agents are used in a design for improving the performance of the release layer by reacting in the drying process or the film forming process. It can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or mixtures thereof exist in the completed release layer.

  In forming the release layer, various polymers such as polyester resin, acrylic resin, urethane resin, vinyl resin can be used to improve the coating appearance and transparency, and to control water repellency and slipperiness. . Among various polymers, polyester resin, acrylic resin, urethane resin, and vinyl resin are preferable from the viewpoint of easy control of water repellency, and polyester resin and acrylic resin are more preferable.

  The polyester resin includes, for example, those composed of the following polyvalent carboxylic acid and polyvalent hydroxy compound as main constituent components. That is, as the polyvalent carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 4,4′-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6 -Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutar Acid, succinic acid, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and ester-forming derivatives thereof can be used. As the polyvalent hydroxy compound, ethylene Recall, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol , Neopentyl glycol, 1,4-cyclohexanedimethanol, p-xylylene glycol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol Polytetramethylene glycol, polytetramethylene oxide glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, sodium dimethylolethylsulfonate, potassium dimethylolpropionate, and the like can be used. One or more compounds may be appropriately selected from these compounds, and a polyester resin may be synthesized by a conventional polycondensation reaction.

  The acrylic resin is a polymer composed of a polymerizable monomer including acrylic and methacrylic monomers (hereinafter, acrylic and methacryl may be abbreviated as (meth) acryl). These may be either homopolymers or copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers.

  Moreover, the copolymer of these polymers and other polymers (for example, polyester, polyurethane, etc.) is also included. For example, a block copolymer or a graft copolymer. Alternatively, a polymer (possibly a mixture of polymers) obtained by polymerizing a polymerizable monomer in a polyester solution or a polyester dispersion is also included. Similarly, a polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or a polyurethane dispersion (sometimes a mixture of polymers) is also included. Similarly, a polymer (in some cases, a polymer mixture) obtained by polymerizing a polymerizable monomer in another polymer solution or dispersion is also included.

  The polymerizable monomer is not particularly limited, but particularly representative compounds include, for example, various carboxyl groups such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, and citraconic acid. Monomers, and salts thereof; such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monobutyl hydroxyl fumarate, monobutyl hydroxy itaconate Various hydroxyl group-containing monomers; various such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate No (meta) acrylic Acid esters; various nitrogen-containing compounds such as (meth) acrylamide, diacetone acrylamide, N-methylolacrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene Various vinyl esters such as vinyl propionate and vinyl acetate; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane; phosphorus-containing vinyl monomers; Examples include various vinyl halides such as vinyl and biliden chloride; and various conjugated dienes such as butadiene.

  The urethane resin is a polymer compound having a urethane bond in the molecule. Usually, urethane resin is prepared by reaction of polyol and isocyanate. Examples of the polyol include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols. These compounds may be used alone or in combination.

  Polycarbonate polyols are obtained from a polyhydric alcohol and a carbonate compound by a dealcoholization reaction. Examples of the polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane and the like can be mentioned. Examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Examples of polycarbonate polyols obtained from these reactions include poly (1,6-hexylene) carbonate, poly (3- And methyl-1,5-pentylene) carbonate.

  Polyester polyols include polycarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.) or their acid anhydrides. Product and polyhydric alcohol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol 2-methyl-2-propyl-1 3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexane Diol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyl dialkanolamine, lactone diol, etc.).

  Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and the like.

  Examples of the polyisocyanate compound used for obtaining the urethane resin include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, and tolidine diisocyanate, α, α, α ′, α ′. -Aliphatic diisocyanates having aromatic rings such as tetramethylxylylene diisocyanate, aliphatic diisocyanates such as methylene diisocyanate, propylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl Methanzi Cyanate, alicyclic diisocyanates such as isopropylidene dicyclohexyl diisocyanates. These may be used alone or in combination.

  A chain extender may be used when synthesizing the urethane resin, and the chain extender is not particularly limited as long as it has two or more active groups that react with an isocyanate group. Alternatively, a chain extender having two amino groups can be mainly used.

  Examples of the chain extender having two hydroxyl groups include aliphatic glycols such as ethylene glycol, propylene glycol and butanediol, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, and esters such as neopentyl glycol hydroxypivalate. And glycols such as glycols. Examples of the chain extender having two amino groups include aromatic diamines such as tolylenediamine, xylylenediamine, and diphenylmethanediamine, ethylenediamine, propylenediamine, hexanediamine, 2,2-dimethyl-1,3- Propanediamine, 2-methyl-1,5-pentanediamine, trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- Aliphatic diamines such as decane diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, dicyclohexylmethanediamine, isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1, 3-Bisaminomethylcyclohexa And alicyclic diamines such as

  The urethane resin may use a solvent as a medium, but preferably uses water as a medium. In order to disperse or dissolve the urethane resin in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group is introduced into the urethane resin, and a water-soluble type. In particular, a self-emulsifying type in which an ionic group is introduced into the structure of a urethane resin to form an ionomer is preferable because of excellent storage stability of the liquid and water resistance and transparency of the obtained release layer.

  Examples of the ionic group to be introduced include various groups such as a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, and quaternary ammonium salt, and a carboxyl group is preferred. As a method for introducing a carboxyl group into a urethane resin, various methods can be taken in each stage of the polymerization reaction. For example, there are a method of using a carboxyl group-containing resin as a copolymer component during prepolymer synthesis, and a method of using a component having a carboxyl group as one component such as polyol, polyisocyanate, and chain extender. In particular, a method in which a desired amount of carboxyl groups is introduced using a carboxyl group-containing diol depending on the amount of this component charged is preferred. For example, dimethylolpropionic acid, dimethylolbutanoic acid, bis- (2-hydroxyethyl) propionic acid, bis- (2-hydroxyethyl) butanoic acid and the like are copolymerized with a diol used for polymerization of a urethane resin. Can do. The carboxyl group is preferably in the form of a salt neutralized with ammonia, amine, alkali metal, inorganic alkali or the like. Particularly preferred are ammonia, trimethylamine and triethylamine. In such a polyurethane resin, a carboxyl group from which the neutralizing agent has been removed in the drying step after coating can be used as a crosslinking reaction point by another crosslinking agent. Thereby, it is possible to further improve the durability, solvent resistance, water resistance, blocking resistance, and the like of the obtained release layer, as well as excellent stability in a liquid state before coating.

  It is also a preferred form that an antistatic agent is contained in the release layer to prevent defects due to adhesion of surrounding dust or the like due to film peeling or frictional charging as the antistatic release layer. The antistatic agent contained in the release layer is not particularly limited, and a conventionally known antistatic agent can be used. However, since it has good heat resistance and moist heat resistance, the polymer type charging agent can be used. An inhibitor is preferred. Examples of the polymer type antistatic agent include a compound having an ammonium group, a polyether compound, a compound having a sulfonic acid group, a betaine compound, and a conductive polymer.

  The compound having an ammonium group is a compound having an ammonium group in the molecule, and examples thereof include aliphatic amines, alicyclic amines, and ammonium compounds of aromatic amines. The compound having an ammonium group is preferably a compound having a polymer type ammonium group, and the ammonium group has a structure incorporated in the main chain or side chain of the polymer, not as a counter ion. It is preferable. For example, a polymer obtained by polymerizing a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine is used as a polymer compound having an ammonium group, which is preferably used. As the polymer, a monomer containing an addition polymerizable ammonium group or a precursor of an ammonium group such as an amine may be polymerized alone, or it may be a copolymer of a monomer containing these and another monomer. May be.

  Among the compounds having an ammonium group, compounds having a pyrrolidinium ring are also preferred in that they are excellent in antistatic properties and heat stability.

The two substituents bonded to the nitrogen atom of the compound having a pyrrolidinium ring are each independently an alkyl group, a phenyl group, and the like. Even if these alkyl groups and phenyl groups are substituted with the groups shown below, Good. Substitutable groups are, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, and halogen. Moreover, the two substituents bonded to the nitrogen atom may be chemically bonded. For example, — (CH ₂ ) _m — (m = 2 to 5), —CH (CH ₃ ) CH (CH ₃ ) —, —CH═CH—CH═CH—, —CH═CH—CH═N—, —CH═CH—N═C—, —CH ₂ OCH ₂ —, — (CH ₂ ) ₂ O (CH ₂ ) ₂ — and the like.

  A polymer having a pyrrolidinium ring can be obtained by cyclopolymerizing a diallylamine derivative using a radical polymerization catalyst. The polymerization is carried out by using a polymerization initiator such as hydrogen peroxide, benzoyl peroxide, tertiary butyl peroxide in a polar solvent such as water or methanol, ethanol, isopropanol, formamide, dimethylformamide, dioxane, acetonitrile as a solvent. Although it can implement by a method, it is not limited to these. In the present invention, a compound having a diallylamine derivative and a polymerizable carbon-carbon unsaturated bond may be used as a copolymerization component.

  Moreover, it is also preferable that it is a polymer which has a structure of following formula (1) at the point which is excellent in antistatic property and wet heat-resistant stability. A single polymer or copolymer, or a plurality of other components may be copolymerized.

For example, in the above formula, the substituent R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a hydrocarbon group such as a phenyl group, R ² is —O—, —NH— or —S—, and R ³ is R ¹ , R ⁵ , R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group. Or a hydrocarbon group provided with a functional group such as a hydroxyalkyl group, and X ⁻ represents various counter ions.

Among these, from the viewpoint of excellent antistatic properties and wet heat resistance, in particular, in the formula (1), the substituent R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ³ is preferably an alkyl group having 1 to 6 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are preferably each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably , R ⁴ , R ⁵ , or R ⁶ is a hydrogen atom, and the other substituent is an alkyl group having 1 to 4 carbon atoms.

  Examples of the anion serving as the counter ion (counter ion) of the ammonium group of the compound having an ammonium group described above include ions such as halogen ions, sulfonates, phosphates, nitrates, alkylsulfonates, and carboxylates.

  Moreover, the number average molecular weight of the compound which has an ammonium group is 1000-500000, Preferably it is 2000-350,000, More preferably, it is 5000-200000. When the molecular weight is less than 1000, the strength of the coating film may be weakened or the heat stability may be poor. On the other hand, when the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.

  Examples of polyether compounds include polyethylene oxide, polyether ester amide, acrylic resins having polyethylene glycol in the side chain, and the like.

  The compound having a sulfonic acid group is a compound containing a sulfonic acid or a sulfonate in the molecule. For example, a compound having a large amount of sulfonic acid or a sulfonate such as polystyrene sulfonic acid is preferably used. It is done.

  Examples of the conductive polymer include polythiophene-based, polyaniline-based, polypyrrole-based, and polyacetylene-based polymers. Among them, for example, polythiophene-based polymers using poly (3,4-ethylenedioxythiophene) in combination with polystyrene sulfonic acid. Are preferably used. The conductive polymer is preferable to the other antistatic agents described above in that the resistance value is low. However, on the other hand, it is necessary to devise measures such as reducing the amount used in applications where coloring and cost are a concern.

  In the range that does not impair the gist of the present invention, particles can be used in combination for the purpose of further improving slipperiness in forming the release layer. However, it may be preferable not to use the particles together from the viewpoint of the appearance of the release layer.

  Further, as long as it does not impair the gist of the present invention, the release layer is formed with an antifoaming agent, a coating property improver, a thickener, an organic lubricant, an ultraviolet absorber, an antioxidant, and a foaming agent as necessary. It is also possible to use dyes, pigments and the like in combination.

  As the ratio in the release layer, the ratio of the release agent cannot be generally specified because the appropriate amount varies depending on the type of the release agent, but is preferably in the range of 3% by weight or more, more preferably 15% by weight or more, Preferably it is the range of 25-99 weight%. If it is less than 3% by weight, the water repellency may not be sufficient.

  When a long-chain alkyl compound or a fluorine compound is used as the release agent, the proportion in the release layer is preferably 5% by weight or more, more preferably 15 to 99% by weight, still more preferably 20 to 95% by weight, Especially preferably, it is the range of 25 to 90 weight%. By using in the said range, water repellency and peelability with an adhesion layer become effective. The proportion of the crosslinking agent is preferably 95% by weight or less, more preferably 1 to 80% by weight, further preferably 5 to 70% by weight, and particularly preferably 10 to 50% by weight. Compounds, oxazoline compounds and isocyanate compounds are preferred, and melamine compounds are particularly preferred from the viewpoint of water repellency and the strength of the release layer.

  When a condensation type silicone compound is used as the release agent, the proportion in the release layer is preferably 3% by weight or more, more preferably 5 to 97% by weight, still more preferably 8 to 95% by weight, particularly preferably. Is in the range of 10 to 90% by weight. By using in the said range, water repellency and peelability with an adhesion layer become effective. The ratio of the crosslinking agent is preferably 97% by weight or less, more preferably 3 to 95% by weight, still more preferably 5 to 92% by weight, and particularly preferably 10 to 90% by weight. As the crosslinking agent, a melamine compound is preferable from the viewpoint of water repellency and the strength of the release layer.

  When an addition-type silicone compound is used as the release agent, the proportion in the release layer is preferably 5% by weight or more, more preferably 25% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70%. It is in the range of weight percent or more. The upper limit of the preferable range is 99% by weight, and the more preferable upper limit is 90% by weight. By using in the said range, water repellency and peelability with an adhesion layer become effective, and the external appearance of a mold release layer also becomes favorable.

  When wax is used as the release agent, the proportion in the release layer is preferably 5% by weight or more, more preferably 10 to 90% by weight, still more preferably 20 to 80% by weight, and particularly preferably 25 to 70%. It is in the range of wt%. By using in the said range, water repellency will become favorable. The proportion of the crosslinking agent is preferably 90% by weight or less, more preferably 10 to 70% by weight, and still more preferably 20 to 50% by weight. As the crosslinking agent, a melamine compound is preferable from the viewpoint of water repellency and the strength of the release layer.

  Furthermore, when an antistatic release layer having antistatic performance is provided in the release layer, the proportion of the antistatic agent as a proportion in the antistatic release layer varies depending on the type of antistatic agent, so it is generally Although it cannot be said, Preferably it is the range of 0.5 weight% or more, More preferably, it is 3-90 weight%, More preferably, it is the range of 5-70 weight%, Especially preferably, it is the range of 8-60 weight%. If it is less than 0.5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  When an antistatic agent other than a conductive polymer is used as the antistatic agent, the proportion in the antistatic release layer is preferably 5% by weight or more, more preferably 10 to 90% by weight, still more preferably 20 to 70% by weight. %, Particularly preferably 25 to 60% by weight. If it is less than 5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  When a conductive polymer is used as the antistatic agent, the proportion in the antistatic release layer is preferably 0.5% by weight or more, more preferably 3 to 70% by weight, even more preferably 5 to 50% by weight, particularly Preferably it is the range of 8-30 weight%. If it is less than 0.5% by weight, the antistatic effect is not sufficient, and the effect of preventing the adhesion of surrounding dust and the like may not be sufficient.

  Analysis of the components in the release layer can be performed by analysis such as TOF-SIMS, ESCA, fluorescent X-ray, IR, and the like.

  Regarding the formation of the release layer, the above-described series of compounds is used as a solution or a dispersion of a solvent, and the solution is prepared by coating a liquid with a solid content concentration adjusted to about 0.1 to 80% by weight as a guide. It is preferable. In particular, when provided by in-line coating, an aqueous solution or a water dispersion is more preferable. A small amount of an organic solvent may be contained in the coating solution for the purpose of improving the dispersibility in water, improving the film forming property, and the like. Moreover, only one type of organic solvent may be used, and two or more types may be used as appropriate.

  The thickness of the release layer is preferably 0.001 to 1 μm, more preferably 0.01 to 0.5 μm, and still more preferably 0.02 to 0.2 μm. By using the film thickness of the release layer within the above range, good appearance, water repellency, and anti-sticking property to the adhesive layer can be obtained.

  As a method for forming the release layer, for example, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, Conventionally known coating methods such as kiss coating, spray coating, calendar coating, extrusion coating and the like can be used.

  The drying and curing conditions for forming the release layer on the film are not particularly limited, but in the case of the method by coating, preferably for the drying of a solvent such as water used in the coating liquid, It is 70-150 degreeC, More preferably, it is 80-130 degreeC, More preferably, it is the range of 90-120 degreeC. The drying time is generally 3 to 200 seconds, preferably 5 to 120 seconds.

  Moreover, you may use together heat processing and active energy ray irradiation, such as ultraviolet irradiation, as needed. The polyester film constituting the laminated polyester film may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  The release polyester layer of the laminated polyester film of the present invention has an adhesive layer on the surface of the polyester film on the hunt side. Although there is no restriction | limiting in particular as how to provide this adhesion layer, The method of sticking the adhesion layer provided on the releasable base material to the film of this invention, and the coating liquid containing an adhesion layer component directly There is a method of applying.

  In the method of bonding from a releasable base material, it is necessary to be concerned about bubbles and wrinkles entering when bonding, but there is an advantage that a process such as heat is not added to the final adhesive film is there. In the method of direct application, since heat is applied to the film for drying and curing when the adhesive layer is provided, it may be necessary to consider changes in the shrinkage of the film, but the resulting adhesive layer is uniform. There is also an advantage of becoming. Generally, it can be appropriately selected according to the configuration and purpose of the final product.

  Although there is no restriction | limiting in particular in the thickness of an adhesion layer, 3-100 micrometers is preferable and 5-40 micrometers is more preferable. If it is thinner than this, it may be difficult to form the coating and the adhesive strength may be insufficient. If it is thicker than this range, the adhesive strength tends to be too high, and the cost tends to be disadvantageous.

  As the pressure-sensitive adhesive, generally known pressure-sensitive adhesives such as acrylic, silicone, rubber, and synthetic rubber can be used. In particular, an acrylic pressure-sensitive adhesive is preferable because it has excellent transparency and heat resistance and can easily adjust the peeling force.

  As the base polymer of the acrylic pressure-sensitive adhesive, a (meth) acrylic acid alkyl ester copolymer is suitable. The alkyl group has an average carbon number of about 1 to 12, and examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. These may be used alone or in combination. What has a C1-C9 alkyl group especially is preferable.

  Further, one or more kinds of various monomers are introduced into the base polymer by copolymerization for the purpose of improving adhesion and heat resistance. Specific examples of such copolymerization monomers include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid 6 Hydroxyl group-containing monomers such as hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Monomer-containing monomer; Caprolac of acrylic acid Adducts such as styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, etc. A sulfonic acid group-containing monomer, and a phosphoric acid group-containing monomer such as 2-hydroxyethylacryloyl phosphate. In addition, (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc. Monomer; (meth) acrylic acid aminoethyl, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid t-butylaminoethyl and other (meth) acrylic acid alkylaminoalkyl monomers; (meth) acrylic (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl acid and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- ( (Meta) acryloyl- -Succinimide monomers such as oxyoctamethylene succinimide and N-acryloylmorpholine are also exemplified as examples of monomers for modification, and vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, Vinyl monomers such as vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic amides, styrene, α-methylstyrene, N-vinylcaprolactam; acrylonitrile, methacrylo Cyanoacrylate monomers such as nitriles; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Polyethyleneglycol (meth) acrylate Glycol-based acrylic ester monomers such as (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) acrylic acid methoxypolypropylene glycol; (meth) acrylic acid tetrahydrofurfuryl, fluorine (meth) acrylate Acrylic acid ester monomers such as silicone (meth) acrylate and 2-methoxyethyl acrylate can also be used. Among these, it is preferable to use a hydroxyl group-containing monomer from the viewpoint of adhesion to a polyester film as a base material and heat resistance.

  In particular, a carboxyl group-containing monomer such as acrylic acid is preferably used. The proportion of the copolymerization monomer in the acrylic polymer is preferably 0.1 to 10% by weight.

  The pressure-sensitive adhesive is preferably a pressure-sensitive adhesive composition containing a crosslinking agent. Examples of the polyfunctional compound that can be incorporated into the pressure-sensitive adhesive include organic crosslinking agents and polyfunctional metal chelates. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, and an imine crosslinking agent. As the organic crosslinking agent, an isocyanate crosslinking agent is preferable.

  The blending ratio of the base polymer such as the acrylic polymer and the crosslinking agent is not particularly limited, but usually 0.01 to 10 parts by weight of the crosslinking agent (solid content) is preferable with respect to 100 parts by weight of the base polymer (solid content). Furthermore, 0.1-5 weight part is more preferable.

  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 measurement method and evaluation method used in the present invention are as follows.

(1) Method for Measuring Intrinsic Viscosity of Polyester 1 g of polyester was precisely weighed, 100 ml of a mixed solvent of phenol / tetrachloroethane = 50/50 (weight ratio) was added and dissolved, and measurement was performed at 30 ° C.

(2) Method of measuring terminal carboxyl group amount equivalent / t When sampling a polyester chip, it is pulverized. When sampling a polyester film, the necessary amount is appropriately cut in advance with a cutter or scissors. Once the sample is obtained, it is dried for 15 minutes at 140 ° C. in a hot air dryer, 1.0 g from the sample cooled to room temperature in a desiccator is accurately weighed and collected in a test tube, and 30 ml of benzyl alcohol is added and dried. The solution was dissolved at 195 ° C. for 3 minutes while blowing nitrogen gas, and then 50 ml of chloroform was gradually added and cooled to room temperature. Add 1-2 drops of phenol red indicator to the resulting solution and titrate with 0.1 (N) benzyl alcohol solution of caustic soda while blowing dry nitrogen gas, and finish when it turns from yellow to red It was. It is assumed that 1.0 g of the polyester raw material is contained in the supernatant. Further, as a blank, the same operation was carried out without a polyester resin sample, and the acid value was calculated by the following formula.

Acid value equivalent / t = (A−B) × 0.1 × f / W
[Where A is the amount of benzyl alcohol solution of 0.1N caustic soda required for titration (μl), B is the amount of benzyl alcohol solution of 0.1N caustic soda required for titration with a blank (μl) , W is the amount (g) of the polyester resin sample, and f is the titer of the benzyl alcohol solution of caustic soda of 0.1 (N)]

  The titer (f) of 0.1N caustic soda benzyl alcohol solution was obtained by taking 5 ml of methanol into a test tube, adding 1 to 2 drops of phenol red ethanol solution as an indicator, and 0.1N caustic soda benzyl alcohol. Titrate to the color change point with 0.4 ml of solution, then add 0.2 ml of 0.1N hydrochloric acid aqueous solution of known titer as a standard solution and add it again to the color change point with 0.1N sodium hydroxide in benzyl alcohol. Titration was performed (the above operation was performed under blowing of dry nitrogen gas). The titer (f) was calculated by the following formula.

  Titer (f) = Titer of 0.1N aqueous hydrochloric acid × Amount of collected 0.1N aqueous hydrochloric acid (μl) / Titration of 0.1N sodium hydroxide in benzyl alcohol (μl)

(3) Measuring method of average particle size (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 defined as the average particle size.

(4) Measuring method of number average molecular weight It measured using GPC (Tosoh Corporation HLC-8120GPC). The number average molecular weight was calculated in terms of polystyrene.

(5) Internal haze measurement method Carefully wipe the adhesive layer of the film with ethyl acetate so as not to damage the film, and the state of the polyester film laminated with the release layer without the adhesive layer (release layer laminated polyester) Film). The measurement was performed according to JIS K 7136 by immersing the film in ethanol using a haze meter “HZ-2” manufactured by Suga Test Instruments Co., Ltd.

  The wiping off of the adhesive layer is not particularly limited as long as the adhesive layer can be wiped off. In addition to ethyl acetate, toluene, dimethylformamide, or the like is preferably used.

(6) Heat shrinkage measuring method Carefully wipe the adhesive layer of the film with ethyl acetate so as not to damage the film, and the state of the polyester film in which the release layer without the adhesive layer is laminated (release layer lamination) Measurement was carried out using a polyester film. The sample was treated for 30 minutes in an oven maintained at 95 ° C. under no tension, the length of the sample before and after that was measured, and the heat shrinkage rate was calculated by the following formula.
Heat shrinkage rate (%) = {(L0−L1) / L0} X100
(In the above formula, L0 is the sample length before the heat treatment, L1 is the sample length after the heat treatment) Five points were measured in the film longitudinal direction (MD) and the width direction (TD), and the average value was obtained for each.

  The wiping off of the adhesive layer is not particularly limited as long as the adhesive layer can be wiped off. In addition to ethyl acetate, toluene, dimethylformamide, or the like is preferably used.

(7) Water drop contact angle On the polyester film surface side forming the release layer, the contact angle between the sample film and distilled water at a temperature of 23 ° C. and a humidity of 50% RH was determined using a contact angle meter CA-DT manufactured by Kyowa Interface Chemical Co., Ltd. -Measured using type A. The contact angle was measured at two points on the left and right and a total of 6 points with 3 samples, and the average value was obtained as the contact angle. The diameter of the water droplet was 2 mm, and the numerical value one minute after the dropping was read.

(8) Color tone Reflection method Method of measuring y value Carefully wipe the adhesive layer of the film with ethyl acetate so as not to damage the film, and the state of the polyester film laminated with the release layer without the adhesive layer (release) Measurement was carried out using a layer-laminated polyester film. The color reflection method y value was measured with a spectrocolorimeter “CM-3700d” manufactured by Konica Minolta Co., Ltd. according to JIS-Z-5722.

  In addition, the measurement is performed by, for example, 43 sheets when the film thickness is 23 μm, 20 sheets when the film is 50 μm, 8 sheets when the film is 125 μm, 5 sheets when the film is 188 μm, and a total thickness of 900 μm to 1100 μm. A plurality of films were overlapped so as to be closest to 1000 μm.

  The wiping off of the adhesive layer is not particularly limited as long as the adhesive layer can be wiped off. In addition to ethyl acetate, toluene, dimethylformamide, or the like is preferably used.

(9) Evaluation method for suitability of protective film member (a) Water repellency Super-Xenon weather meter manufactured by Suga Test Instruments Co., Ltd .: From a film roll slitted to a product width of 800 mm using SX75, MD: 135 mm × TD : A 55 mm rectangular sample was cut out, attached to a tester so that the release layer surface side could be tested, and the film surface properties on the release layer surface side when processed under the following conditions were evaluated from the following viewpoints.

[conditions]
Irradiance: 100 W / m2 (in the range of 300-400 nm)
Filter: Inner / Outer = Quartz / # 275
Black panel temperature: spraying / non-spraying = non-control / 50 ° C
Temperature in the test tank: spraying / non-spraying = 24 ° C./non-control Humidity in the testing tank: spraying / non-spraying = 95% RH / 50% RH
Cycle time: spraying / non-spraying = 20 minutes / 20 minutes Test time: 24 hours

[Evaluation]
A: There is no adhesion of water droplets, and the condition before the test can be maintained, and transparency can be confirmed. B: Adhesion of water droplets remains in a very small part. C: Adhesion of water droplets partially remains. D: Adhesion of water droplets. Remains and the traces of water droplets can be confirmed

(B) Hydrolysis resistance Using a personal pressure cooker (manufactured by Hirayama Seisakusho Co., Ltd.), the polyester film is treated in an atmosphere of 120 ° C.-100% RH. With Autograph AG-I (manufactured by Shimadzu Corp., Shimadzu Corp.), the tensile elongation at break as the mechanical properties of the film at a speed of 200 mm / min with respect to the film forming direction (MD) in the same direction (MD) Is measured to determine the tensile elongation at break rate. The tensile breaking elongation maintenance ratio is obtained from the following formula, that is, the quotient of the tensile breaking elongation before and after the personal pressure cooker treatment.

Tensile rupture elongation retention rate [%] = “tensile rupture elongation after personal pressure cooker treatment” ÷ “tensile rupture elongation before personal pressure cooker treatment” × 100
From the time when the tensile elongation at break maintenance rate reached less than 10%, the following criteria were used for evaluation.
○: Time at which the tensile elongation at break was less than 10%: 72 hr or more Δ: Time at which the tensile elongation at break was less than 10%: from 36 hr to less than 72 hr ×: Tensile elongation at break was 10 Time to reach less than%: Less than 36 hr

(C) Transparency The film was cut into A4 size, observed under a three-wavelength fluorescent lamp, and evaluated according to the following criteria.
○: There is no white cloudiness and there is transparency ×: White cloudiness is seen and there is no transparency

(10) Measuring method of surface resistance Using a high resistance measuring instrument made by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B, the polyester film is fully conditioned in a measurement atmosphere of 23 ° C. and 50% RH, and then applied. The surface resistance of the antistatic layer after 1 minute at a voltage of 100 V was measured.

(11) Dust adhesion evaluation method on the release layer (antistatic layer) side After sufficiently adjusting the humidity of the polyester film in a measurement atmosphere of 23 ° C. and 50% RH, the antistatic layer is rubbed 10 times with a cotton cloth. This was brought close to the finely crushed cigarette ash and the ash adhesion was evaluated according to the following criteria.
○: Even if the film is brought into contact with ash, it does not adhere. Δ: When the film is brought into contact with ash, it adheres a little.

Examples and Comparative Examples are shown below, and the method for producing the polyester used in the Examples and Comparative Examples is as follows.
<Method for producing polyester (a)>
Using 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol as starting materials, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is placed in the reactor, the reaction start temperature is set to 150 ° C., and the methanol is distilled off gradually. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. After 0.04 part of ethyl acid phosphate was added to this reaction mixture, 0.03 part of antimony trioxide was added and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.67 due to a change in stirring power of the reaction vessel, and the polymer was discharged under nitrogen pressure. The obtained polyester (a) had an intrinsic viscosity of 0.67 dl / g and a terminal carboxyl group content of 33 equivalents / t.

<Method for producing polyester (b)>
In the method for producing polyester (a), after adding 0.04 part of ethyl acid phosphate, 0.3 part of silica particles having an average particle diameter of 2.2 μm dispersed in ethylene glycol and 0.04 part of antimony trioxide are added. In addition, polyester (b) was obtained using the same method as the production method of polyester (a) except that the polycondensation reaction was stopped at the time corresponding to the intrinsic viscosity of 0.64. The obtained polyester (b) had an intrinsic viscosity of 0.64 dl / g and a terminal carboxyl group content of 32 equivalents / t.

<Method for producing polyester (c)>
Continuous polymerization apparatus comprising one slurry preparation tank, a two-stage esterification reaction tank connected in series thereto, and a three-stage melt polycondensation tank connected in series to the second esterification reaction tank And terephthalic acid and ethylene glycol are continuously fed to the slurry preparation tank at a weight ratio of 100: 45, and an ethylene glycol solution of ethyl acid phosphate is contained as a phosphorus atom in the produced polyester resin. A slurry is prepared by continuously adding, stirring and mixing in an amount of 4 ppm by weight, and this slurry is set at 267 ° C., a relative pressure of 100 kPa, and an average residence time of 4 hours under a nitrogen atmosphere. , Continuously fed to the first stage esterification reaction tank where the reaction product exists at a flow rate of 120 kg / hr, and then the first stage esterification The reaction product was continuously transferred to a second stage esterification reaction tank set at 265 ° C., a relative pressure of 5 kPa, and an average residence time of 2 hours under a nitrogen atmosphere, and further esterified. At that time, an amount of 322 mol / ton was continuously supplied to the polyester resin producing ethylene glycol through an upper pipe provided in the second stage esterification reaction tank. In this case, the esterification rate in the second stage esterification reaction tank was 97%.

  The above esterification reaction product was continuously supplied to the first stage polycondensation reaction tank via the transfer pipe. At this time, the discharge pressure of the transfer pump provided in the transfer pipe was 500 kPa. A 0.6 wt% solution of magnesium acetate tetrahydrate in ethylene glycol is continuously added to the esterification reaction product in the transfer pipe in such an amount that the content as magnesium atoms is 7 ppm by weight with respect to the produced polyester resin. Added to. Using an addition pipe, an ethylene glycol solution of tetra-n-butyl titanate was continuously added to the resulting polyester resin in an amount such that the content as titanium atoms was 4 ppm by weight.

  The melt polycondensation reaction conditions were 269 ° C. in the first stage polycondensation reaction tank, absolute pressure 4 kPa, average residence time 1 hour, 274 ° C. in the second stage polycondensation reaction tank, 0.4 kPa absolute pressure, average residence time The time was 0.9 hours, the third stage polycondensation reaction tank was 277 ° C., the absolute pressure was 0.2 kPa, and the average residence time was 1 hour. The melt polycondensation reaction product taken out from the third stage polycondensation reaction tank is extruded from a die into a strand, cooled and solidified, cut with a cutter, and one piece of polyester resin chip having an average particle weight of 24 mg: polyester (C). The intrinsic viscosity of the polyester (c) was 0.64 dl / g, and the amount of terminal carboxyl groups was 15 equivalents / t.

<Method for producing polyester (d)>
Polyester (c) is used as a starting material, and continuously fed in a stirrer crystallizer maintained at about 160 ° C. in a nitrogen atmosphere in a state where the chips do not overlap so that the residence time is about 60 minutes. After crystallizing, the residence time is adjusted so that the intrinsic viscosity of the resulting polyester resin is 0.85 dl / g at 215 ° C. in a nitrogen atmosphere continuously supplied to a tower-type solid phase polycondensation device. To obtain a polyester (d). The amount of terminal carboxyl groups was 6 equivalent / t.

Examples of the compounds constituting the release layer and the adhesive layer are as follows.
(Example compounds)
・ Releasing agent (long chain alkyl group-containing compound): (IA)
To a four-necked flask, 200 parts of xylene and 600 parts of octadecyl isocyanate were added and heated with stirring. From the time when xylene began to reflux, 100 parts of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 88 mol% was added in small portions over a period of about 2 hours. After the addition of polyvinyl alcohol, the reaction was completed by further refluxing for 2 hours. When the reaction mixture was cooled to about 80 ° C. and added to methanol, the reaction product was precipitated as a white precipitate. This precipitate was filtered off, added with 140 parts of xylene, and heated to dissolve completely. After repeating the operation of adding methanol again to precipitate several times, the precipitate was washed with methanol and dried and ground.

・ Releasing agent (fluorine compound): (IB)
Fluorine compound aqueous dispersion having the following composition: Octadecyl acrylate / perfluorohexyl ethyl methacrylate / vinyl chloride = 66/17/17 (% by weight)

-Polyether group-containing condensed silicone: (IC)
Polyether group-containing silicone having a number average molecular weight of 7000 (silicone siloxane) containing 1 polyethylene glycol (terminated with a hydroxyl group) having an ethylene glycol chain of 8 with respect to dimethylsiloxane 100 in the dimethyl silicone side chain in a molar ratio. When the bond is 1, the ether bond of the polyether group is 0.07 at a molar ratio). 3% of low molecular components having a number average molecular weight of 500 or less, no vinyl group (vinyl silane) and hydrogen group (hydrogen silane) bonded to silicon exist. In addition, this compound mix | blends the water which disperse | distributes sodium dodecyl benzenesulfonate in the ratio of 0.25 by making polyether group containing silicone 1 by weight ratio.

・ Wax: (ID)
An emulsification facility with an internal capacity of 1.5 L equipped with a stirrer, thermometer, temperature controller, melting point 105 ° C., acid value 16 mgKOH / g, density 0.93 g / mL, number average molecular weight 5000 polyethylene oxide wax 300 g, ion-exchanged water 650 g After adding 50 g of decaglycerin monooleate surfactant and 10 g of 48% potassium hydroxide aqueous solution and replacing with nitrogen, the mixture was sealed, stirred at 150 ° C. for 1 hour at high speed, cooled to 130 ° C., and a high-pressure homogenizer at 400 atm. A wax emulsion passed through and cooled to 40 ° C.

・ Polyester resin: (IIA)
Water dispersion of polyester resin having the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 50 / 46/4 // 70/20/10 (mol%)

・ Acrylic resin: (IIB)
Acrylic resin aqueous dispersion having the following composition: ethyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 48/45/4/3 (% by weight)

Melamine compound: (III) Hexamethoxymethylolmelamine Antistatic agent (quaternary ammonium salt compound): (IVA)
Polymer polymerized with the following composition having a pyrrolidinium ring in the main chain: Diallyldimethylammonium chloride / dimethylacrylamide / N-methylolacrylamide = 90/5/5 (mol%). Number average molecular weight 30000.
・ Antistatic agent (compound having ammonium group): (IVB)
A polymer compound having a number average molecular weight of 50000, wherein the counter ion is a methanesulfonic acid ion, comprising a structural unit of the following formula (2).

The coating solution for forming the adhesive layer is prepared as follows.
<Adjustment of adhesive solution>
Japan is an isocyanate crosslinking agent for a solution of acrylic polymer having a weight average molecular weight of 2 million consisting of a copolymer of butyl acrylate / acrylic acid / 2-hydroxyethyl acrylate in a weight ratio of 100/6 / 0.1. Coronate L manufactured by Polyurethane Industry Co., Ltd., 3-glycidoxypropyltrimethoxysilane as a silane coupling agent, and ethyl acetate were added to prepare a pressure-sensitive adhesive solution having a solid content concentration of 10%. In terms of solid content in the solution, acrylic copolymer / coronate L / 3-glycidoxypropyltrimethoxysilane = 100/3 / 0.6.

Example 1:
Mixing the above-mentioned polyesters (a) and (b) in proportions of 85% and 15%, respectively, using the mixed raw material as the raw material for the A layer and the raw material for the B layer as 100% for the polyester (a). Each is supplied to a screw extruder, melted at 285 ° C., and two types and three layers (A / B / A = 4: 42: 4) with the A layer as the outermost layer (surface layer) and the B layer as the intermediate layer (Amount) was coextruded from the die, extruded from the die, and cooled and solidified on a cooling roll set at a surface temperature of 22 ° C. using an electrostatic application adhesion method to obtain an unstretched sheet. Next, the film was stretched 3.3 times in the machine direction at a film temperature of 83 ° C. using the roll peripheral speed difference, and then the coating solution 1 shown in Table 1 below was applied to one side of the longitudinally stretched film. (After drying) is applied to 0.03 μm, led to a tenter, stretched 4.3 times in the transverse direction at 130 ° C., heat-treated at a main crystallization zone temperature of 236 ° C., and then transversely The obtained master roll was slit into a film roll having a product width of 800 mm and a winding length of 1000 m to obtain a biaxially stretched polyester film roll having a thickness of 50 μm. Further, the pressure-sensitive adhesive solution is applied to the surface of the polyester film opposite to the release layer so that the thickness (after drying) of the pressure-sensitive adhesive layer is 25 μm and dried to obtain a laminated polyester film having the pressure-sensitive adhesive layer. It was.

  When the obtained laminated polyester film was evaluated, the water droplet contact angle was as high as 103 degrees, the water repellency was good, and there was no concern about water droplet traces or dirt adhesion. The properties of this film are shown in Tables 2 and 3 below.

Examples 2-4:
In Example 1, except having changed a mold release layer composition into the composition shown in Table 1, it manufactured like Example 1 and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film had a high water droplet contact angle and good water repellency.

Example 5:
A mixed raw material obtained by mixing polyester (a) and (b) in proportions of 86% and 14%, respectively, and a mixed raw material obtained by mixing polyester (a) and (d) in proportions of 90% and 10%. Co-extruded as a raw material for layer B with a layer configuration with a discharge rate of A / B / A = 3: 44: 3, heat-treated at a main crystallization zone temperature of 215 ° C., and then relaxed 9% in the lateral direction A laminated polyester film was obtained in the same manner as in Example 1 except that.

  When the obtained laminated polyester film was evaluated, the water droplet contact angle was as high as 103 degrees, the water repellency was good, and there was no concern about water droplet traces or dirt adhesion. Moreover, the hydrolysis resistance was also good. The properties of this film are shown in Tables 2 and 3 below.

Examples 6-8:
In Example 5, it manufactured like Example 5 except having changed a mold release layer composition into the composition shown in Table 1, and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film had a high water droplet contact angle, good water repellency, and good hydrolysis resistance.

Example 9:
A heat treatment was carried out at a main crystallization zone temperature of 240 ° C., and then production was carried out in the same manner as in Example 5 except that the film was relaxed by 5% in the transverse direction to obtain a laminated polyester film.

  When the obtained laminated polyester film was evaluated, the water droplet contact angle was as high as 103 degrees, the water repellency was good, and there was no concern about water droplet traces or dirt adhesion. Moreover, the hydrolysis resistance was also good. The properties of this film are shown in Tables 2 and 3 below.

Examples 10-20:
In Example 9, it manufactured like Example 9 except having changed a mold release layer composition into the composition shown in Table 1, and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film had a high water droplet contact angle, good water repellency, and good hydrolysis resistance. Moreover, about Examples 18-20, as shown in Table 4, it was excellent also in antistatic property.

Comparative Example 1:
A laminated polyester film was obtained in the same manner as in Example 1 except that the release layer was not provided in Example 1. However, the water droplet contact angle is low, water repellency is not observed, and there is a concern about water droplet traces and dirt adhesion. The properties of this film are shown in Tables 2 and 3 below.

Comparative Example 2:
In Example 1, except having changed a mold release layer composition into the composition shown in Table 1, it manufactured like Example 1 and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film was a film having a low water droplet contact angle, no water repellency, and concerns about water droplet traces and dirt adhesion.

Comparative Example 3:
In Example 5, it manufactured like Example 5 except having changed a mold release layer composition into the composition shown in Table 1, and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film was a film having a low water droplet contact angle, no water repellency, and concerns about water droplet traces and dirt adhesion.

Comparative Example 4:
In Example 9, it manufactured like Example 9 except having changed a mold release layer composition into the composition shown in Table 1, and obtained the laminated polyester film. As shown in Tables 2 and 3 below, the finished film was a film having a low water droplet contact angle, no water repellency, and concerns about water droplet traces and dirt adhesion.

Comparative Examples 5 and 6:
A mixed raw material in which polyesters (a) and (b) were mixed at a ratio of 86% and 14%, respectively, was used as a raw material for the A layer, and polyester (a) 15%, polyester (d) 10%, A mixed raw material obtained by mixing 75% of the regenerated product from the generated ear part or master roll ear part is used as a B layer, and co-extruded with a discharge amount of A / B / A = 3: 44: 3, and a release layer A laminated polyester film was obtained in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The completed film was a film having poor hydrolysis resistance and transparency as shown in Tables 2 and 3 below.

  The laminated polyester film of the present invention can be suitably used as various protective films.

Claims (1)

It is a laminated polyester film having a release layer on one surface of the polyester film and an adhesive layer on the other surface, and the internal haze of the laminated film of the release layer and the polyester film is 1.0% or less A laminated polyester film characterized by being: