JP5778472B2 - Laminated polyester film - Google Patents

Description

  The present invention relates to a laminated polyester film, and more particularly to a polyester film for decorative film that cuts ultraviolet rays and has both excellent antistatic performance and easy adhesion performance.

  Biaxially stretched polyester film excels in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, gas barrier properties, chemical resistance, etc., packaging materials, plate making materials, display materials, transfer materials, building materials, It is used for window paste materials, membrane switches, antireflection films used for flat displays, optical films such as diffusion sheets and prism sheets, and transparent touch panels. However, when other materials are applied and laminated on the polyester film in such applications, there is a drawback that the adhesiveness is poor depending on the materials used. As one of the methods for improving the adhesiveness of the biaxially stretched polyester film, there is known a method of applying various resins to the surface of the polyester film and providing a coating layer having easy adhesion performance (Patent Documents 1 and 2). .

  However, such an existing easily-adhesive coating layer may still not have sufficient adhesion depending on the type of the topcoat layer. For example, when a so-called solventless UV curable coating is used as the topcoat, the solventless topcoat has a low penetration and swelling effect on the easy-adhesion layer compared to the solvent-based topcoat, and therefore the adhesion is poor. It tends to be enough.

  For these problems, for example, by providing an easy-adhesion layer having a specific composition, a method of imparting better adhesiveness has been proposed and improved (Patent Documents 3 to 5).

  Recently, however, for decorative films based on polyester films, when used outdoors for long-term POPs at convenience stores, pharmacies, etc., not only adhesiveness but also long-term adhesive weather resistance performance. It has been demanded.

  Decorative films are widely used in a configuration where a polyester film substrate is provided with a slightly adhesive layer on one side and a printed layer or hard coat layer on the other side. It is known to provide a silicone-based micro-adhesive layer that can be pasted and peeled off many times, but in decorative films for window displays etc. in the outdoors or indoors exposed to direct sunlight, When re-peeling, there is a problem that the trace of the adhesive layer remains. In particular, when the adherend is glass, it becomes a significant problem (Patent Document 6).

  In addition, polyester film is easily charged during friction, peeling, etc., and when applying a silicone coating solution, there is a problem of uneven coating due to charging of the base material. There is also a demand for imparting antistatic performance.

  Therefore, a coating layer having adhesion weather resistance and antistatic properties as described above is required, but any conventional easy adhesion coating layer and easy adhesion coating layer having antistatic properties still have sufficient effects. It is not done.

JP-A-2002-53687 Japanese Patent Laid-Open No. 11-286092 JP 2009-220376 A JP 2009-221359 A JP 2010-13550 A JP 2007-254565 A

  The present invention has been made in view of the above circumstances, and the problem to be solved is to provide a polyester film having an application layer that cuts ultraviolet rays and has both excellent antistatic properties, easy adhesion properties, and adhesion weather resistance. is there.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by providing a specific polyester film with a coating layer containing a specific type of compound. It came to complete.

That is, the gist of the present invention is a laminated polyester film having a coating layer on at least one side of a polyester film, and the coating layer has an antistatic agent, a compound having an isocyanate-based reactive group and a urethane bond as a core, and the outside thereof. Formed from a coating solution containing resin emulsion particles having a core-shell structure covered with another resin, a urethane resin having no isocyanate-based reactive group at the terminal, and one or more cross-linking agents. It exists in the laminated polyester film characterized by a rate being 5% or less.

  ADVANTAGE OF THE INVENTION According to this invention, the polyester film which has the coating layer which was excellent in ultraviolet-ray cut-off property, and was excellent in antistatic property, easy-adhesion property, and adhesion weather resistance with respect to topcoat agent can be provided. Value is high.

  The base film used in the present invention is made of polyester. Such polyesters include dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, 4,4′-diphenyldicarboxylic acid, 1,4-cyclohexyldicarboxylic acid or esters thereof. It is a polyester produced by melt polycondensation with glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. Polyesters composed of these acid components and glycol components can be produced by arbitrarily using a commonly used method. For example, a transesterification reaction between a lower alkyl ester of an aromatic dicarboxylic acid and a glycol, or a direct esterification of an aromatic dicarboxylic acid and a glycol, to form a substantially bisglycol of an aromatic dicarboxylic acid A method is employed in which an ester or a low polymer thereof is formed and then polycondensed by heating under reduced pressure. Depending on the purpose, an aliphatic dicarboxylic acid may be copolymerized.

  Typical examples of the polyester of the present invention include polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and the like. It may be a polymerized polyester and may contain other components and additives as necessary.

  The polyester film in the present invention can contain particles for the purpose of ensuring the film runnability and preventing scratches. Examples of such particles include inorganic particles such as silica, calcium carbonate, magnesium carbonate, calcium phosphate, kaolin, talc, aluminum oxide, titanium oxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. Further, organic particles such as crosslinked polymer particles and calcium oxalate, and precipitated particles during the polyester production process can be used.

  The film of the present invention has an internal haze of usually 1.5% or less, preferably 1.0% or less. When the internal haze exceeds 1.5%, the transparency tends to be inferior, and thus visibility may be impaired.

  The particle size and content of the particles used are selected according to the use and purpose of the film, but the average particle size is usually in the range of 0.01 to 5.0 μm. If the average particle size exceeds 5.0 μm, the surface roughness of the film becomes too rough, or the particles are likely to fall off from the film surface. When the average particle size is less than 0.01 μm, the surface roughness is too small and sufficient slipperiness may not be obtained. The particle content can be adjusted within the range if the internal haze is 1.5% or less.

  In addition, when it is particularly desired to ensure the transparency and smoothness of the film, the film may be substantially free of particles. Further, various stabilizers, lubricants, antistatic agents and the like can be appropriately added to the film.

  As a film forming method of the film of the present invention, a generally known film forming method can be adopted, and there is no particular limitation. For example, a sheet obtained by melt extrusion is first stretched 2 to 6 times at 70 to 145 ° C. by a roll stretching method to obtain a uniaxially stretched polyester film, and then perpendicular to the previous stretching direction in the tenter. A film is obtained by extending | stretching 2 to 6 times at 80-160 degreeC to the direction, and also heat-processing at 150-250 degreeC for 1 to 600 seconds. Further, at this time, a method of relaxing 0.1 to 20% in the longitudinal direction and / or the transverse direction in the heat treatment zone and / or the cooling zone at the heat treatment outlet is preferable.

  The polyester film in the present invention has a single layer or multilayer structure. In the case of a multilayer structure, the surface layer and the inner layer, or both the surface layer and each layer can be made of different polyesters depending on the purpose.

  The polyester film of the present invention has a coating layer on at least one surface, but even if a similar or other coating layer or functional layer is provided on the opposite surface of the film, it is naturally included in the concept of the present invention.

  The film of the present invention contains an ultraviolet absorber in an amount of usually 0.20 to 10.0% by weight, preferably 0.30 to 1.8% by weight. When the ultraviolet absorber is less than 0.10% by weight, the polyester film may be deteriorated by ultraviolet rays. When the ultraviolet absorber is contained in an amount exceeding 10.0% by weight, the ultraviolet absorber is bleeded on the surface. May cause deterioration of surface functionality such as adhesion loss.

  The film of the present invention has a light transmittance at a wavelength of 380 nm of 5.0% or less, preferably 2.0% or less, more preferably 1.0% or less. When the light transmittance at a wavelength of 380 nm is larger than 5.0%, it is not sufficient to prevent the fine adhesive layer from being deteriorated by ultraviolet rays transmitted through the polyester film. Then, the trace of the adhesive layer remains and becomes a problem.

  Examples of ultraviolet absorbers include benzophenone compounds, 1,3,5-triazine compounds, benzoxazinone compounds, and the like, which can be used alone or in combination of two or more. In consideration of this, a benzoxazinone-based compound that is difficult to be yellowed is preferably used.

  An example of a benzoxazine-based compound used as an ultraviolet absorber is 2,2- (1,4-phenylene) bis [4H-3,1-benzoxazin-4-one].

  In the present invention, the coating layer may be provided by various known coating methods. However, it is desirable to provide the coating layer by a so-called in-line coating in which a coating layer is formed during film formation, particularly by a coating stretching method in which stretching is performed after coating.

  In-line coating is a method of coating within the process of manufacturing a polyester film. Specifically, it is a method of coating at any stage from melt extrusion of polyester to biaxial stretching and then heat setting and winding. is there. Normally, it is coated on either a substantially amorphous unstretched sheet obtained by melting and quenching, then a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction), or a biaxially stretched film before heat setting. To do. In particular, as a coating stretching method, a method of stretching in the transverse direction after coating on a uniaxially stretched film is excellent.

  According to such a method, since film formation and coating layer coating can be performed simultaneously, there is an advantage in manufacturing cost, and since the film is stretched after coating, it becomes a uniform coating with a thin film, so that the adhesive performance is stable. To do. Moreover, the polyester film before biaxially stretching is first covered with an easy-adhesive resin layer, and then the film and the coating layer are stretched simultaneously, whereby the base film and the coating layer are firmly adhered.

  In addition, biaxial stretching of the polyester film is achieved by stretching the film in the lateral direction while holding the film edge with a tenter, so that the film is constrained in the longitudinal / lateral direction. High temperature can be applied while maintaining 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 polyester film are firmly adhered. As an easily-adhesive polyester film, the uniformity of the coating layer, the improvement of the film-forming property, and the adhesion between the coating layer and the film often produce favorable characteristics.

  In this case, the coating solution to be used is preferably an aqueous solution or an aqueous dispersion for safety reasons in terms of handling, working environment, and may contain an organic solvent if water is the main medium.

  Next, the coating layer provided on the film in the present invention will be described.

  In the coating liquid for providing the coating layer in the present invention, an antistatic agent (A), a compound having an isocyanate-based reactive group and a urethane bond (B), and a urethane resin having no isocyanate-based reactive group at the terminal (C) And one or more crosslinking agents (D).

  The antistatic agent (A) in the present invention is not particularly limited as long as it is a compound capable of imparting antistatic properties. For example, a metal compound, an electron conductive polymer, a charge transfer complex compound, conductive carbon, And high molecular weight ionic compounds. In particular, a high molecular weight ionic compound is preferably used from the viewpoints of adhesiveness and antistatic performance.

Examples of the high molecular weight ionic compound include an anionic compound and a cationic compound, and the cationic compound is particularly preferable from the viewpoint of adhesiveness and antistatic performance.
As the high molecular weight cationic compound, for example, a compound containing a quaternary ammonium salt in the molecule is used, and a compound containing a quaternary ammonium salt in the main chain structure is particularly preferable from the viewpoint of thermal stability.

  The content of the antistatic agent (A) in the coating layer is not limited and can be appropriately selected within the range where the desired properties are exhibited. However, in view of adhesiveness and antistatic properties, the antistatic agent ( A) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight in the coating solution.

  In the present invention, the compound (B) having an isocyanate-based reactive group and a urethane bond is a compound containing in the molecule at least one isocyanate-based reactive group and a urethane bond.

  For example, a compound obtained by reacting a hydroxyl group-containing compound and diisocyanate, a compound obtained by reacting a hydroxyl group-containing compound and polyisocyanate, a compound obtained by reacting a polyol and polyisocyanate, and the like has an isocyanate group not reacted with a hydroxyl group at the terminal. Such a compound is mentioned.

In addition, what is called block isocyanate which protected this terminal isocyanate with the blocking agent can also be used. In the present invention, from the viewpoint of liquid stability and the like, a form using blocked isocyanate as the compound (B) is preferable.
Such a compound (B) may be a urethane resin having an isocyanate group at the terminal produced by reacting an excess polyisocyanate with a polyol. For the synthesis of this resin, the synthesis of a urethane resin (C) described later is used. It is possible to use the raw material components used in

  In the present invention, for example, a compound having a core-shell structure produced by a method as described in JP-A-2008-45072 can also be used as the compound (B). That is, for example, resin emulsion particles having a core-shell structure in which compound (B) is used as a core and the outside is covered with another resin can be used as compound (B) of the present invention. From the viewpoint of the stability of the coating solution and the adhesiveness of the resulting coating layer. Moreover, it is good also as urethane resin (C) in this invention using the urethane resin mentioned later for resin of this shell part.

  In the present invention, when the isocyanate group of the compound (B) is blocked and used in the form of a blocked isocyanate, the blocking agent to be used is not particularly limited, and one or more types can be appropriately selected from known ones. . Examples of the blocking agent include phenolic, alcoholic, active methylene, mercaptan, acid amide, lactam, acid imide, imidazole, urea, oxime, and amine compounds.

  More specifically, for example, phenol compounds such as phenol, cresol and ethyl phenol, alcohol compounds such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol and ethanol, and active methylene compounds such as dimethyl malonate and acetylacetone. , Mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, acid amide compounds such as acetanilide and acetic acid amide, lactam compounds such as ε-caprolactam and δ-valerolactam; acid imide compounds such as succinimide and maleic acid imide Oxime compounds such as acetoaldoxime, acetone oxime, methyl ethyl ketoxime, amine compounds such as diphenylaniline, aniline, ethyleneimine, Examples thereof include sodium sulfite.

  The compound (A) in the present invention preferably has a tetramethylene to decamethylene structure (4 to 10 carbon atoms) in the resin structure, particularly from the viewpoint of adhesion weather resistance. The tetramethylene to decamethylene structure referred to here may be a derivative obtained by modifying the tetramethylene to decamethylene structure, such as a methyl chain introduced into the side chain.

  In this invention, a compound (B) may be used independently and may be used in combination of multiple types.

  In the present invention, the urethane resin (C) having no isocyanate-based reactive group at the terminal (hereinafter sometimes simply referred to as a urethane resin) is obtained by combining a polyisocyanate component and a polyol component by a known aqueous urethane resin synthesis method. The ionicity of the synthesized resin can be any of cation, anion, and nonionicity, but the terminal does not have an isocyanate-based reactive group.

  In the synthesis of such a urethane resin of the present invention, the usual polyisocyanate component is used as the component of the polyisocyanate, and is not particularly specified. However, in order to avoid yellowing of the coating film due to ultraviolet rays, an aromatic compound is used. Aliphatic or alicyclic diisocyanates are preferred over diisocyanates.

  Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene- Aliphatic diisocyanates such as 1,6-diisocyanate and 2,4,4-trimethylhexamethylene-1,6-diisocyanate are exemplified, and isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethyl There are alicyclic diisocyanates such as xylylene diisocyanate. These diisocyanates are used individually by 1 type or in mixture of 2 or more types.

  Furthermore, these adduct modified products, carbodiimide modified products, allophanate modified products, burette modified products, uretdione modified products, uretoimine, such as allophanate modified polyisocyanates obtained from hexamethylene diisocyanate and monools having 1 to 6 carbon atoms. Modified products, isocyanurate modified products, and the like can also be used.

  As aromatic diisocyanates, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, p Examples include -phenylene diisocyanate and naphthylene-1,4-diisocyanate.

  Polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, acrylic polyols, polyalkylene polyols, polyolefin polyols, etc. are used as polyols in the synthesis of such urethane resins, and these polyols may be used in combination. Good. Moreover, as a polyol component, it is usually the number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC), and it is preferable that it is 300-5000.

  In the synthesis of the urethane resin (C) in the present invention, a chain extender is usually used, and the chain extender to be used is not particularly limited, but an amine compound such as diamine or polyamine is used rather than a diol compound as a chain extender. It is advantageous in terms of physical properties such as water resistance, solvent resistance and contamination resistance because it is easily highly crosslinked.

  Specific examples of these amine compounds include diamines such as ethylenediamine and isophoronediamine, and polyamines such as diethylenetriamine, triethylenetetramine, tetraethylene represented by H2N- (C2H4NH) n-C2H4NH2 (n = 1-8). Examples include ethylene pentamine and pentaethylene hexamine.

In the urethane resin (C) in the present invention, it is desirable that the urethane resin (C) has a tetramethylene to decamethylene structure in order to express the adhesion weather resistance in the present invention particularly well.
The urethane resin (C) having a tetramethylene to decamethylene structure can be obtained by using, for example, a polyisocyanate component, a polyol component, a chain extender or the like having a tetramethylene to decamethylene structure as a part of the constituent components. In order to obtain a urethane resin having particularly excellent characteristics, it is industrially easy to use a polyol having a tetramethylene to decamethylene structure. In addition, the polyol having a tetramethylene to decamethylene structure may be a derivative obtained by modifying the tetramethylene to decamethylene structure, for example, a methyl group introduced into the side chain.

  The urethane resin (C) in the present invention preferably has a glass transition point (hereinafter sometimes referred to as Tg) of 10 ° C. or less, more preferably 0 ° C. or less, and still more preferably −10 ° C. or less. When it is used, it is easy to obtain the effect of adhesion weather resistance. When Tg is higher than 10 ° C., easy adhesion may be insufficient. The measurement of Tg here refers to the temperature at which E ″ is maximized by preparing a dry film of urethane resin (C) and performing dynamic viscoelasticity measurement.

  In the present invention, the compound (B) and the urethane resin (C) may use a solvent as a medium, but preferably use water as a medium. In order to disperse or dissolve polyurethane in water, there are a forced emulsification type using an emulsifier, a self-emulsification type in which a hydrophilic group or an ionic group is introduced into a polyurethane resin, or a water-soluble type. In particular, the self-emulsifying type that introduces nonionic hydrophilic groups such as ethylene oxide chains into the polyurethane resin skeleton, or introduces ionic groups into the skeleton to form ionomers, is the storage stability of the liquid and the water resistance of the resulting coating layer. It is preferable because of its excellent adhesiveness.

  When an ionic group is introduced, examples of the ionic group to be introduced include a carboxyl group, sulfonic acid, phosphoric acid, phosphonic acid, quaternary ammonium and the like, and a carboxyl group and quaternary ammonium are preferable.

  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, at the time of prepolymer synthesis, a resin having a carboxyl group can be used as a copolymerization component, or a component having a carboxyl group can be used as one component such as a polyol, polyisocyanate, or 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 may be neutralized with a neutralizing agent. As the neutralizing agent, an ordinary one is arbitrarily used. For example, organic amines such as ethylamine, trimethylamine, triethylamine, triisopropylamine, triethanolamine, triisopropanolamine, morpholine, N-methylmorpholine are preferably used, and inorganic alkalis such as sodium hydroxide and potassium hydroxide, and ammonia Are also illustrated. In order to improve the weather resistance and water resistance after drying, a highly volatile one that is easily dissociated by heat or an amino alcohol that reacts with a polyisocyanate curing agent is more preferred.

  In such a polyurethane resin, a carboxyl group from which a neutralizing agent is removed in a 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 coating layer, as well as excellent stability in a liquid state before coating.

  When quaternary ammonium is introduced to impart a cationic property to the urethane resin, a tertiary amino group is introduced in the step of synthesizing the urethane prepolymer, and the tertiary amino group is neutralized with an acid or a quaternizing agent. A cationic aqueous urethane resin is obtained by quaternizing with and dispersing in water.

  An example of introducing a tertiary amino group is the use of a chain extender having a tertiary amino group. Specific examples of such chain extenders include N-methyldiethanolamine, N -N-alkyl dialkanolamines such as ethyldiethanolamine, N-alkyldiaminoalkylamines such as N-methyldiaminoethylamine and N-ethyldiaminoethylamine, and triethanolamine.

  The content of the compounds (B) and (C) in the coating layer is not particularly limited and can be appropriately selected within the range where the desired properties are obtained. However, if the amount is too small, the effect is obtained. It's hard to be done

  Therefore, the compound (B) is preferably 5 to 90% by weight, more preferably 5 to 70% by weight, and particularly preferably 5 to 50% by weight, which is highly effective. Further, the urethane resin (C) is preferably 10 to 90% by weight, more preferably 20 to 60% by weight, and particularly preferably 20 to 50% by weight.

  Examples of the crosslinking agent (D) in the present invention include different types of isocyanate compounds, oxazoline compounds, epoxy compounds, melamine compounds, carbodiimide compounds, alkoxysilane compounds, silane coupling agents, organometallic complexes, etc. Among these known crosslinking agents, at least one kind is used, but from the viewpoint of adhesion weather resistance, it is preferable to use at least one kind from among oxazoline compounds, epoxy compounds, melamine compounds, and carbodiimide compounds.

The oxazoline compound is a compound having an oxazoline group in the molecule, and is particularly preferably a polymer containing an oxazoline group, 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, such as alkyl acrylate, alkyl methacrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a (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, Unsaturated carboxylic acids such as styrenesulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, methacrylamide, N-alkyl Acrylamide, N-alkyl methacrylate N, N-dialkylacrylamide, N, N-dialkylmethacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2- Ethyl hexyl group, cyclohexyl group, etc.); vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; vinyl chloride and chloride Halogen-containing α, β-unsaturated monomers such as vinylidene and vinyl fluoride; α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene, and the like, and one or two of these The above monomers can be used as the epoxy compound , Diepoxy compounds, glycidylamine compounds and the like. Examples of polyepoxy compounds include sorbitol, polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2- Hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diepoxy compound, for example, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl Examples of ethers, polypropylene glycol diglycidyl ether, polytetramethylene 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-xylylenediamine, 1,3-bis (N, N-diglycidylamino) cyclohexane and the like can be mentioned.

  The melamine compound is not particularly limited, but melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting a methylolated melamine with a lower alcohol, or a mixture thereof, etc. Can be used.

  Moreover, as a melamine compound, the condensate which consists of a monomer, a dimer or more multimer, a mixture thereof, etc. can be used. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. The functional group is an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and an imino group type methylated melamine resin, a methylol group type melamine resin, or a methylol group type. A carbodiimide compound, such as a methylated melamine resin and a fully alkyl-type methylated melamine resin, refers to a compound having two or more carbodiimide groups in the molecule. For example, JP-A-10-316930 and JP-A-11- As shown in Japanese Patent No. 140164, an organic polyisocyanate, particularly preferably an organic diisocyanate, is mainly used as a raw material for synthesis.

  In the present invention, the amount of the crosslinking agent (D) in the coating solution is not limited, but is preferably 10 to 80% by weight, more preferably 10 to 50% by weight, and particularly preferably 10 to 30%. % By weight. If it is out of this range, there is a tendency that the adhesion weather resistance is lowered.

  In the present invention, in order to prevent blocking, it is preferable to contain 3% by weight or more of the entire coating layer. When the content is less than this ratio, the effect of preventing blocking tends to be insufficient. If the content is too large, the blocking prevention effect is high, but the transparency of the coating layer may be reduced, the continuity of the coating layer may be impaired, and the coating strength may be reduced. May decrease. Specifically, it is preferably 15% by weight or less, more preferably 10% by weight or less. By this method, it becomes possible to achieve both easy adhesion performance and anti-blocking performance.

  As the particles, for example, inorganic particles such as silica, alumina, and metal oxide, or organic particles such as crosslinked polymer particles can be used. In particular, silica particles are preferred from the viewpoint of dispersibility in the coating layer and transparency of the resulting coating film.

  If the particle size is too small, the effect of preventing blocking is difficult to obtain, and if the particle size is too large, dropping from the coating film tends to occur. The average particle size is preferably about 1/2 to 10 times the thickness of the coating layer. Furthermore, if the particle size is too large, the transparency of the coating layer may be inferior, so the average particle size is preferably 300 nm or less, and more preferably 150 nm or less. The average particle diameter of the particles described here can be obtained by measuring the 50% average diameter of the number average of the particle dispersion with Microtrac UPA (Nikkiso Co., Ltd.).

  In the present invention, the coating liquid for providing the easy-adhesive coating layer may contain components other than those described above as necessary. For example, surfactants, other binders, antifoaming agents, coatability improvers, thickeners, antioxidants, ultraviolet absorbers, foaming agents, dyes, pigments and the like. These additives may be used alone or in combination of two or more as necessary.

  In the present invention, as a method for providing a coating layer on a polyester film, for example, a coating technique as shown in “Coating system” published by Yuji Harasaki, Tsuji Shoten, published in 1979 can be used. Specifically, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater And techniques such as an extrusion coater and a bar coater.

  In addition, in order to improve the applicability | paintability to the film of a coating agent and adhesiveness, you may give a chemical process, a corona discharge process, a plasma process, etc. to a film before application | coating.

The coating amount of the coating layer provided on the polyester film is usually 0.002 to 1.0 g / m ² , preferably 0.005 to 0.5 g / m ² , more preferably when viewed as the final coating. Is 0.01 to 0.2 g / m ² . If the coating amount is less than 0.002 g / m ^2, sufficient adhesion performance may not be obtained. If the coating layer exceeds 1.0 g / m ² , the appearance / transparency deteriorates, the film is blocked, It is easy to invite cost increase.

The laminated polyester film of the present invention preferably has a surface resistivity of 1 × 10 ¹² Ω or less, more preferably 1 × 10 ¹⁰ Ω or less. The surface specific resistance said here can be measured by the method described in JIS: C-2318 etc., for example.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the evaluation method in an Example and a comparative example is as follows.

(1) Internal haze The internal haze of the sample film was measured with a haze meter “HM-150” manufactured by Murakami Color Research Laboratory according to JIS-K-7136. In addition, it measured in the quartz cell by using ethanol as a rough surface compensation solvent.

(2) Light transmittance at 380 nm Using a spectrophotometer UV3100 manufactured by Shimadzu Corporation, the light transmittance is measured continuously at a low scanning speed, a sampling pitch of 2 nm, and a wavelength range of 300 to 700 nm. Was detected.

(3) Adhesiveness On the polyester film coating layer, a hard coat composition as shown below was applied so that the thickness after curing was 3 μm, and an ultraviolet irradiation device UVC-402 manufactured by USHIO INC. Was used. The active energy ray-curable resin composition is cured by irradiating ultraviolet rays with a high-pressure mercury lamp at 160 W / cm, an irradiation distance of 100 mm, and a conveyor speed of 3 m / min. <Polyester film / Easily adhesive coating layer / Hard coat layer> A laminated film having the structure was obtained.
The active energy ray-cured resin layer of the obtained laminated film is cross-cut so that there are 100 grids in a 1-inch width, and a rapid peel test is performed with cello tape (registered trademark). Evaluated. The judgment criteria are as follows.
5: 0 ≦ Number of cross-cuts ≦ 10
4: 11 ≦ number of cross-cuts ≦ 20
3: 21 ≦ number of cross-cuts ≦ 40
2: 41 ≦ number of cross-cuts ≦ 80
1: 81 ≦ Number of cross-cuts peeled

Hard coat composition: A composition comprising 70 parts by weight of Kayrad DPHA (manufactured by Nippon Kayaku Co., Ltd.), 30 parts by weight of Kayarad R128H (manufactured by Nippon Kayaku Co., Ltd.) and 5 parts by weight of IRGACURE 651 (manufactured by Ciba Specialty Chemicals).

(4) Adhesive weather resistance The polyester film surface of the laminated film obtained in the same manner as in (1) is attached to a glass plate, and the active energy ray-curable resin layer is placed below the glass plate in a container containing boiling water. Then, the active energy ray-curable resin layer was exposed to steam for 5 minutes to give a wet heat load, and then UVC-402 was used to irradiate ultraviolet rays with a high-pressure mercury lamp at 160 W / cm, an irradiation distance of 100 mm, and a conveyor speed of 1 m / min. . After seven sets of this operation were performed alternately, the active energy ray-cured resin layer of the obtained laminated film was cross-cut so that there were 100 grids in a 1-inch width, and rapid peeling with cello tape (registered trademark). A test was conducted, and the adhesion was evaluated by the peeled area. The criterion is the same as (1).

(5) Surface resistivity (Ω / □)
Using a high resistance measuring instrument: HP4339B and measuring electrode: HP16008B manufactured by Hewlett-Packard Japan, the sample was conditioned for 30 minutes in a measurement atmosphere at 23 ° C. and 50% RH, and then the surface resistivity was measured. It can be said that if the surface specific resistance is 1 × 10 ¹² Ω or less, it can be said that there is good antistatic performance, and if it is 1 × 10 ¹⁰ Ω or less, it can be said that there is sufficient antistatic performance.

(6) Light resistance test of adhesive layer After setting the sample so that UV light hits the opposite side of the film surface provided with the fine adhesive layer, the sample was irradiated with a xenon lamp for 200 hours, and then the edges of the sample were rubbed with fingers. The degree of layer peeling was evaluated according to the following criteria. The evaluation results were as shown in Table 2.
○: No peeling at all ×: Partial peeling

(7) Comprehensive evaluation as a decorative film ○: Adhesion, adhesion weather resistance, antistatic property, light resistance of the adhesive layer are all good,
Suitable for decorative film x: Adhesiveness, adhesion weather resistance, antistatic property, light resistance of pressure-sensitive adhesive layer is inferior, and unsuitable for protective film

The polyester raw materials used in Examples and Comparative Examples are as follows.
(Polyester 1): Polyethylene terephthalate having an intrinsic viscosity of 0.66 substantially containing no particles (Polyester 2): containing 0.2 parts by weight of amorphous silica having an average particle diameter of 2.5 μm Polyethylene terephthalate No. 66 (Polyester 3): (Polyester 1) was subjected to a twin screw extruder with a vent, and 2,2- (1,4-phenylene) bis [4H-3,1-benzoxazine- 4-one] (CYTECOR UV-3638, molecular weight 369, benzoxazine-based CYTEC Co., Ltd.) was supplied at a concentration of 10% by weight, and the intrinsic viscosity was 0.59 polyethylene terephthalate.

Moreover, the following was used as a coating composition. However, “part” in the text represents the weight ratio in the resin solid content.
(AS1): a high molecular compound having a number average molecular weight of 21,000, obtained by copolymerizing a structural unit of the following formula 1, a structural unit of the following formula 2, and a structural unit of the following formula 3 at a weight ratio of 80/10/10. .

(AS2): homopolymer of poly (trimethylammonium ethyl methacrylate) monomethyl sulfate A polymer compound having a number average molecular weight of about 30,000.
(UA)
: Containing 312.5 parts of hexamethylene diisocyanate trimer and 55.4 parts of methoxypolyethylene glycol having a number average molecular weight of 700, containing a urethane bond and a terminal isocyanate group in the molecule, and blocking the isocyanate group with methyl ethyl ketone oxime However, the surface is 80 parts of isophorone diisocyanate, 20.2 parts of hexamethylene diisocyanate trimer, 229 parts of polyhexamethylene carbonate having a number average molecular weight of 1000, 2.6 parts of trimethylolpropane, and 16.1 of dimethylolpropionic acid. It has a core-shell structure that is coated with a urethane resin that is neutralized with triethylamine and chain-extended with diethylenetriamine.

(UB1): consisting of 78.7 parts of 4,4′-dicyclohexylmethane diisocyanate, 570 parts of terminal OH-modified polyhexamethylene carbonate having a number average molecular weight of 1000, and 15.5 parts of N-methyl-N, N-diethanolamine. An aqueous dispersion (A1) of a polyurethane resin having a Tg of −20 ° C. obtained by reacting a prepolymer with dimethyl sulfate: an acrylic resin. Primal HA-16 (manufactured by Rohm and Haas Japan) (F1): Silica sol aqueous dispersion having an average particle size of 0.07 μm (C1): a polymer type crosslinking agent in which an oxazoline group is branched to an acrylic resin. Epocross WS-500 (Nippon Shokubai Co., Ltd.)
(C2): a polyfunctional epoxy compound having glycidyl ether. Denacor EX-521 (manufactured by Nagase ChemteX Corporation)
(C3): Methoxymethylol melamine. Becamine J-101 (Dainippon Ink Chemical Co., Ltd.)
(C4): A carbodiimide compound aqueous solution. Carbodilite SV-02 (Nisshinbo Co., Ltd.).

Example 1:
A mixed raw material in which the polyester 1 and the polyester 2 are mixed at a ratio of 85% and 15%, respectively, is used as a raw material for the A layer, and a mixed raw material is mixed at a ratio of 95%, 5%, and the mixed raw material is used as a raw material for the B layer. Each was supplied to two extruders and each was melted at 285 ° C., and then two layers and three layers on a casting drum cooled to 40 ° C. with the A layer as the outermost layer (surface layer) and the B layer as the intermediate layer In (ABA), the coextruded product was cooled and solidified so that the thickness composition ratio was A: B: A = 3: 94: 3 to obtain a non-oriented sheet. Next, the film is stretched 3.4 times in the machine direction at a film temperature of 85 ° C. using the roll peripheral speed difference, and then the coating amount after transverse stretching and drying is 0.03 g / m ^{2 on} both surfaces of the machined film. After coating the coating liquid P1 (see Table 1 below), the film was guided to a tenter, stretched 4.0 times at 120 ° C in the transverse direction, heat treated at 230 ° C, and then rolled up on a roll and coated on both sides. A laminated polyester film having a thickness of 100 μm was obtained. The properties of the obtained film are shown in Table 2 below.

Examples 2-6, Comparative Examples 1-6:
Laminated polyester films of Examples 2 to 6 and Comparative Examples 1 to 6 were obtained in the same manner as in Example 1 except that the coating liquids P2 to P12 shown in Table 1 were applied. Of the resulting film

The characteristics are shown in Table 2 below.
Example 7:
A laminated polyester film was obtained in the same manner as in Example 1 except that the mixed raw material in which the polyester 1 and the polyester 2 were mixed at a weight ratio of 60% and 40%, respectively, was used as the raw material for the A layer. The properties of the obtained film are shown in Table 2 below.

Comparative Example 7:
A laminated polyester film was obtained in the same manner as in Example 1 except that the raw material of layer B was 100% of the above polyester 1. The properties of the obtained film are shown in Table 2 below. Next, on one side of this film, 100 parts of silicone coating liquid (linear polyorganosilicone having a vinyl group only at the terminal group (“X-62-1347” manufactured by Shin-Etsu Chemical Co., Ltd.)) as a fine adhesion layer (solid weight) 2 parts) of platinum catalyst (“CAT-PL-56” manufactured by Shin-Etsu Chemical Co., Ltd.) using a bar coater, and drying and curing the coating film at 150 ° C. for 2 minutes. A thin adhesive layer having a thickness of 25 μm was provided, and the film thus obtained has excellent properties as shown in Table 2. Therefore, the film was actually attached to a display screen of a mobile phone as a protective film. The visibility when used was good except for Comparative Example 7 and could be used preferably.

  The film of the present invention can be suitably used as a laminated polyester film for outdoor use which requires excellent antistatic properties, easy adhesion, and adhesion weather resistance while being excellent in ultraviolet ray cutting properties.

Claims (2)

It is a laminated polyester film having a coating layer on at least one side of the polyester film, and the coating layer has an antistatic agent, a compound having an isocyanate-based reactive group and a urethane bond as a core, and the outside is covered with another resin. It is formed from a resin emulsion particle having a core-shell structure, a urethane resin having no isocyanate-based reactive group at the terminal, and a coating liquid containing one or more crosslinking agents, and the light transmittance at 380 nm is 5% or less. A laminated polyester film characterized by A polyester film for decorative film comprising a slightly adhesive layer on at least one surface of the laminated polyester film according to claim 1.