JP2015217547A - Laminated polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester film which can be suitably used in an application requiring excellent releasability and antistatic properties, especially in an application requiring heat resistance, for example, as a process film used in various processes such as a process sheet for transfer such as simultaneous molding and transferring and producing a flexible printed wiring board and a plastic sheet.SOLUTION: There is provided a laminated polyester film which has a coating layer formed from a coating liquid containing a mold release agent, a compound having a pyrrolidinium ring and an isocyanate-based compound on at least one surface of a polyester film.

Description

  The present invention relates to a release film, and particularly for applications requiring heat resistance, for example, for transfer such as molding simultaneous transfer, for manufacturing flexible printed wiring boards, for process paper for manufacturing plastic sheets, etc. A release polyester film suitable as a process film used in the process is provided.

  Conventionally, polyester films represented by polyethylene terephthalate and polyethylene naphthalate have excellent mechanical properties, dimensional stability, flatness, heat resistance, chemical resistance, optical properties, etc., and cost performance. It is used for various purposes. When a polyester film is used as a release film, it has a drawback of poor practicality because of its insufficient release properties for various resins and adhesives. For this reason, a method for laminating a releasable coating film on the surface of a polyester film has been studied. For example, a method of applying and laminating a long chain alkyl group-containing resin on a polyester film surface (Patent Documents 1 and 2) has been proposed.

  On the other hand, polyester films have a characteristic that they are easily charged due to static electricity as a problem common to plastic films. Therefore, there are problems such as poor runnability of the processed product or processed product, the problem of attracting surrounding dust and the like, and the problem of causing trouble in the product due to charging when peeling for process paper. As for suppression of charging of the polyester film, there is a method of providing a coating layer having antistatic performance on the film.

  In relation to the above problems, Patent Documents 3 to 6 propose a polyester film having a coating layer containing a cationic antistatic agent and having good runnability on a coater.

  Examples of applications that use polyester film as a release film include heat and pressure applied to the film during various processes, such as transfer for molding simultaneous transfer, manufacturing of flexible printed wiring plates, and process paper for manufacturing plastic sheets. There is something. When used for these heat-sensitive applications, the release film created by the above method has a problem that the release property of the film deteriorates and the film cannot be removed smoothly, and has excellent heat resistance. There is a need for a release film.

JP 2002-240016 A JP 2006-022136 A JP-A-5-1164 Japanese Patent Laid-Open No. 8-143691 JP 2008-81551 A JP 2008-81552 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is in various processes such as transfer for molding simultaneous transfer, for manufacturing a flexible printed wiring board, for process paper for manufacturing a plastic sheet, etc. An object of the present invention is to provide a release polyester film having excellent antistatic properties as a process film to be used, and having little deterioration of release properties due to heat during processing.

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

  That is, the gist of the present invention is a laminated polyester film characterized by having a coating layer formed from a coating solution containing a release agent, a compound having a pyrrolidinium ring, and an isocyanate compound on at least one side of the polyester film. Exist.

  According to the laminated polyester film of the present invention, when used as a film for various processes such as for production of an antireflection film for transfer, it has excellent antistatic properties, high heat resistance, and depends on heat during processing. A release polyester film with little deterioration in releasability can be provided, and its industrial value is high.

  The polyester film constituting the 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 the gist of the present invention is not exceeded other than the two-layer or three-layer structure. It may be a multilayer and is not particularly limited. For example, it is possible to change the raw material of the surface layer and the intermediate layer into a three-layer structure for the purpose of effectively improving various properties using a polyester film with high functionality as the surface layer raw material.

  The polyester used in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, the dicarboxylic acid component of the copolyester includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.), etc. 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexane dimethanol, neopentyl glycol, is mentioned.

  There is no restriction | limiting in particular as a polymerization catalyst of polyester, A conventionally well-known compound can be used, For example, an antimony compound, a titanium compound, a germanium compound, a manganese compound, an aluminum compound, a magnesium compound, a calcium compound etc. are mentioned. Among these, antimony compounds have the advantage of being inexpensive and having high catalytic activity.

  In the polyester layer of the film of the present invention, particles can be blended mainly for the purpose of imparting slipperiness and preventing scratches in each step. When the particles are blended, the kind of the particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness, and specific examples thereof include, for example, silica, calcium carbonate, magnesium carbonate, barium carbonate, sulfuric acid. Examples thereof include inorganic particles such as calcium, calcium phosphate, magnesium phosphate, 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.

  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 the range of 0.1-3 micrometers. By using the average particle diameter in the above range, an appropriate surface roughness can be imparted to the film, and good slipperiness and smoothness can be ensured.

  Furthermore, the particle content in the polyester layer is preferably 5% by weight or less, more preferably in the range of 0.0003 to 3% by weight. When there are no or few particles, the film becomes highly transparent and a good film is obtained, but the slipperiness may be insufficient, so the slipperiness is improved by putting particles in the coating layer. Etc. may be necessary. Moreover, when there is too much particle content, the transparency of a film may be inadequate.

  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.

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

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

  The thickness of the polyester film in the present invention is not particularly limited as long as it can be formed as a film, but it is preferably from 5 to 300 μm, more preferably from the viewpoint of mechanical strength, handling properties and productivity. Is in the range of 10-125 μm.

  Next, although the manufacture example of the polyester film in this invention is demonstrated concretely, it is not limited to the following manufacture examples at all. That is, a method is preferred in which pellets obtained by drying the polyester raw material described above are extruded as a molten sheet from a die using an extruder and cooled and solidified with a cooling roll to obtain an unstretched 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, and an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed. Next, the obtained unstretched sheet is stretched in the biaxial direction. In that case, first, the unstretched sheet is stretched in one direction by a roll or a tenter type stretching machine. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, the film is stretched in the direction perpendicular to the first stretching direction. In that case, the stretching temperature is usually 70 to 170 ° C., and the stretching ratio is usually 3.0 to 7 times, preferably 3.5 to 6 times. is there. Subsequently, heat treatment is performed at a temperature of 180 to 270 ° C. under tension or under relaxation within 30% to obtain a biaxially oriented film. In the above-described stretching, a method in which stretching in one direction is performed in two or more stages can be employed. In that case, it is preferable to carry out so that the draw ratios in the two directions finally fall within the above ranges.

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

  Next, formation of the coating layer which comprises the laminated polyester film in this invention is demonstrated. Regarding the coating layer, it may be provided by in-line coating which treats the film surface during the process of forming a polyester film, or offline coating which is applied outside the system on a once produced film may be adopted. More preferably, it is formed by in-line coating.

  In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of the polyester to heat setting after stretching and winding up. 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 this method, film formation and coating layer formation can be performed at the same time. In order to perform stretching after coating, the thickness of the coating layer can be changed depending on the stretching ratio, and thin film coating can be performed more easily than an off-line coating film. Further, by providing the coating layer on the film before stretching, the coating layer can be stretched together with the base film, whereby the coating 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 coating layer is improved, and the coating layer and the base film can be more firmly adhered to each other. .

  In the present invention, it is an essential requirement to have a coating layer formed from a coating solution containing a release agent, a compound having a pyrrolidinium ring, and an isocyanate compound.

  The coating layer in the present invention has a release performance suitable as a process film used in various processes such as transfer for molding simultaneous transfer, for manufacturing flexible printed wiring boards, for process paper for manufacturing plastic sheets, etc. It is provided in order to improve.

  The release agent used for forming the coating layer of the film of the present invention is used for improving the release property of the film, and is not particularly limited, and a conventionally known release agent can be used. Examples thereof include long-chain alkyl compounds, waxes, fluorine compounds, and silicone compounds. Among these, a long-chain alkyl compound, a wax, and a fluorine compound are preferable because they are less contaminated, and a long-chain alkyl compound and a fluorine compound are preferable because they are excellent in releasability. Moreover, a long-chain alkyl compound is preferable from the viewpoint that the peeling force after heating is relatively difficult to increase. These release agents may be used alone or in combination.

  The long-chain alkyl compound is a compound having a linear or branched alkyl group having usually 6 or more, preferably 8 or more, 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, and long-chain alkyl group-containing ether compounds. 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, in view of releasability and ease of handling, the long chain alkyl group-containing isocyanate preferably has 8 or more carbon atoms, more preferably 12 or more, and particularly preferably 18 or more.

  Polymer compounds having a long-chain alkyl group in the side chain are polymers of long-chain alkyl (meth) acrylates, copolymerization of long-chain alkyl (meth) acrylates with other vinyl group-containing monomers, or long-chain alkyls. It can also be obtained by transesterification with other vinyl group-containing monomers after polymerization of (meth) acrylate. 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 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, and jojoba oil. Animal waxes include beeswax, lanolin, and whale wax. 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, and ketones. As synthetic hydrocarbons, Fischer-Tropsch wax (also known as Sazoir wax) and polyethylene wax are famous, but in addition to this, low molecular weight polymers (specifically, polymers having a viscosity number average molecular weight of 500 to 20000) Some of the following polymers are also included. That is, there are polypropylene, ethylene / acrylic acid copolymer, polyethylene glycol, polypropylene glycol, polyethylene glycol and polypropylene glycol block or graft conjugate. 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.

  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. . In view of heat resistance and contamination, a polymer compound is preferable.

  The silicone compound is a compound having a silicone structure in the molecule, and examples thereof include silicone emulsion, acrylic graft silicone, silicone graft acrylic, amino-modified silicone, perfluoroalkyl-modified silicone, and alkyl-modified silicone. In view of heat resistance and contamination, it is preferable to contain a curable silicone resin. As the kind of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, and an electron beam curable type can be used.

  The compound having a pyrrolidinium ring used for forming the coating layer of the film of the present invention is a compound having a structure represented by the formula (1) in the molecule. From the viewpoint of good heat resistance, a compound having a pyrrolidinium ring is preferable. Among these compounds, a polymer is preferable from the viewpoint that bleeding out is difficult.

In the above formula ^{(1), R 1, R} 2 are each independently a proton, an alkyl group, a phenyl group, these alkyl groups, a phenyl group may be substituted by the following groups. Substitutable groups include, for example, hydroxyl group, amino group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy group, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, Halogen and the like. R ¹ and R ² 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 - Etc.

X ⁻ in the above formula (1) can be appropriately selected within a range not impairing the gist of the present invention. For example, alkyl sulfate ion, alkyl sulfonate ion, trifluoroacetate ion, trichloroacetate ion, halogen ion, phosphate, nitrate, carboxylate and the like can be mentioned.

  Moreover, the number average molecular weights of the compound containing a pyrrolidinium ring are 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.

  The isocyanate compound used for forming the coating layer of the film of the present invention is used to make the coating layer strong and to provide stable release performance and antistatic performance. As a result of further investigations, it was found that in addition to these performances, mold release performance can be maintained even after heat treatment. Usually, by heat treatment, the mold release performance deteriorates, the peeling force becomes heavy, and it is difficult to develop the application through the heating process, but by using an isocyanate compound in combination with the mold release agent It has been found that the peeling force due to heating can be reduced.

  The isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of the 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. Reaction products of these isocyanates with various polymers and compounds may be used. 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. Further, when an aqueous coating solution is used, it is more preferably a blocked isocyanate.

  When used in the state of blocked isocyanate, the blocking agent includes, for example, active methylene compounds, bisulfites, phenol compounds such as phenol, cresol, ethylphenol, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, Alcohol compounds such as ethanol, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam, amine compounds such as diphenylaniline, aniline and ethyleneimine, acetanilide and acetic acid amide Oxime such as acid amide compounds, formaldehyde, acetoaldoxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime These compounds may be used, and these may be used alone or in combination of two or more. Among these, an active methylene compound is preferable from the viewpoint that the peeling property hardly changes even after heating.

  Examples of the active methylene-based blocking agent include isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2-ethylheptanoyl acetate, malonate, Examples thereof include acetoacetic acid esters and acetylacetone. Among them, isobutanoyl acetate, n-propanoyl acetate, n-butanoyl acetate, n-pentanoyl acetate, n-hexanoyl acetate, 2- Ethylheptanoyl acetate is preferable, more preferably isobutanoyl acetate, n-propanoyl acetate, n-pentanoyl acetate, and still more preferably isobutanoyl acetate. More specifically, examples of isobutanoyl acetate include methyl isobutanoyl acetate, ethyl isobutanoyl acetate, n-propyl isobutanoyl acetate, isopropyl isobutanoyl acetate, n-butyl isobutanoyl acetate, isobutyl isobutanoyl acetate, t-butyl isobutanoyl acetate, and isobutanoyl acetate. Examples include n-pentyl, n-hexyl isobutanoyl acetate, 2-ethylhexyl isobutanoyl acetate, phenyl isobutanoyl acetate, and benzyl isobutanoyl acetate. Of these, methyl isobutanoyl acetate and ethyl isobutanoyl acetate are preferred. Examples of n-propanoyl acetate include n-propanoyl methyl acetate, n-propanoyl ethyl acetate, n-propanoyl acetate isopropyl, n-propanoyl acetate n-butyl, n-propanoyl acetate t-butyl and the like. Among these, n-propanoyl methyl acetate and n-propanoyl ethyl acetate are preferable. Examples of n-pentanoyl acetate include n-pentanoyl methyl acetate, n-pentanoyl ethyl acetate, n-pentanoyl acetate isopropyl, n-pentanoyl acetate n-butyl, and n-pentanoyl acetate t-butyl. Among these, n-pentanoyl methyl acetate and n-pentanoyl ethyl acetate are preferable.

  In addition, the isocyanate compound in the present invention 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-based compound, it is possible to use a mixture or bonded product with a polyester resin or a polyurethane resin.

  In the formation of the coating layer of the film of the present invention, various polymers can be used in combination in order to improve the coating appearance and transparency and to control the releasability.

  Specific examples of the polymer include polyester resin, acrylic resin, urethane resin, polyvinyl (polyvinyl alcohol, vinyl chloride vinyl acetate copolymer, etc.), polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches and the like. . Among these, polyester resin, acrylic resin, urethane resin, and polyvinyl alcohol are preferable, and acrylic resin and polyvinyl alcohol are more preferable in terms of easy release control.

  The acrylic resin is a polymer composed of a polymerizable monomer including acrylic and methacrylic monomers. 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. Moreover, in order to improve adhesiveness more, it is also possible to contain a hydroxyl group and an amino group.

  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 (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate; (Meth) acrylamide, Various nitrogen-containing compounds such as acetone acrylamide, N-methylol acrylamide or (meth) acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, vinyltoluene, and various vinyls such as vinyl propionate Esters; various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc .; phosphorus-containing vinyl monomers; various vinyl halides such as vinyl chloride and biridene chloride Various conjugated dienes such as butadiene.

  Polyvinyl alcohol is a compound having a polyvinyl alcohol moiety. For example, conventionally known polyvinyl alcohol can be used, including knitted compounds that are partially acetalized or brachiralized with respect to polyvinyl alcohol. The degree of polymerization of polyvinyl alcohol is not particularly limited, but is usually 100 or more, preferably in the range of 300 to 40,000. When the degree of polymerization is less than 100, the water resistance of the coating layer may decrease. The saponification degree of polyvinyl alcohol is not particularly limited, but is usually 70 mol% or more, preferably in the range of 70 to 99.9 mol%, more preferably 80 to 97 mol%, and particularly preferably 86 to 97 mol%. A saponified polyvinyl acetate of 95 mol% is practically used.

  In the formation of the coating layer of the film of the present invention, a crosslinking agent other than the isocyanate compound can be used in combination in order to control antistatic properties and improve the strength of the coating layer. As the crosslinking agent, various conventionally known crosslinking agents can be used, and examples thereof include melamine compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, silane coupling compounds, and the like. Among these, a melamine compound and an oxazoline compound are preferable from the viewpoint of increasing the strength of the coating layer, and a melamine compound is particularly preferable from the viewpoint of hardly affecting the antistatic property.

  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. 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.

  Moreover, in the range which does not impair the main point of this invention, it is also possible to use particle | grains together for the purpose of the formation of the coating layer of the film of this invention for the purpose of the blocking property of a coating layer, slipperiness improvement, etc.

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

  As a ratio with respect to all the non-volatile components in the coating liquid for forming the coating layer of the present invention, the release agent is usually in the range of 5 to 90% by weight, preferably 10 to 75% by weight, and more preferably 15 to 50% by weight. is there. If the amount is less than 5% by weight, sufficient release performance may not be obtained. If the amount exceeds 90% by weight, sufficient heat resistance and antistatic property may not be obtained due to the small amount of other components. There is.

  As a ratio with respect to all the non-volatile components in the coating liquid for forming the coating layer of the present invention, the compound having a pyrrolidinium ring is usually 5 to 90% by weight, preferably 8 to 75% by weight, more preferably 15 to 45% by weight. It is a range. When the amount is less than 5% by weight, the antistatic property may not be sufficient. When the amount exceeds 90% by weight, sufficient heat resistance and releasability may not be obtained because other components are small.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer which comprises the laminated polyester film in this invention, an isocyanate type compound is 2-90 weight% normally, Preferably it is 5-70 weight%, More preferably, 8- It is in the range of 40% by weight, particularly preferably 10-25% by weight. When the amount is less than 2% by weight, there is a possibility that the release performance after heating may be greatly deteriorated. When the amount exceeds 90% by weight, sufficient heat resistance and releasability cannot be obtained because there are few other components. there is a possibility. In addition, it has been found out that the antistatic property may deteriorate if the amount is large.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer which comprises the laminated polyester film in this invention, a polymer is 80 weight% or less normally, Preferably it is 5-70 weight%, More preferably, it is 15-35 weight%. Range. By using it in the above-mentioned range, it becomes easy to improve the coating appearance and adjust the releasability and antistatic property.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer which comprises the laminated polyester film in this invention, crosslinking agents other than an isocyanate type compound are 50 weight% or less normally, Preferably it is 3-40 weight%, More preferably, Is in the range of 5 to 25% by weight. By using in the above range, it becomes easy to improve the strength of the coating layer and adjust the antistatic property. However, the peeling force after heating may be easily deteriorated compared to the peeling force before heating.

  Analysis of components in the coating layer can be performed by analysis such as TOF-SIMS and ESCA.

  When providing a coating layer by in-line coating, the above-mentioned series of compounds is applied as an aqueous solution or dispersion, and the coating solution adjusted to a solid content concentration of about 0.1 to 50% by weight as a guide is applied onto the polyester film. It is preferable to produce a laminated polyester film. Moreover, in the range which does not impair the main point of this invention, a small amount of organic solvents may be contained in the coating liquid for the purpose of improving dispersibility in water, improving film-forming properties, and the like. Only one type of organic solvent may be used, or two or more types may be used as appropriate.

  Regarding the laminated polyester film in the present invention, the thickness of the coating layer provided on the polyester film is usually 0.003 to 1 μm, preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.2 μm. It is. When the film thickness exceeds 1 μm, the appearance and transparency may be deteriorated, and when the film thickness is less than 0.005 μm, sufficient releasability may not be obtained.

  Examples of the method for forming the coating layer of the present invention include 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, and impregnation. Conventionally known coating methods such as coat, kiss coat, spray coat, calendar coat, and extrusion coat can be used.

  In the present invention, the drying and curing conditions for forming the coating layer on the polyester film are not particularly limited. For example, when the coating layer is provided by off-line coating, it is usually 3 to 40 at 80 to 200 ° C. The heat treatment may be performed for 2 seconds, preferably 100 to 180 ° C. for 3 to 40 seconds.

  On the other hand, when the coating layer is provided by in-line coating, heat treatment is usually performed at 70 to 270 ° C. for 3 to 200 seconds as a guide.

  Further, irrespective of off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as required. The polyester film constituting the laminated polyester film in the present invention may be subjected to surface treatment such as corona treatment or plasma treatment in advance.

  The peeling force before heating of the coating layer in the present invention is preferably 2000 mN / cm or less, more preferably 1500 mN / cm or less, and still more preferably 1000 mN / cm or less. By setting it as the said range, a peeling operation | work will become easy.

  The peeling force after heating the coating layer in the present invention at 100 degrees for 1 hour is preferably 3500 mN / cm or less, more preferably 3000 mN / cm or less. By setting it as the said range, peeling can be fully performed even after heat processing.

  Considering the ease of controlling the peel strength of the release layer before and after heating, the peel strength before and after heating is compared, and the value of the difference in heat peel strength = (peeling force after heating−peeling force before heating) is 3000 mN / cm or less, preferably 2500 mN / cm or less, more preferably 2000 mN / cm or less.

The surface resistance value of the coating layer in the present invention is preferably 1 × 10 ¹³ Ω or less, more preferably 5 × 10 ¹² Ω or less, and further preferably 1 × 10 ¹² Ω or less. By setting it as the said range, it can be set as the film in which peeling electrification does not occur easily.

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

(2) Method for measuring film thickness of coating layer The surface of the coating layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by ultramicrotomy stained with RuO _4, a coating layer cross-section was measured by using a TEM (Hitachi High Technologies Corporation H-7650, accelerating voltage 100 V).

(3) Measuring method of peel force before heating of release film Adhesive tape (“No. 31B” manufactured by Nitto Denko Corporation) is pressure-bonded once with a 2 kg rubber roller on the coating layer surface, and left at room temperature for 1 hour. The peel force was measured. The peel force was “Ezgraph” manufactured by Shimadzu Corporation, and was peeled 180 ° under a condition of a tensile speed of 300 mm / min, and the peel force at that time was measured.

(4) Measuring method of peel force after heating of release film After pressure-bonding adhesive tape (“No. 31B” manufactured by Nitto Denko Corporation) 1 reciprocating with a 2 kg rubber roller on the coating layer surface, in a 100 degree oven. And heated for 1 hour. Thereafter, the peel force after standing at room temperature for 1 hour was measured. The peel force was “Ezgraph” manufactured by Shimadzu Corporation, and was peeled 180 ° under a condition of a tensile speed of 300 mm / min, and the peel force at that time was measured.

(5) Evaluation of heat resistance of release layer Using the peel force measured in the above (3) and (4), the difference in heat peel force = (heat peel force difference− (heat peel force before heating)) Was calculated.

(6) Measuring method of surface resistance value Using a high resistance measuring instrument manufactured by Hewlett-Packard Japan: HP4339B and measuring electrode: HP16008B, the sample was conditioned in a measurement atmosphere of 23 ° C. and 50% RH for 30 minutes, and then the surface resistance value was measured. Was measured.

(7) Evaluation method of strength of coating layer The surface of the coating layer was rubbed once with the finger pad around which ERI-EL (registered trademark) Pro Wipe Soft Micro Wiper S220 manufactured by Daio Paper Co., Ltd. was observed, and the surface was observed. The case where the scraped area of the coating layer was less than 10% was evaluated as ◯, the case where it was 10% or more and less than 50% was evaluated as Δ, and the case where it was 50% or more was evaluated as ×.

The polyester used in the examples and comparative examples was prepared 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 adding 0.04 part by weight of ethyl acid phosphate to this reaction mixture, 0.04 part by weight 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 0.63 due to a change in stirring power of the reaction tank, and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester (A) was 0.63.

<Method for producing polyester (B)>
In the polyester (A) production method, after adding 0.04 part by weight of ethyl acid phosphate, 0.2 part by weight of silica particles having an average particle diameter of 2 μm and 0.04 part by weight of antimony trioxide are added to obtain the intrinsic viscosity. A polyester (B) was obtained using the same method as the production method of the polyester (A) except that the polycondensation reaction was stopped at a time corresponding to 0.65. The obtained polyester (B) had an intrinsic viscosity of 0.65.

Examples of compounds constituting the coating layer are as follows.
(Example compounds)
・ Releasing agent (long-chain alkyl compound): (I)
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.

Antistatic agent: (II) A 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.

Active methylene block polyisocyanate: (IIIA) Block polyisocyanate synthesized by the following method.
1000 parts of hexamethylene diisocyanate was stirred at 60 ° C., and 0.1 part of tetramethylammonium capryate was added as a catalyst. After 4 hours, 0.2 part of phosphoric acid was added to stop the reaction, and an isocyanurate type polyisocyanate composition was obtained. 100 parts of the obtained isocyanurate type polyisocyanate composition, 42.3 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and 29.5 parts of propylene glycol monomethyl ether acetate were charged and maintained at 80 ° C. for 7 hours. Thereafter, the reaction solution temperature was kept at 60 ° C., 35.8 parts of methyl isobutanoyl acetate, 32.2 parts of diethyl malonate, and 0.88 part of 28% methanol solution of sodium methoxide were added and kept for 4 hours. Block polyisocyanate obtained by adding 58.9 parts of n-butanol, maintaining the reaction solution temperature at 80 ° C. for 2 hours, and then adding 0.86 part of 2-ethylhexyl acid phosphate.

Amine-based blocked isocyanate: (IIIB) Blocked polyisocyanate synthesized by the following method.
100 parts of triisocyanurated hexamethylene diisocyanate was heated to 50 ° C. under nitrogen, and 58.5 parts of methyl isobutyl ketone was added. Thereafter, 83.5 parts of di-n-butylamine was added while maintaining the reaction solution temperature at 60 to 70 ° C. Block polyisocyanate obtained by adding 2.0 parts of n-butanol after adding for 1 hour at 75 ° C.

Acrylic resin: (IVA) Aqueous dispersion of acrylic resin polymerized with the following composition: ethyl acrylate / n-butyl acrylate / methyl methacrylate / N-methylol acrylamide / acrylic acid = 65/21/10/2/2 (% by weight) Emulsion polymer (emulsifier: anionic surfactant).

・ Polyvinyl alcohol: (IVB)
Polyvinyl alcohol having a saponification degree of 88 mol% and a polymerization degree of 500

・ Hexamethoxymethylolmelamine: (VA)
・ Epoxy compounds: (VB)

Example 1:
The mixed raw materials obtained by mixing the polyesters (A) and (B) at a ratio of 90% and 10%, respectively, are used as the outermost layer (surface layer) raw material, and only the polyester (A) is used as the intermediate layer raw material in two extruders. Each is supplied, melted at 285 ° C., and then coextruded in a layer configuration of two types and three layers (surface layer / intermediate layer / surface layer = 1: 8: 1 discharge amount) on a cooling roll set at 40 ° C. Cooled and solidified to obtain an unstretched sheet. Next, the film was stretched 3.4 times in the longitudinal direction at a film temperature of 85 ° C. using the difference in peripheral speed of the roll, and then the coating solution 1 shown in Table 1 below was applied to one side of the longitudinally stretched film, which was led to a tenter. The film was stretched 4.3 times at 110 ° C. in the transverse direction, heat treated at 235 ° C., then relaxed by 2% in the transverse direction, and having a release layer with a thickness (after drying) of 0.03 μm. A polyester film was obtained.

  When the releasability of the obtained polyester film was evaluated, it was good before and after heating, the change in peeling force due to heating was small, and the antistatic property was good. The properties of this film are shown in Table 2 below.

Examples 2-12:
In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. The finished polyester film was as shown in Table 2. The peel strength was low, and the releasability and antistatic property were good.

Comparative Example 1:
In Example 1, it manufactured like Example 1 except not providing an application layer, and obtained the polyester film. When the completed laminated polyester film was evaluated, it was as shown in Table 2. It was high in heat peelability and poor in releasability and antistatic properties.

Comparative Examples 2-6:
In Example 1, it manufactured similarly to Example 1 except having changed the coating agent composition into the coating agent composition shown in Table 1, and obtained the polyester film. When the finished laminated polyester film was evaluated, it was as shown in Table 2. It was inferior in releasability before and after heating, a large change in peel strength due to heating, and inferior in antistatic properties. It was.

  The release film of the present invention is particularly heat-resistant, for example, as a process film used in various processes such as transfer for molding simultaneous transfer, for manufacturing flexible printed wiring boards, and for process paper for manufacturing plastic sheets. Can be suitably used in applications requiring the above.

Claims (1)

A laminated polyester film comprising a coating layer formed from a coating solution containing a release agent, a compound having a pyrrolidinium ring, and an isocyanate compound on at least one surface of the polyester film.