JP5560693B2 - Hard coat film for molding and molded body - Google Patents

Description

  The present invention relates to a molding polyester film and a molding hard coat film. The present invention relates to a molding polyester film which is attached to a front surface of a member, a molded body, etc. and has excellent adhesion to a hard coat layer under high temperature and high humidity, and a molding hard coat film using the same.

  Conventionally, a polyvinyl chloride film is typical as a film for molding. However, in recent years, a film made of polyester, polycarbonate and acrylic resin having a small environmental load is used due to the need for environmental resistance. Especially, the polyester film containing copolyester has the characteristic excellent in the moldability in low temperature and low pressure (patent document 1).

  For example, when a molding film is attached to a position where it touches the outside, such as a home appliance, a car nameplate or a building material member, in order to prevent scratches, the surface hardness of the molding film is supplemented and the scratch resistance is improved. A hard coat layer is provided on the surface. Moreover, in order to improve the adhesiveness of the polyester film of a base material and a hard-coat layer, the adhesive property modification layer which has easy-contact property in many cases is provided as these intermediate | middle layers.

  For example, a method of imparting easy adhesion to the surface of a polyester film as a base material by providing an adhesive modified layer mainly composed of various resins such as polyester, acrylic, polyurethane, and acrylic graft polyester is generally used. Known.

  In recent years, portable devices using a hard coat film as a member are used in various environments, both indoors and outdoors. In particular, portable devices may require moisture and heat resistance that can withstand a bathroom, a hot and humid area, and the like. When used in such applications, high adhesion is required so that delamination does not occur even under high temperature and high humidity. Therefore, in the following patent document, a cross-linking agent is added to the coating solution, and a cross-linking structure is formed in the adhesive modified layer resin when forming the adhesive modified layer by the in-line coating method. Thermoplastic resin films are disclosed (Patent Documents 1 to 4).

  On the other hand, since the thermoplastic resin film is insulative, there is a problem of dust adhesion due to electrification and deterioration of handling properties. For this reason, methods for imparting antistatic properties to the surface of a biaxially oriented thermoplastic resin film by various methods have been proposed.

  For example, Patent Documents 5 and 6 propose a method of imparting antistatic properties to a substrate film by providing a coating layer containing an ion conductive antistatic agent on the surface of the thermoplastic resin film of the substrate. ing. However, these methods are highly dependent on humidity because of the conductive mechanism that depends on the adsorption of moisture in the air. When a functional layer is provided on the antistatic layer, sufficient antistatic performance cannot be obtained.

  Patent Documents 7 and 8 propose providing an application layer containing a conductive polymer that does not depend on humidity. However, although it has sufficient antistatic performance, it has not yet achieved sufficient adhesion under high temperature and high humidity.

JP 2000-141574 A Japanese Patent No. 3773738 Japanese Patent No. 3900191 JP 2007-253512 A JP-A-60-141525 JP-A-61-204240 Japanese Patent No. 3966171 JP 2006-294532 A

  Longer life expectancy is expected for home appliances and other products to reduce the global environmental impact. Therefore, it was considered that the molding polyester film used as a member also needs to maintain adhesion for a long time even under high temperature and high humidity. However, although the adhesion modified layer as disclosed in the above-mentioned patent document initially shows good adhesion, a decrease in adhesion strength is inevitable in long-term use under high temperature and high humidity. It was. Due to such a decrease in adhesion, there is a problem that the initial performance is not maintained for a long time.

  In view of the above-mentioned problems, the present invention provides a molding polyester film that hardly causes deterioration of the coating layer under high temperature and high humidity, which has been conventionally considered to be unavoidable, in other words, hardly causes a decrease in adhesion under high temperature and high humidity. To do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a coating layer containing a urethane resin containing a polycarbonate polyol as a constituent, a carbodiimide compound and / or a resin having an oxazoline group, and a π-electron conjugated conductive polymer. As a result, the present inventors have found the fact that the conventional technical common sense that adhesiveness is improved under high temperature and high humidity with sufficient antistatic performance has been achieved, and the present invention has been achieved. As described in the above-mentioned patent document, in order to improve the adhesion of the coating layer in the conventional technical common sense, it is mixed with a crosslinking agent and a resin having a functional group capable of reacting with it, and a highly crosslinked structure is formed when the coating layer is formed. It has been considered desirable to form. However, the present invention uses a polyester resin that does not substantially have a carboxylic acid group that is a functional group that reacts with a carbodiimide group and / or an oxazoline group, thereby improving adhesion at high temperatures and high humidity. It is an easy-adhesion film based on a new technical idea that goes against technology.

The above-described problem can be achieved by the following solution means.
(1) At least one surface of a polyester film having a copolymer component has an adhesive modified layer containing a urethane resin having a polycarbonate polyol as a constituent component and a crosslinking agent, and the urethane resin has a polyoxyalkylene group. The molding hard coat having a hard coat layer formed by coating and curing a coating solution on the surface of the adhesive modified layer of the molding polyester film , wherein the crosslinking agent is a resin having a carbodiimide compound and / or an oxazoline group. It is a film, and the coating solution contains at least an ionizing radiation curable compound having three or more functional groups and a monofunctional and / or bifunctional ionizing radiation curable compound, and the ionizing radiation curable contained in the coating solution. The content of mono- and / or bifunctional ionizing radiation-curable compounds in the mold compound is 5% by mass or more and 9 Molding the hard coat film is less mass%.
(2) The hard coat film for molding, wherein the adhesion modified layer further contains a π-electron conjugated conductive polymer.
(3) The hard coating film for molding, wherein the π-electron conjugated conductive polymer has thiophene or a thiophene derivative as a repeating unit.
( 4 ) The hard coat film for molding comprising particles having an average particle diameter of 10 nm or more and 300 nm or less in the hard coat layer, and the content of the particles in the hard coat layer is 5 mass% or more and 70 mass% or less.
( 5 ) The hard coating film for molding, wherein at least one ionizing radiation curable compound contained in the coating solution is an ionizing radiation curable compound having an amino group.
( 6 ) The hard coat layer contains an ionizing radiation curable silicone resin, and the content of the ionizing radiation curable silicone resin in the hard coat layer is 0.15 mass relative to 100 parts by mass of the ionizing radiation curable compound. The hard coat film for molding which is at least 15 parts by mass.
( 7 ) A molded body formed by molding the molding hard coat film.

  The molding polyester film of the present invention is excellent in adhesiveness (moisture heat resistance) with the functional layer under high temperature and high humidity. Therefore, as a preferred embodiment, the adhesion at the high temperature and high humidity treatment is equal to or improved from the initial adhesion. As a preferred embodiment of the present invention, when the molding polyester film of the present invention is used as a base material for a molding hard coat film, the adhesion with the molding hard coat layer under high temperature and high humidity is good. Further, in a preferred embodiment of the present invention, it has further sufficient antistatic performance while having the above effects. Therefore, it is excellent in handling property and dustproof property. Furthermore, in a preferred embodiment of the present invention, while having the above-mentioned effects, both the properties of excellent surface hardness as a molding hard coat film and moldability capable of following deformation during molding are highly compatible. Therefore, it can be suitably used for members for nameplates and building materials.

(Adhesive modified layer)
The polyester film for molding according to the present invention includes an adhesive modified layer containing a urethane resin having a polycarbonate polyol as a constituent component and a resin having a carbodiimide compound and / or an oxazoline group on at least one side of a polyester film having a copolymer component. It is important to provide

  Conventionally, it has been considered desirable to positively introduce a crosslinked structure from the viewpoint of improving the heat-and-moisture resistance of the adhesive modified layer. However, in the present invention, it has been found that the heat-and-moisture resistance is improved by configuring the adhesive modified layer as described above. Although the mechanism by which the adhesiveness under high temperature and high humidity is improved by such a configuration is not well understood, the present inventor thinks as follows. Unreacted carbodiimide groups and / or oxazoline groups remain in the adhesion modified layer of the present invention. Thereafter, the polyester resin constituting the base material is hydrolyzed under a high temperature and high humidity environment, the ester bond is broken, and a carboxylic acid group terminal is generated. Here, the unreacted carbodiimide group and / or oxazoline group remaining in the adhesion modified layer reacts with the generated carboxylic acid terminal to form a crosslink. In other words, it is believed that a decrease in adhesion due to hydrolysis can be prevented by self-healing. Furthermore, in this invention, the more excellent heat-and-moisture resistance can be exhibited by using the polycarbonate-type urethane resin excellent in durability.

  Further, by containing a π-electron conjugated conductive polymer in the adhesive modified layer, stable antistatic performance can be imparted even under low humidity. By such an embodiment, the present invention improves the adhesion (humidity heat resistance) under high temperature and high humidity with the molding hard coat layer and further functional layers in a state having sufficient antistatic performance. Can do. Further, the configuration of the present invention will be described in detail below.

  The adhesion modified layer of the present invention needs to contain a urethane resin. Adhesion can be improved by including a urethane resin.

  The urethane resin of the present invention includes at least a polyol component and a polyisocyanate component as constituent components, and further includes a chain extender as necessary. The urethane resin of the present invention is a polymer compound in which these constituent components are mainly copolymerized by urethane bonds. In this invention, it has the polycarbonate polyol as a structural component of a urethane resin, It is characterized by the above-mentioned. Moisture heat resistance can be improved by including a urethane resin containing polycarbonate as a constituent component in the coating layer of the present invention. The components of these urethane resins can be specified by nuclear magnetic resonance analysis or the like.

  Examples of the polycarbonate polyol which is a constituent component of the urethane resin of the present invention include polycarbonate diol and polycarbonate triol. Polycarbonate diol can be preferably used. Examples of the polycarbonate diol that is a constituent component of the urethane resin of the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, A polycarbonate diol obtained by reacting one or more diols such as bisphenol-A with carbonates such as dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and phosgene. , And the like. The number average molecular weight of the polycarbonate diol is preferably 300 to 5000, and more preferably 500 to 3000.

  In the present invention, the composition molar ratio of the polycarbonate polyol which is a constituent component of the urethane resin is preferably 3 to 100 mol%, and preferably 5 to 50 mol% when the total polyisocyanate component of the urethane resin is 100 mol%. More preferably, it is 6 to 20 mol%. When the composition molar ratio is low, the durability effect by the polycarbonate polyol may not be obtained. Moreover, when the said composition molar ratio is high, initial adhesiveness may fall.

  Examples of the polyisocyanate that is a constituent component of the urethane resin of the present invention include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, Aliphatic diisocyanates such as isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, aliphatic diisocyanates such as hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate Or polyisocyanates obtained by adding these compounds in advance with trimethylolpropane or the like alone or in plural.

  Chain extenders include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol, polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, ethylenediamine Diamines such as hexamethylenediamine and piperazine, aminoalcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol, and water.

  The coating layer of the present invention is preferably provided by an in-line coating method described later using an aqueous coating solution. Therefore, it is desirable that the urethane resin of the present invention is water-soluble. When a water-soluble urethane resin is used, compatibility with a carbodiimide compound increases, and transparency can be improved. The “water-soluble” means that it dissolves in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.

  In order to impart water solubility to the urethane resin, a sulfonic acid (salt) group or a carboxylic acid (salt) group can be introduced (copolymerized) into the urethane molecular skeleton. Since the sulfonic acid (salt) group is strongly acidic and it may be difficult to maintain moisture resistance due to its hygroscopic performance, it is preferable to introduce a weakly acidic carboxylic acid (salt) group.

  In order to introduce a carboxylic acid (salt) group into a urethane resin, for example, as a polyol component, a polyol compound having a carboxylic acid group such as dimethylolpropionic acid or dimethylolbutanoic acid is introduced as a copolymer component to form a salt. Neutralize with an agent. Specific examples of the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, N such as N-methylmorpholine and N-ethylmorpholine. -N-dialkylalkanolamines such as alkylmorpholines, N-dimethylethanolamine, N-diethylethanolamine and the like. These can be used alone or in combination of two or more.

  In order to impart water solubility, when a polyol compound having a carboxylic acid (salt) group is used as a copolymerization component, the composition molar ratio of the polyol compound having a carboxylic acid (salt) group in the urethane resin is the same as that of the urethane resin. When the total polyisocyanate component is 100 mol%, it is preferably 3 to 60 mol%, more preferably 10 to 40 mol%. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult. Moreover, when the said composition molar ratio exceeds 60 mol%, since the residual carbodiimide group and / or oxazoline group at the time of coating layer formation reduce, heat-and-moisture resistance may fall.

  However, when a urethane resin into which a carboxylic acid is introduced as described above is used, it reacts with a carbodiimide group and / or an oxazoline group in the coating solution, and unreacted carbodiimide group and / or oxazoline group at the time of forming a coating layer. May decrease. Therefore, it is desirable that the coating layer has substantially no carboxylic acid (salt) group. Therefore, in order to impart water solubility to the urethane resin, it is a preferred embodiment of the present invention to introduce a polyoxyalkylene group instead of the carboxylate group. When using the urethane resin which introduce | transduced the polyoxyalkylene group as a urethane resin, a coating layer does not have a carboxyl group substantially. Therefore, unreacted carbodiimide groups and / or oxazoline groups remain stably, and more excellent wet heat resistance can be exhibited.

  Examples of the polyoxyalkylene group introduced into the urethane resin include a polyoxyethylene group, a polyoxypropylene group, and a polytetramethylene glycol chain. These can be used alone or in combination of two or more. Among these, a polyoxyethylene group can be preferably used.

  In order to introduce a polyoxyethylene group into a urethane resin, for example, polyisocyanate and one-end blocked polyoxyethylene glycol (alkoxyethylene glycol having one end sealed with an alkyl group having 1 to 20 carbon atoms) are blocked at one end. After the urethanation reaction at an excess ratio of the isocyanate group of the diisocyanate with respect to the hydroxyl group of the polyoxyethylene glycol, the polyoxyethylene chain-containing monoisocyanate was obtained by removing the unreacted polyisocyanate if necessary. Then, the obtained polyoxyethylene chain-containing monoisocyanate and diisocyanate can be obtained by an allophanatization reaction.

  In order to impart water solubility, when introducing polyoxyethylene groups into the urethane resin, the composition molar ratio of the polyoxyethylene groups in the urethane resin is 100 mol% of the total polyisocyanate component of the urethane resin. It is preferably 3 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. If the composition molar ratio is less than 3 mol%, water dispersibility may be difficult.

  The urethane resin is preferably contained in the coating layer in an amount of 30% by mass to 90% by mass, and when it contains a π-electron conjugated conductive polymer, it is preferably contained in an amount of 30% by mass to 85% by mass. In particular, when high adhesion is required as in a hard coat layer, it is more preferably 40% by mass or more and 70% by mass or less. When the content of the urethane resin is large, the adhesiveness under high temperature and high humidity is lowered, and conversely, when the content is small, the initial adhesiveness is lowered.

  In the present invention, a resin other than the urethane resin may be contained in order to improve adhesion. For example, an acrylic resin, a polyester resin, etc. are mentioned. Preferably, the carboxylic acid group content is low. More preferably, it does not contain a carboxylic acid group. When there are many carboxylic acid groups, it reacts with the carbodiimide group and / or oxazoline group, and the carbodiimide group and / or oxazoline group reacts with the carboxylic acid group generated from the polyester substrate under high temperature and high humidity. .

  In the present invention, it is necessary to contain a carbodiimide compound and / or a resin having an oxazoline group. Examples of the carbodiimide compound include a monocarbodiimide compound and a polycarbodiimide compound.

  Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-6-naphthylcarbodiimide, and the like. .

  As the polycarbodiimide compound, those produced by a conventionally known method can be used. For example, it can be produced by synthesizing an isocyanate-terminated polycarbodiimide by a condensation reaction involving decarbonization of diisocyanate.

  Examples of the diisocyanate that is a raw material for synthesizing a polycarbodiimide compound include isomers of toluylene diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, aromatic aliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate and 4 , 4-dicyclohexylmethane diisocyanate, alicyclic diisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and aliphatic diisocyanates such as 2,2,4-trimethylhexamethylene diisocyanate. From the problem of yellowing, aromatic aliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates are preferred.

The diisocyanate may be used with a molecule controlled to an appropriate degree of polymerization using a compound that reacts with a terminal isocyanate such as monoisocyanate. Examples of monoisocyanates for sealing the ends of polycarbodiimide and controlling the degree of polymerization thereof include phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. In addition, a compound having an OH group, —NH ₂ group, COOH group, or SO ₃ H group can be used as a terminal blocking agent.

  The condensation reaction involving decarbonization of diisocyanate proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-methyl-1-phenyl-2. -Phosphorene-1-oxide, phospholene oxides such as these 3-phospholene isomers and the like can be mentioned, and 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable from the viewpoint of reactivity. The amount of the catalyst used can be a catalyst amount.

  The mono- or polycarbodiimide compound described above is desirably kept in a uniform dispersed state when blended with an aqueous coating material. For this purpose, it is emulsified with an appropriate emulsifier and used as an emulsion, or a polycarbodiimide compound. It is preferable to add a hydrophilic segment in the molecular structure of the compound and mix it with the paint in the form of a self-emulsified product or in the form of a self-dissolved product.

  Examples of the carbodiimide compound used in the present invention include water dispersibility and water solubility. Water solubility is preferred because it is highly compatible with other water-soluble resins and improves the transparency and cross-linking reaction efficiency of the adhesive modified layer.

  In order to make a carbodiimide compound water-soluble, an isocyanate-terminated polycarbodiimide is synthesized by a condensation reaction involving decarbonization of isocyanate, and then a hydrophilic part having a functional group having reactivity with an isocyanate group is added. Can be manufactured.

  Examples of hydrophilic sites include (1) quaternary ammonium salts of dialkylamino alcohols and quaternary ammonium salts of dialkylaminoalkylamines, (2) alkyl sulfonates having at least one reactive hydroxyl group, and the like (3) Examples thereof include poly (ethylene oxide) end-capped with an alkoxy group, a mixture of poly (ethylene oxide) and poly (propylene oxide), and the like. The carbodiimide compound is (1) cationic, (2) anionic, and (3) nonionic when the above hydrophilic moiety is introduced. Especially, the nonionic property which can be compatible regardless of the ionicity of other water-soluble resin is preferable. Moreover, in order to improve heat-and-moisture resistance, nonionic property which does not need to introduce | transduce an ionic hydrophilic group is preferable.

  Examples of the resin having an oxazoline group include water dispersibility and water solubility. The resin having an oxazoline group is preferably water-soluble because it has good compatibility with other water-soluble resins and improves the transparency of the coating layer and the crosslinking reaction efficiency. The above water-soluble means to dissolve in water or an aqueous solution containing less than 50% by mass of a water-soluble organic solvent.

  In order to make the resin having an oxazoline group water-soluble, it is preferable to contain a hydrophilic monomer. As the hydrophilic monomer, a monomer having a polyethylene glycol chain such as 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, a monoester compound of (meth) acrylic acid and polyethylene glycol, (Meth) acrylic acid 2-aminoethyl and its salts, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, (meth) acrylonitrile, sodium styrenesulfonate, etc. Can be mentioned. Especially, it is preferable to contain the monomer which has polyethyleneglycol chains, such as (meth) acrylic-acid methoxypolyethylene glycol with high solubility to water, and the monoester compound of (meth) acrylic acid and polyethyleneglycol.

  The resin having a carbodiimide compound and / or an oxazoline group is 5% by mass or more and 90% by mass or less in the adhesive modified layer, and 5% by mass or more and 50% by mass or less when a π-electron conjugated conductive polymer is contained. It is preferable to contain. In particular, when high adhesion is required like a hard coat layer, it is more preferably 10% by mass or more and 40% by mass or less. When the content of the carbodiimide compound and / or the resin having an oxazoline group is large, the adhesion to the functional layer is lowered, and conversely, when the content is small, it is generated from the polyester resin under high temperature and high humidity. Since the carbodiimide group and / or the oxazoline group that reacts with the carboxylic acid group decreases, the restoration function of the coating film decreases and the adhesion decreases.

  In the present invention, in order to improve the coating film strength, a cross-linking agent different from the carbodiimide compound and / or the resin having an oxazoline group or a resin having a cross-linking group may be contained in the adhesive modified layer. . Examples of the crosslinking agent include urea, epoxy, melamine, isocyanate, and silanol. Moreover, in order to promote a crosslinking reaction, a catalyst etc. are used suitably as needed.

  In the present invention, a π-electron conjugated conductive polymer is preferably contained in order to maintain stable and excellent antistatic properties. As the π-electron conjugated conductive polymer, the repeating unit is aniline and / or a derivative thereof, pyrrole and / or a derivative thereof, isothianaphthene and / or a derivative thereof, acetylene and / or a derivative thereof, thiophene and / or A derivative thereof or the like is preferable. Among them, thiophene and / or its derivatives are particularly preferable because they are less colored and can provide a high total light transmittance.

  Examples of the thiophene and / or derivatives thereof include compounds having a structure in which the positions of the 3-position and 4-position of the thiophene ring are substituted. Those in which an oxygen atom is bonded to the 3rd and 4th carbon atoms are preferred. Some hydrogen atoms or carbon atoms bonded directly to carbon atoms have insufficient water solubility.

  Moreover, what is polymerized in presence of the said thiophene and / or its derivative polyanion is mentioned. Examples of the polyanion include polyacrylic acid, polymethacrylic acid, polymaleic acid, polystyrene sulfonic acid, and the like, and polystyrene sulfonic acid is preferable from the viewpoint of conductivity.

  Moreover, by using a high-boiling solvent, thiophene dissolves, and the density of thiophene and / or its derivative on the coating surface layer after drying increases, and the conductivity can be improved. As the high boiling point solvent, those having a boiling point of 100 degrees or more are preferable. Examples of the highly polar water-miscible solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, furfural, acetonitrile, propylene carbonate, and tetrahydrothiophene-1,1-dioxide. (Sulfolane), sugars and derivatives thereof include, for example, sucrose, glucose, fructose, lactose, sorbitol, mannitol, and derivatives thereof, and alcohols and derivatives thereof include (poly) ethylene glycol, (poly) propylene glycol , (Poly) glycerin, and derivatives thereof, and the most suitable one is selected depending on the drying temperature.

  In the case of imparting antistatic properties, the thiophene and / or derivative thereof is preferably contained in the adhesive property modified layer in an amount of 10% by mass to 70% by mass. More preferably, it is 20 mass% or more and 50 mass% or less. When the content is large, the adhesion to the functional layer is lowered, and conversely, when the content is small, sufficient antistatic performance cannot be obtained.

  In the present invention, particles can also be contained in the adhesive modification layer. Particles are (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, aluminum silicate, diatomaceous earth Inorganic particles such as soil, calcium silicate, aluminum hydroxide, hydrous halloysite, magnesium carbonate, magnesium hydroxide, (2) acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / Butadiene, polystyrene / acrylic, polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, di Rirufutareto systems include organic particles of polyester or the like.

  The average particle diameter of the particles is not particularly limited, but from the viewpoint of maintaining the transparency of the film, the average particle diameter of the particles is preferably 1 to 500 nm, and more preferably 1 to 100 nm. The average particle diameter is an average particle diameter measured by using a Coulter Counter (manufactured by Beckman Coulter, Multisizer II type) dispersed in a solvent that does not swell.

  Two or more kinds of particles having different average particle diameters may be used as the particles.

  The content of the particles in the modified adhesive layer is preferably 0.5% by mass or more and 20% by mass or less. When the amount is small, sufficient blocking resistance cannot be obtained. Further, scratch resistance is deteriorated. When the amount is large, not only the transparency of the coating layer is deteriorated, but also the coating strength is lowered.

  The adhesive property modifying layer may contain a surfactant for the purpose of improving leveling properties during coating and defoaming the coating solution. The surfactant may be any of cationic, anionic and nonionic surfactants, but is preferably a silicon-based, acetylene glycol-based or fluorine-based surfactant. These surfactants are preferably contained in the coating layer within a range that does not impair the adhesion to the functional layer.

In the present invention, when the antistatic property is imparted, the surface resistance of the adhesive modified layer is preferably 1 × 10 ⁵ to 1 × 10 ¹² Ω / □. When the surface resistance is lower than 1 × 10 ¹² Ω / □, when a functional layer is provided using a roll-to-roll method, charging (unwinding charging) when unwinding the film from the roll, film and metal Charging (friction charging) due to friction with a roll or rubber roll can be greatly reduced. For this reason, the adhesion of foreign matter or the like is greatly reduced before the coating liquid for forming the functional layer is applied. As the surface resistance of the coating layer is lower, the amount of foreign matter attached can be reduced, and the attachment of minute foreign matter can also be prevented. However, lowering the surface resistance below 1 × 10 ⁵ Ω / □ has not only a cost problem but also a problem that the transparency of the film deteriorates.

  The molding polyester film of the present invention preferably has a haze value of 2.0% or less, more preferably 1.5% or less. Such an easily-adhesive thermoplastic resin film improves the compatibility with other resins by making the carbodiimide compound and / or the resin having an oxazoline group contained in the above-mentioned adhesive modified layer water-soluble. can get.

  In order to impart other functionality to the adhesion modified layer, various additives may be contained within a range that does not impair the adhesion to the functional layer. Examples of the additive include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam suppressors, antifoaming agents, and preservatives.

  In the present invention, examples of the method for providing the adhesive modified layer on the polyester film include a method in which a coating liquid for forming an adhesive modified layer containing a solvent, particles and a resin is applied to the polyester film and dried. Examples of the solvent include organic solvents such as toluene, water, and a mixed system of water and a water-soluble organic solvent. Preferably, water alone or a mixture of a water-soluble organic solvent and water is used from the viewpoint of environmental problems. preferable.

(Base polyester film)
(Copolymerized polyester)
As the base film of the present invention, a copolymer polyester is used as a constituent component from the viewpoint of high moldability. Here, moldability means that a molded body can be formed by a molding process such as mold molding, pressure molding, or vacuum molding. Specifically, it has a film stress characteristic that can form a molded body without breaking the base film even when a high stress is partially generated in a portion that is locally elongated by molding.

  Examples of the copolyester include (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol, or (b) terephthalic acid and isophthalic acid. A copolyester composed of an aromatic dicarboxylic acid component containing an acid and a glycol component containing ethylene glycol is preferred. Moreover, it is preferable from the point which improves the moldability that the polyester which comprises a polyester film contains a 1, 3- propanediol unit or a 1, 4- butanediol unit as a glycol component further. In the case of (a) above, the copolymerization polyester used in the present invention is preferably added with a copolymerization component so that the proportion of ethylene glycol in the total glycol component is 20 mol% to 95 mol%. The lower limit of the proportion of ethylene glycol in the total glycol component is preferably 30 mol%, more preferably 40 mol%, and the upper limit is preferably 90 mol%, more preferably 80 mol%, still more preferably. Is 70 mol%. In the case of the above (b), the copolymerized polyester used in the present invention is added with a copolymer component such that the proportion of terephthalic acid in the total aromatic dicarboxylic acid component is 50 mol% to 95 mol%. It is preferable. The lower limit of the proportion of terephthalic acid in the total aromatic dicarboxylic acid component is preferably 60 mol%, more preferably 70 mol%, and the upper limit is preferably 90 mol%.

  In the present invention, as the film raw material, any method of copolymerized polyester alone, one or more homopolyesters or a blend of copolymerized polyesters, or a combination of homopolyester and copolymerized polyester is possible. Among these, the blending method is preferable from the viewpoint of suppressing the lowering of the melting point.

  When using a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol or alicyclic glycol as the copolymer polyester, the aromatic dicarboxylic acid component is Terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more. Particularly preferred is 95 mol% or more, and particularly preferred is 100 mol%.

  Examples of branched aliphatic glycols include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.

  Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. Furthermore, in the present invention, it is a more preferable embodiment that 1,3-propanediol or 1,4-butanediol is used as a copolymerization component in addition to the glycol component. Use of these glycols as a copolymerization component is suitable for imparting the above-mentioned properties, and is also excellent in transparency and heat resistance, and from the viewpoint of improving the adhesion with the adhesion modified layer. Is also preferable.

  When the copolymer polyester is composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol, the amount of ethylene glycol is based on the total glycol component. It is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 100 mol%. As the glycol component other than ethylene glycol, the above-mentioned branched aliphatic glycol, alicyclic glycol, or diethylene glycol is preferable.

  The polyester used as a film raw material preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, particularly preferably 0.60 dl / g or more from the viewpoint of film formation stability. is there. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

(Polyester film containing copolymer polyester)
In the present invention, the film raw material is a polyester resin obtained by blending a copolyester alone or one or more homopolyesters or copolyesters. It is preferable that the polyester-type resin used for this invention contains 5-50 mass% of copolymerization components. Here, examples of the homopolyester include polyethylene terephthalate, polyethylene naphthalate, polytetramethylene terephthalate, and polybutylene terephthalate.

  The melting point of the polyester resin is preferably 180 to 250 ° C. from the viewpoint of heat resistance and moldability. By controlling the type and composition of the polymer used within the range of the melting point, it is possible to economically produce a high-quality molded product having excellent moldability. Here, the melting point is an endothermic peak temperature at the time of melting, which is detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC). The melting point was determined by measuring at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.). The lower limit of the melting point is more preferably 190 ° C, further preferably 200 ° C, and particularly preferably 210 ° C or higher. If the melting point is less than 180 ° C, the heat resistance tends to deteriorate. Therefore, it may become a problem when exposed to high temperature during molding or use of a molded product.

  The upper limit of the melting point is preferably higher from the viewpoint of heat resistance, but when the polyethylene terephthalate unit is the main component, the film having a melting point exceeding 250 ° C. tends to deteriorate moldability. In addition, transparency tends to deteriorate. Furthermore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 250 ° C.

  The base film used in the present invention may be a single layer film or a composite film having two or more layers in which a surface layer and a center layer are laminated. In the case of a composite film, there is an advantage that the functions of the surface layer and the center layer can be designed independently. For example, by containing particles only on the thin surface layer and forming irregularities on the surface, the handling property is maintained, but the thick central layer does not substantially contain particles, so that the composite film as a whole is transparent. Can be further improved.

  The thickness of the substrate film used in the present invention varies depending on the material, but when a polyester film is used, the lower limit is preferably 35 μm or more, more preferably 50 μm or more. On the other hand, the upper limit of the thickness is preferably 500 μm or less, more preferably 300 μm or less. When the thickness is small, the handling property is poor. On the other hand, when the thickness is large, not only is there a problem in terms of cost, but flatness due to curling tends to occur when the material is wound and stored in a roll shape.

(Manufacture of polyester film for molding)
The polyester film for molding of the present invention is preferably a biaxially stretched polyester obtained by sequential biaxial stretching or simultaneous biaxial stretching from the viewpoint of solvent resistance and dimensional stability. Hereinafter, the most preferred sequential biaxial stretching method will be described.

  First, the raw material pellets are sufficiently vacuum-dried. Next, the polyester sheet is melted at a temperature equal to or higher than the melting point using an extruder, the polyester sheet is extruded from a die by a co-extrusion method, and is closely adhered to a rotary cooling roll to obtain an unstretched polyester film. The unstretched polyester film is guided to a roll-type longitudinal stretching machine and heated to 80 to 125 ° C., and then stretched 2.5 to 5.0 times in the longitudinal direction due to the peripheral speed difference of the roll to obtain a uniaxially stretched film.

  Thereafter, the uniaxially stretched polyester film is guided to a transverse stretching machine, heated to 80 to 180 ° C., then stretched 2.5 to 5.0 times in the transverse direction, and then heat set at 200 to 240 ° C., then necessary. In accordance with the above, 1-10% relaxation treatment is carried out in the longitudinal direction and / or the transverse direction, and then wound up with a film winder to obtain a polyester film for molding.

  As the step of applying the adhesive modification layer, any method such as a method of applying before stretching of the film, a method of applying after longitudinal stretching, and a method of applying to the film surface after the orientation treatment can be used. The in-line coating method is applied before the crystal orientation of the base polyester film is completed, and then stretched in at least one direction, and then the crystal orientation of the polyester film is completed. Is the preferred method

  As a method for providing an adhesion modified layer, a conventionally used method such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method is applied. it can

(Hard coat film for molding)
Another embodiment of the present invention is a molding hard coat film provided with a hard coat layer via an adhesive property modification layer of the molding polyester film. The hard coat layer in the present invention forms a hard coat layer formed by coating and curing a coating solution on the surface of the adhesion-modified layer of the molding polyester film. In the present invention, the hard coat layer has a coating film having a hardness higher than that of the base material in order to supplement the surface hardness of the base material made of the base film and improve the scratch resistance, and is stretched during molding. The layer which has the outstanding moldability which can also follow a deformation | transformation is shown. That is, the hard coat film for molding is a molded film having a hard coat layer in advance before molding processing, instead of providing a hard coat layer after molding a base film as in the prior art. This not only stabilizes the quality of the hard coat molded body, but also enables continuous formation of a stable hard coat layer, thereby suppressing the occurrence of interference fringes due to fluctuations in the hard coat layer, etc. This is preferable.

  The layer having a hard coat property that can be used in the present invention is not particularly limited, and examples thereof include melamine-based, acrylic-based, and silicone-based ionizing radiation curable compounds. Ionizing radiation curable compounds are preferred. Here, the ionizing radiation curable compound refers to a compound that is polymerized and / or reacted by irradiating any one of electron beam, radiation, and ultraviolet rays, and the compound is polymerized and / or reacted. A hard coat layer is formed. In the present invention, the ionizing radiation curable compound includes naturally not only monomers and precursors but also ionizing radiation curable resins obtained by polymerization and / or reaction thereof.

  In the present invention, the ionizing radiation curable compound contained in the coating solution for forming the hard coat layer includes a trifunctional or higher functional ionizing radiation curable compound in addition to the mono- or bifunctional ionizing radiation curable compound. It is preferable that 1 or more types are included. Thus, by adjusting two or more types of ionizing radiation curable compounds having different functional numbers within a specific concentration range, a hetero-crosslinked structure is introduced into the hard coat layer, and the surface hardness and scratch resistance are improved by the hard segment. The moldability is suitably imparted by the stretchability of the soft segment.

  In the present invention, in order to achieve both high surface hardness and excellent moldability, the content of the mono- and / or bifunctional ionizing radiation-curable compound in the ionizing radiation-curable compound contained in the coating solution is 5 It is preferable that they are mass% or more and 95 mass% or less. When the content is less than 5% by mass, cracks occur in the hard coat layer during molding, which is not preferable. Moreover, when the said content exceeds 95 mass%, it is difficult to obtain the cured film which has sufficient surface hardness and abrasion resistance. The lower limit of the content is more preferably 10% by mass or more, and further preferably 20% by mass or more. Moreover, 90 mass% or less is more preferable, as for the upper limit of the said content, 80 mass% or less is more preferable, and 70 mass% or less is more preferable.

  When an acrylate ionizing radiation curable compound is used as the ionizing radiation curable compound, the monofunctional (monofunctional) acrylate ionizing radiation curable compound in the present invention has at least one (meth) acryloyl group in the molecule. If it is a compound to contain, it will not restrict | limit in particular. For example, acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, di Cyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) Kurylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichloro Phenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinyl Pyrrolidone, N-vinylformamide, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, Tabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenyl (meth) ) Derivatives such as acrylate and its modified caprolactone, acrylic acid and the like, and mixtures thereof.

  When an acrylate ionizing radiation curable compound is used as the ionizing radiation curable compound, the bifunctional acrylate ionizing radiation curable compound in the present invention is a polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule. A compound in which the hydroxyl group is an esterified product of two (meth) acrylic acids can be used. Specifically, (a) C2-C12 alkylene glycol (meth) acrylic acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, etc. (b) (meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (C) (meth) acrylic acid diesters of polyhydric alcohols: (e) pentaerythritol di (meth) acrylate, etc. (d) bisphenol A or bisphenol A hydride ethylene oxide and propylene oxide adduct (meth) acrylic acid diester Class: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis (4-acryloxypropoxyphenyl) propane, etc. (e) a polyvalent isocyanate compound and two or more alcoholic hydroxyl groups Urethane (meth) acrylate having two (meth) acryloyloxy groups in the molecule obtained by further reacting an alcoholic hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by reacting the containing compound in advance (F) two or more epoxies in the molecule Epoxy (meth) acrylates having two (meth) acryloyloxy groups in the resulting molecule to a compound having a sheet group by reacting acrylic acid or methacrylic acid, and the like.

  When an acrylate ionizing radiation curable compound is used as the ionizing radiation curable compound, the trifunctional or higher functional acrylate ionizing radiation curable compound in the present invention includes (a) specifically pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meta) ) Such as acrylate, (b) a terminal isocyanate group-containing compound obtained by previously reacting a polyvalent isocyanate compound with two or more alcoholic hydroxyl group-containing compounds, and further containing an alcoholic hydroxyl group Urethane (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by reacting (meth) acrylate, (c) Acrylic acid or a compound having 3 or more epoxy groups in the molecule Examples thereof include epoxy (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by reacting methacrylic acid.

  In the present invention, it is preferable that at least one ionizing radiation curable compound contained in the coating solution has an amino group in order to better achieve both high surface hardness and excellent moldability. When a compound having an amino group is used as the ionizing radiation curing compound, the amino group traps radical oxygen, and the influence of oxygen inhibition on the curing reaction of the surface layer portion of the hard coat layer is reduced. The reaction proceeds. Thereby, the stress applied to the hard coat layer at the time of molding is dispersed throughout the layer, and the generation of cracks at the time of molding is easily suppressed.

  The content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is preferably 2.5% by mass or more and 95% by mass or less. The lower limit of the content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is more preferably 5% by mass or more, and further preferably 10% by mass or more. . The upper limit of the content is more preferably 92.5% by mass or less, further preferably 90% by mass or less, and further preferably 50% by mass or less. When the content of the ionizing radiation curable compound containing an amino group in the ionizing radiation curable compound contained in the coating solution is less than 2.5% by mass, it is difficult to uniformly cure the entire hard coat layer. It becomes difficult to obtain resistance to cracks. Further, when the ionizing radiation curable compound containing an amino group becomes high in concentration, yellowing of the hard coat layer becomes strong due to the amino group. Therefore, when the content exceeds 95% by mass, high transparency is impaired. May be. For example, when printing is performed on the surface on which the hard coat layer is not laminated, the color b value of the film is preferably 2 or less. In this case, the ionizing radiation curable compound containing the amino group is 92.5% by mass or less. It is preferable that

  In the present invention, the coating solution contains a monofunctional and / or bifunctional ionizing radiation curable compound and an ionizing radiation curable compound having three or more functional groups. The ionizing radiation curable compound of the part may be any one containing an amino group. Further, any one of a monofunctional ionizing radiation curable compound, a bifunctional ionizing radiation curable compound, or an ionizing radiation curable compound having three or more functional groups is an ionizing radiation curable compound containing an amino group. Is also a preferred embodiment.

  When an acrylate ionizing radiation curable compound is used as the ionizing radiation curable compound having an amino group, examples of the acrylate ionizing radiation curable compound having an amino group include acrylamide, 7-amino-3,7-dimethyloctyl ( (Meth) acrylate, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide Examples include tetrachlorophenyl (meth) acrylate and N-vinylformamide.

  Further, in the present invention, it is preferable to contain particles in the hard coat layer in order to better achieve both high surface hardness and excellent moldability. Due to the presence of particles in the hard coat layer, the internal stress applied to the hard coat layer during molding is relaxed at the interface between the ionizing radiation curable compound and the particles, cracks are suppressed, and the appearance of the hard coat layer is improved. There is an effect that fine cracks that cannot be visually confirmed to the extent that they are not damaged are generated in advance, and fatal cracks (all-layer cracks) in the hard coat layer are suppressed.

  Examples of the particles included in the hard coat layer include amorphous silica, crystalline silica, silica-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, vaterite type), zeolite, alumina, hydroxyapatite, and the like. Heat-resistant polymer particles such as inorganic particles, crosslinked acrylic particles, crosslinked PMMA particles, crosslinked polystyrene particles, nylon particles, polyester particles, benzoguanamine / formalin condensate particles, benzoguanamine / melamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, Organic / inorganic hybrid fine particles such as silica / acrylic composite compounds may be mentioned, but in the present invention, the type of particles is not particularly limited.

  In the present invention, the average particle diameter of the particles is preferably 10 nm or more and 300 nm or less, the lower limit is preferably 40 nm or more, and the upper limit is preferably 200 nm or less, particularly the lower limit is 50 nm or more and the upper limit is 100 nm or less. preferable. When the average particle diameter of the particles is smaller than 10 nm, the average particle diameter is too small, and therefore, any or all of the effects of improving the surface hardness, scratch resistance, and moldability described above may be small. Moreover, when it exceeds 300 nm, a hard-coat layer becomes weak and a moldability may fall. The average particle diameter is an average particle diameter measured by dispersing the particles in a solvent that does not swell using a Coulter counter (manufactured by Beckman Coulter, Multisizer II type).

  In the present invention, the content of the particles to be contained in the hard coat layer is preferably 5% by mass or more and 70% by mass or less as a solid component in the hard coat layer, and particularly preferably, the lower limit of the content is 15% by mass. The upper limit is 50% by mass or less. When the content of the particles is less than 5% by mass, any of the above-described effects of improving the surface hardness, scratch resistance, and moldability due to the addition of the particles may be reduced. On the other hand, when the content of the particles exceeds 70% by mass, a large amount of the fine cracks described above are generated at the time of molding, and haze increases (whitens), thereby impairing the transparency of the molded body.

  Furthermore, in the present invention, it is preferable that the hard coat layer contains an ionizing radiation curable silicone resin. Thereby, slipperiness is imparted, the scratch resistance of the surface is improved, and both surface hardness and moldability can be achieved at a high level.

  The ionizing radiation curable silicone resin is, for example, a radical addition type having an alkenyl group and a mercapto group, a hydrosilylation reaction type having an alkenyl group and a hydrogen atom, a cationic polymerization type having an epoxy group, and a (meth) acryl group. A radical polymerization type silicone resin having Among these, a cationic polymerization type having an epoxy group and a radical polymerization type having a (meth) acryl group are preferable.

  Examples of silicone resins having an epoxy group or (meth) acryl group in the molecule include epoxypropoxypropyl-terminated polydimethylsiloxane, (epoxycyclohexylethyl) methylsiloxane-dimethylsiloxane copolymer, methacryloxypropyl-terminated polydimethylsiloxane, and acryloxy. And propyl-terminated polydimethylsiloxane. Examples of the silicone resin having a vinyl group in the molecule include terminal vinyl polydimethylsiloxane and vinylmethylsiloxane homopolymer.

  In the present invention, the addition amount of the ionizing radiation curable silicone resin to be contained in the hard coat layer is preferably 0.15 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable compound for constituting the hard coat layer. More preferably, 0.3 to 13 parts by mass, and still more preferably 0.5 to 5 parts by mass are blended. When the blending amount of the ionizing radiation curable silicone resin is less than the lower limit, the effect of improving the scratch resistance when formed into a molded product is poor, and when it exceeds the upper limit, the hard coat layer is sufficiently cured when formed. It may not be possible. The ionizing radiation curable silicone resin contained in the hard coat layer may be used alone or in combination of two or more.

  In the present invention, depending on the use of the film for molding as described above, a compound having an amino group is used as the ionizing radiation curable compound, particles are added to the hard coat layer, and ionizing radiation curing is performed on the hard coat layer. It is desirable to appropriately select or combine containing a type silicone resin.

  In the present invention, as a method of polymerizing and / or reacting the coating solution, a method of irradiating with an electron beam, radiation, or ultraviolet rays may be mentioned. When ultraviolet rays are irradiated, a photopolymerization initiator is added to the coating solution. Is desirable.

  Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiuramdis Examples thereof include sulfur compounds such as rufide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone, and peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide. Examples of these photopolymerization-initiated peroxide compounds such as t-butyl peroxide. These photopolymerization initiators may be used alone or in combination of two or more. The addition amount of the photopolymerization initiator is suitably 0.01 parts by weight or more and 15 parts by weight or less per 100 parts by weight of the ionizing radiation curable compound contained in the coating solution, and the reaction is slow when the amount used is small. In addition to the poor quality, the remaining unreacted material does not provide sufficient surface hardness and scratch resistance. On the other hand, when the addition amount is large, there is a problem that the hard coat layer is yellowed by the photopolymerization initiator.

  In the present invention, an organic solvent can be blended in the coating solution for the purpose of improving workability during coating and controlling the coating film thickness as long as the object of the present invention is not impaired. Moreover, various additives can be mix | blended with the hard-coat layer of this invention as needed. Examples thereof include fluorine and silicon compounds for imparting water repellency, antifoaming agents for improving coatability and appearance, and antistatic agents and coloring dyes and pigments.

  As a method for laminating the hard coat layer, a known method may be mentioned, and a method in which the coating liquid is applied and dried on a base film and then cured is preferable. As a coating method, there are known coating methods such as a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, a bar coating method, and a lip coating method. Can be mentioned. Among these, a gravure coating method, particularly a reverse gravure method, which can be applied by a roll-to-roll method and can be applied uniformly, is preferable.

  The concentration of the solid content of the ionizing radiation curable compound, particles, photopolymerization initiator and the like contained in the coating solution is preferably 5% by mass or more and 70% by mass. By adjusting the concentration of the solid content of the coating liquid to 5% by mass or more, it is possible to suppress a decrease in productivity due to a long drying time after coating. On the other hand, by adjusting the concentration of the solid content of the coating solution to 70% by mass or less, it is possible to prevent deterioration in leveling properties due to an increase in the viscosity of the coating solution and accompanying deterioration in coating appearance. From the viewpoint of coating appearance, the solid content concentration of the coating liquid, the type of organic solvent, and the type of surfactant are adjusted so that the viscosity of the coating liquid is in the range of 0.5 cps to 300 cps. It is preferable.

  The thickness of the hard coat layer after coating and curing depends on the degree of elongation during molding, but it is preferable that the thickness of the hard coat layer after molding be 0.5 μm or more and 50 μm or less. Specifically, the lower limit of the thickness of the hard coat layer before molding is preferably 0.6 μm or more, and more preferably 1.0 μm or more. Further, the upper limit of the thickness of the hard coat layer before molding is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, and further preferably 20 μm or less. When the thickness of the hard coat layer is less than 0.6 μm, it is difficult to obtain hard coat properties. Conversely, when the thickness exceeds 100 μm, the hard coat layer tends to be poorly cured or curled due to cure shrinkage.

  The molding hard coat film of the present invention is a film having excellent surface hardness. Specifically, the measured value of pencil hardness is preferably H or more, and more preferably 2H or more. Here, the pencil hardness was evaluated according to JIS-K5600.

  As a method for adjusting the surface hardness, the content of mono- or bifunctional ionizing radiation-curable compounds in the ionizing radiation-curable compound contained in the coating solution for forming the hard coat layer and the ionizing radiation-curable compound having an amino group The content can be changed depending on the amount of particles, the amount of particles present in the hard coat layer, and the thickness of the hard coat layer.

  Further, the molding hard coat film of the present invention is excellent in scratch resistance. Specifically, in accordance with JIS-K5600, the surface is reciprocated 20 times with # 0000 steel wool at a load of 500 gf, the presence or absence of scratches and the degree of scratches are visually observed, and a small amount of deep scratches of 10 or less It is particularly preferable that there is no deep scratch.

  As a method for adjusting the scratch resistance, the content of the monofunctional or bifunctional ionizing radiation curable compound in the ionizing radiation curable compound contained in the coating solution for forming the hard coat layer or the ionizing radiation curable type having an amino group. It can be changed depending on the content of the compound and the amount of particles present in the hard coat layer.

  Furthermore, the hard coat film for molding of the present invention is excellent in moldability. Specifically, the elongation is preferably 10% or more at room temperature and the actual film temperature of 160 ° C., more preferably 20% or more, and particularly preferably 30% or more. Here, the elongation means that a hard coat film for molding was cut into a strip shape having a length of 10 mm and a width of 150 mm, and when the actual film temperature was pulled at 160 ° C., cracks or whitening occurred in the hard coat layer. The stretching ratio at the time was defined as the degree of elongation (%).

  As a method for adjusting the moldability (elongation), the content of mono- or bifunctional ionizing radiation-curable compound in the ionizing radiation-curable compound contained in the coating solution for forming the hard coat layer or ionization having an amino group It can be changed depending on the content of the radiation curable compound and the amount of particles present in the hard coat layer.

(Molded body)
The molding hard coat film of the present invention is suitable as a molding material to be molded using a molding method such as vacuum molding, pressure molding, mold molding, press molding, in-mold molding, draw molding, or stretch molding. In the case of molding using the molding hard coat film of the present invention, the hard coat layer follows the deformation during molding and no cracks are generated, and the surface hardness and scratch resistance can be maintained.

  Since the molded body molded in this way has a hard coat layer to supplement the surface hardness, it is mounted at a position where it touches the outside and is suitable for applications that require scratch resistance. Such molded articles are, for example, interior decorations and exterior decorations for automobiles, personal computers, televisions, refrigerators, washing machines, stereos, home appliances such as portable devices, mirror products such as compact mirrors for makeup, automobiles, etc. It is suitable for nameplates (including display plates and panels) used in vehicles, ships, aircraft, buildings, play equipment (ski goggles, etc.), amusement devices, and other various mechanical devices.

  EXAMPLES Next, although this invention is demonstrated in detail using an Example and a comparative example, naturally this invention is not limited to a following example. The evaluation method used in the present invention is as follows.

(1) Intrinsic viscosity Based on JIS K7367-5, it measured at 30 degreeC, using the mixed solvent of phenol (60 mass%) and 1,1,2,2-tetrachloroethane (40 mass%) as a solvent.

(2) Glass transition temperature In accordance with JIS K7121, using a differential scanning calorimeter (Seiko Instruments, DSC6200), the temperature was raised at a rate of 20 ° C / min over a temperature range of 25 to 300 ° C, and obtained from a DSC curve. The extrapolated glass transition start temperature was defined as the glass transition temperature.

(3) Number average molecular weight 0.03 g of resin was dissolved in 10 ml of tetrahydrofuran, and a GPC-LALLS apparatus low-angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene) was used at a column temperature of 30 ° C. The number average molecular weight was measured using a flow rate of 1 ml / min and a column (showex KF-802, 804, 806 manufactured by Showa Denko KK).

(4) Resin composition The resin is dissolved in deuterated chloroform, and ¹ H-NMR analysis is performed using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian, and the mol% ratio of each composition is determined from the integral ratio. Were determined.

(5) Acid value 1 g (solid content) of a sample was dissolved in 30 ml of chloroform or dimethylformamide, and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator to determine the carboxyl groups per gram of the sample. The amount (mg) of KOH required for neutralization was determined.

(6) Refractive index The refractive index of the hard coat layer was measured using an Abbe refractometer based on JIS K 7142 for a film obtained by curing each resin used in the hard coat layer.
The refractive index of the particles A is such that the particles A dried at 90 ° C. are suspended in various liquids of 25 ° C. having different refractive indexes, and the refractive index of the liquid in which the suspension looks most transparent is the Abbe refractive index. It was measured by a meter.

(7) Surface resistance of polyester film for molding The surface resistance of the coating layer surface of the obtained polyester film for molding was measured using a surface resistance meter (manufactured by Mitsubishi Chemical, Lorester UP MCP-HT450), applied voltage 500 V, 20 ° C., 55 It was measured under the condition of% RH.

(8) Adhesiveness Specifically, 100 grid-shaped cuts that penetrate the hard coat layer and reach the base film are made on the hard coat layer surface using a cutter guide with a gap interval of 2 mm. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., No. 405; 24 mm width) was attached to the cut surface of the grid, and rubbed with an eraser for complete adhesion. Thereafter, the cellophane adhesive tape is peeled off from the hard coat layer surface of the molding hard coat film vertically, and the number of squares peeled off from the hard coat layer surface of the base film is visually counted. The adhesion with the material film was determined. In addition, what peeled partially among squares was also counted as the square which peeled, and was ranked according to the following references | standards.
Adhesiveness (%) = (1−number of peeled squares / 100) × 100
A: 100%
○: 99-90%
Δ: 90-70%
X: 69 to 0%

(9) Moisture and heat resistance The obtained hard coat film for molding was left in an environment of 80 ° C. and 95% RH for 48 hours in a high-temperature and high-humidity tank. Next, the molding hard coat film was taken out and allowed to stand at room temperature and humidity for 12 hours. Thereafter, contact adhesion between the hard coat layer and the substrate film was determined in the same manner as in (8) above, and ranked according to the following criteria.
A: 100%, or material breakage of hard coat layer B: 99-90%
Δ: 89-70%
X: 69 to 0%

(10) Elongation A strip-shaped sample piece having a length of 10 mm and a width of 150 mm was cut out from the molding hard coat film. In an environment where the actual temperature of the film sample piece is 160 ° C., while visually observing the appearance, the film is gripped at both ends and pulled at a test speed of 250 mm / min, and when the hard coat layer is cracked or whitened, The length was measured.
When the length of the film sample piece before the test was a and the length of the film sample piece after the test was b, the elongation was calculated by the following formula.
Elongation (%) = (b−a) × 100 / a
Here, it was judged that those having an elongation of 10% or more were excellent in moldability, and those having an elongation of 30% or more were particularly excellent in moldability.

(11) Pencil hardness The pencil hardness of the hard coat layer of the molding hard coat film was measured according to JIS-K5600. The indentation (scratch) was judged visually.
Here, those having a pencil hardness of H or higher were judged to have excellent surface hardness, and those having a pencil hardness of 2H or higher were judged to have particularly excellent surface hardness.

(12) Scratch resistance The scratch resistance of the hard coat layer of the molding hard coat film was measured according to JIS-K5600. The hard coat layer surface was reciprocated 20 times with # 0000 steel wool at a load of 500 gf, and the presence or absence of scratches and the extent of the scratches were visually observed. The rank was determined according to the following criteria based on the observation results. The scratch resistance rank was C or higher, and there was scratch resistance, and those of B or higher were judged to have good scratch resistance.
A: There is no generation of scratches or thin scratches are observed in a small amount.
B: Although a thin wound is observed, a deep wound is not observed.
C: Narrow scratches are observed, and a small amount of deep scratches are also observed.
D: A lot of deep scratches are observed.

(13) Moldability of molding hard coat film After 5 mm square printing was performed on the molding hard coat film, the film was heated with an infrared heater heated to 500 ° C. for 10 to 15 seconds, and then the mold temperature was 100. Vacuum molding was performed at a temperature of ℃ or lower. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 45 mm, the depth was 5 mm, and all corners were curved with a diameter of 0.5 mm. .

(Polymerization of urethane resin containing polycarbonate polyol)
In a four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 72.96 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane, 12.60 dimethylolpropionic acid. Mass part, 11.74 parts by mass of neopentyl glycol, 112.70 parts by mass of polycarbonate diol having a number average molecular weight of 2000, and 85.00 parts by mass of acetonitrile and 5.00 parts by mass of N-methylpyrrolidone as a solvent were added, and a nitrogen atmosphere Under stirring at 75 ° C. for 3 hours, it was confirmed that the reaction solution reached a predetermined amine equivalent. Next, after lowering the temperature of the reaction solution to 40 ° C., 9.03 parts by mass of triethylamine was added to obtain a polyurethane prepolymer D solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and mixed with stirring at 2000 min −1 while adding an isocyanate group-terminated prepolymer to disperse in water. did. Then, water-soluble polyurethane resin (A-1) with a solid content of 35% was prepared by removing a portion of acetonitrile and water under reduced pressure.

In the same manner, water-soluble polyurethane resins (A-2) to (A-3) having different compositions were obtained. Table 1 shows the composition (mole% ratio) and other characteristics measured by ¹ H-NMR for these water-soluble polyurethane resins.

(Polymerization of polycarbonate resin and polyoxyethylene group urethane resin)
In a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, while introducing nitrogen gas, 627.1 parts by mass of hexamethylene diisocyanate and methoxypolyethylene glycol 372.9 having a number average molecular weight of 1000 heated to 50 ° C. A mass part was charged and reacted at 80 ° C. for 6 hours. After reaching a predetermined isocyanate group content, unreacted hexamethylene diisocyanate was removed with a Smith type thin film distiller to obtain a polyoxyethylene group-containing monoisocyanate (A). The calculated number average molecular weight of this polyoxyethylene chain-containing monoisocyanate (A) was 1168 g / mol.

  Next, 83.9 parts by mass of diethanolamine was charged while introducing nitrogen gas at room temperature in a reactor equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. While cooling, 916.1 parts by mass of polyisocyanate chain-containing monoisocyanate A was added and reacted at 60 ° C. for 3 hours. Formation of urea bonds was confirmed by infrared spectrum, and a polyoxyethylene group-containing polyol (A) was obtained.

  In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 53.69 parts by mass of 1,3-cyclohexanebis (methyl isocyanate) as a polyisocyanate and several as a hydrophobic macropolyol Polycarbonate diol having an average molecular weight of 2000, 88.6 parts by mass, 14.97 parts by mass of neopentyl glycol, 52.87 parts by mass of the polyoxyethylene group-containing polyol (A), 60 parts by mass of acetonitrile as an organic solvent, N -30 parts by mass of methylpyrrolidone was charged, the temperature of the reaction solution was adjusted to 75 to 78 ° C under a nitrogen atmosphere, 0.06 parts by mass of stannous octylate was added as a reaction catalyst, and the reaction rate was 99 in 7 hours. It was made to react to more than%. Subsequently, this was cooled to 30 degreeC and the isocyanate group terminal prepolymer was obtained. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and mixed with stirring at 2000 min −1 while adding an isocyanate group-terminated prepolymer to disperse in water. did. Then, water-soluble polyurethane resin (A-4) with a solid content of 35% was prepared by removing a portion of acetonitrile and water under reduced pressure.

(Polymerization of urethane resin with polyester polyol as a constituent)
In a four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 72.96 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane, 12.60 dimethylolpropionic acid. Mass part, neopentyl glycol 11.74 parts by mass, number average molecular weight 2000 polyester diol 112.70 parts by mass, acetonitrile 85.00 parts by mass, N-methylpyrrolidone 5.00 parts by mass as a solvent, nitrogen atmosphere Under stirring at 75 ° C. for 3 hours, it was confirmed that the reaction solution reached a predetermined amine equivalent. Next, after lowering the temperature of the reaction solution to 40 ° C., 9.03 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and mixed with stirring at 2000 min −1 while adding an isocyanate group-terminated prepolymer to disperse in water. did. Thereafter, a part of acetonitrile and water was removed under reduced pressure to prepare a water-soluble polyurethane resin (A-5) having a solid content of 35%.

(Polymerization of urethane resin containing polyether polyol)
In a four-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 72.96 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane, 12.60 dimethylolpropionic acid. Mass part, 11.74 parts by mass of neopentyl glycol, 112.70 parts by mass of polyether diol having a number average molecular weight of 2000, and 85.00 parts by mass of acetonitrile and 5.00 parts by mass of N-methylpyrrolidone as a solvent, The mixture was stirred at 75 ° C. for 3 hours under an atmosphere, and it was confirmed that the reaction solution reached a predetermined amine equivalent. Next, after lowering the temperature of the reaction solution to 40 ° C., 9.03 parts by mass of triethylamine was added to obtain a polyurethane prepolymer solution. Next, 450 g of water was added to a reaction vessel equipped with a homodisper capable of high-speed stirring, adjusted to 25 ° C., and mixed with stirring at 2000 min −1 while adding an isocyanate group-terminated prepolymer to disperse in water. did. Thereafter, a part of acetonitrile and water was removed under reduced pressure to prepare a water-soluble polyurethane resin (A-6) having a solid content of 35%.

(Polymerization of water-soluble carbodiimide compounds)
In a flask equipped with a thermometer, nitrogen gas introduction tube, reflux condenser, dropping funnel, and stirrer, 200 parts by mass of isophorone diisocyanate and 4 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide as a carbodiimidization catalyst And stirred at 180 ° C. for 10 hours under a nitrogen atmosphere to obtain an isocyanate-terminated isophorone carbodiimide (degree of polymerization = 5). Next, 111.2 g of the obtained carbodiimide and 80 g of polyethylene glycol monomethyl ether (molecular weight 400) were reacted at 100 ° C. for 24 hours. Water was gradually added thereto at 50 ° C. to obtain a yellow transparent water-soluble carbodiimide compound (B) having a solid content of 40% by mass.

(Polymerization of oxazoline crosslinking agent)
A mixture of 58 parts by mass of ion-exchanged water and 58 parts by mass of isopropanol as an aqueous medium in a flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux condenser, a dropping funnel, and a stirrer, and a polymerization initiator (2, 2 4 parts by mass of '-azobis (2-amidinopropane) dihydrochloride) was added. On the other hand, in a dropping funnel, 16 parts by mass of 2-isopropenyl-2-oxazoline as a polymerizable unsaturated monomer having an oxazoline group, methoxypolyethylene glycol acrylate (average number of moles of ethylene glycol added: 9 moles, Shin Nakamura Chemical) A mixture of 32 parts by mass and 32 parts by mass of methyl methacrylate was added, and the mixture was added dropwise at 70 ° C. for 1 hour in a nitrogen atmosphere. After completion of dropping, the reaction solution was stirred for 9 hours and cooled to obtain a water-soluble resin (C) having an oxazoline group with a solid content concentration of 40% by mass.

(Polyaniline resin polymerization)
In a flask equipped with a dropping funnel and a stirrer, 100 mmol of 2-aminoanisole-4-sulfonic acid was stirred and dissolved in an aqueous ammonia solution of 4 mol / liter, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise at 24 ° C. After completion of the dropwise addition, the mixture was further stirred at 24 ° C. for 10 hours, washed by filtration and dried to obtain 14 g of a powdered polyaniline resin. A 0.3 mol / liter sulfuric acid aqueous solution was added to obtain an aqueous dispersion (D) of a polyaniline resin having a solid content concentration of 3%.

Hereinafter, Examples 1-7 and 9-21 are read as Reference Examples 1-7 and 9-21, respectively.
Example 1
(1) Adjustment of Adhesive Modified Layer Forming Coating Solution The following coating agent was mixed to prepare an adhesive modified layer forming coating solution.
16.97% by mass of water
Isopropanol 21.96 mass%
Sorbitol 5.00% by mass
Thiophene resin 51.02 mass%
(Bytron P AG manufactured by Starck, solid content concentration 1.2% by mass)
Water-soluble polyurethane resin (A-1) 3.27% by mass
Water-soluble carbodiimide compound (C) 1.22% by mass
0.51% by mass of particles
(Silica sol with an average particle size of 40 nm, solid content concentration of 40% by mass)
Surfactant 0.05% by mass
(Silicon, solid content concentration of 100% by mass)

(2) Manufacture of film raw material The intrinsic viscosity is 0.69 dl / with 100 mol% of terephthalic acid unit as an aromatic dicarboxylic acid component and 40 mol% of ethylene glycol unit and 60 mol% of neopentyl glycol unit as diol components. g of copolymer polyester chip (A) and polyethylene terephthalate containing 0.04% by mass of silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method, the same applies hereinafter) of 2.7 μm. Each chip (B) was dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75.

(3) Manufacture of polyester film for molding Next, these chip mixtures were melt-extruded at 270 ° C. from a slit of a T-die by an extruder, rapidly solidified on a chill roll having a surface temperature of 40 ° C., and simultaneously using an electrostatic application method. An amorphous unstretched sheet was obtained in close contact with the chill roll.

  The obtained unstretched sheet was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll.

  Subsequently, the above-described coating solution for forming an adhesive modification layer was applied to one side of the film by a roll coating method and dried at 130 ° C. for 3 seconds to remove moisture.

Subsequently, after apply | coating the said coating liquid to the single side | surface of the uniaxially stretched film obtained by the roll coat method, it dried at 80 degreeC for 20 second. The coating amount after drying (after biaxial stretching) was adjusted to 0.10 g / m ² . Subsequently, by heating with a tenter at a setting of 100 ° C. and transversely stretching 3.8 times, heat treatment at 230 ° C. for 5 seconds while fixing the width, and further relaxing by 5% in the width direction at 205 ° C. A polyester film for molding having a thickness of 100 μm was obtained. The evaluation results are shown in Table 2.

(4) Production of hard coat film for molding The following hard coat coating solution A was applied to the obtained base film using a wire bar so that the coating thickness after drying was 2 μm, and hot air at a temperature of 80 ° C. Was dried for 60 seconds, and passed through a 20 cm position under a high pressure mercury lamp with an output of 120 W / cm at a speed of 10 m / min to obtain a hard coat film for molding. The refractive index of the hard coat layer was 1.48.
(Hard coat coating solution A)
The following materials were mixed at the mass ratio shown below, and dissolved by stirring for 30 minutes or more. Subsequently, the undissolved material was removed using a filter having a nominal filtration accuracy of 1 μm to prepare a hard coat coating solution A.
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 11.45% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 5.73% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 5.72% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

  The moldability of the obtained molding hard coat film was evaluated according to the molding method of (13). The resulting molded product was not broken. In addition, the obtained results are shown in Table 1.

Comparative Example 1
A molding polyester film and a molding hard coat film were obtained in the same manner as in Example 1 except that the water-soluble polyurethane resin was changed to A-5.

Comparative Example 2
A molding polyester film and a molding hard coat film were obtained in the same manner as in Example 1 except that the water-soluble polyurethane resin was changed to A-6.

Comparative Example 3
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the water-soluble carbodiimide compound (B) was changed to an epoxy compound (Denacol EX-521 solid concentration 100% manufactured by Nagase ChemteX Corporation). It was.

Comparative Example 4
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the water-soluble carbodiimide compound (B) was changed to a melamine compound (Beccamin M-3 solid content concentration 60% manufactured by DIC).

Example 2
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the thiophene resin was removed.

Example 3
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the thiophene resin was changed to an ion conductive antistatic agent (Semiyo Kasei Chemistat 3500 solid content concentration 100%).

Example 4
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution B)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 22.90 mass%
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 made by Ciba Specialty)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 5
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution C)
Methyl ethyl ketone 64.48% by mass
Tripropylene glycol diacrylate 11.45% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 11.45% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 made by Ciba Specialty)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 6
A molding polyester film and a molding hard coat film were obtained in the same manner as in Example 1 except that the water-soluble polyurethane resin was changed to A-2.

Example 7
A molding polyester film and a molding hard coat film were obtained in the same manner as in Example 1 except that the water-soluble polyurethane resin was changed to A-3.

Example 8
A molding polyester film and a molding hard coat film were obtained in the same manner as in Example 1 except that the water-soluble polyurethane resin was changed to A-4.

Example 9
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the water-soluble carbodiimide compound (B) was changed to the water-soluble resin (C) having an oxazoline group.

Example 10
A polyester film for molding and a hard coat film for molding were obtained in the same manner as in Example 1 except that the thiophene resin was changed to an aqueous dispersion (D) of a polyaniline resin.

Example 11
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution D)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 17.18% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 2.86% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 2.86% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 12
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution E)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 8.02 mass%
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 7.44% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 7.44% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 13
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution F)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 21.75% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 0.58% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 0.57% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 14
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution G)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 1.15% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 0.58% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 21.17% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 15
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution H)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 21.75% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 1.15% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 16
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution I)
Methyl ethyl ketone 64.48% by mass
Pentaerythritol triacrylate 1.15% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 21.75% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 17
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution J)
Methyl ethyl ketone 67.93 mass%
Pentaerythritol triacrylate 11.58 mass%
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 5.79% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 5.79% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 7.72% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 1.16% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 18
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution K)
Methyl ethyl ketone 4.24% by mass
Pentaerythritol triacrylate 6.22% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 3.12% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 3.12% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 82.73 mass%
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Photopolymerization initiator 0.55% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.02% by mass
(Toray Dow Corning DC57)

Example 19
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution L)
Methyl ethyl ketone 75.08% by mass
Pentaerythritol triacrylate 11.85% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 5.93% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 5.92% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Photopolymerization initiator 1.19% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 20
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution M)
Methyl ethyl ketone 63.62% by mass
Pentaerythritol triacrylate 11.45% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 5.73% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 5.72% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Ionizing radiation curable silicone compound polyether acrylate 0.86% by mass
(Germany Chemie Service, TEGO Rad2200N)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

Example 21
In Example 1, a molding hard coat film was obtained in the same manner as in Example 1 except that the coating liquid for forming the hard coat layer was changed to the following hard coat coating liquid.
(Hard coat coating solution N)
Methyl ethyl ketone 61.62% by mass
Pentaerythritol triacrylate 11.45% by mass
(Manufactured by Shin-Nakamura Chemical, NK ester A-TMM-3LM-N, functional group number 3)
Tripropylene glycol diacrylate 5.73% by mass
(Shin Nakamura Chemical, NK Ester APG-200, 2 functional groups)
Dimethylaminoethyl methacrylate 5.72% by mass
(Kyoeisha Chemical Co., Ltd., light ester DM, functional group number 1)
Silica fine particles 11.45% by mass
(Nissan Chemical Industries, MEK-ST-L, solid content concentration 30%, average particle size: 50 nm)
Ionizing radiation curable silicone compound polyether acrylate 2.86% by mass
(Germany Chemie Service, TEGO Rad2200N)
Photopolymerization initiator 1.14% by mass
(Irgacure 184 manufactured by Ciba Specialty Chemicals)
Silicone surfactant 0.03% by mass
(Toray Dow Corning DC57)

  The polyester film for molding of the present invention is excellent in appearance quality, adhesion and adhesion under high temperature and high humidity (moisture and heat resistance) when a hard coat layer is laminated on the adhesion modified layer of the film. Molded hard coat film for molding of home appliances that require scratch resistance, automotive nameplate or building material members, mobile phones, audio, portable players / recorders, IC recorders, car navigation systems, PDAs, etc. It is suitable as a housing for portable devices and notebook PCs. In a preferred embodiment, since sufficient antistatic properties are imparted, there is little adhesion of dust and workability is good. Furthermore, on the manufacturing side of the molding process, processing and laminating the hard coat layer on the base film before molding can contribute to improving the productivity and stability of the quality, contributing greatly to the industry. .

Claims (7)

At least one surface of the polyester film having a copolymer component has an adhesive reforming layer containing a urethane resin having a polycarbonate polyol as a constituent component and a crosslinking agent, the urethane resin has a polyoxyalkylene group, and the crosslinking The molding agent is a molding hard coat film having a hard coat layer obtained by coating and curing a coating solution on the surface of the adhesive modified layer of the molding polyester film which is a resin having a carbodiimide compound and / or an oxazoline group. In the ionizing radiation curable compound contained in the coating liquid, the coating liquid contains at least an ionizing radiation curable compound having three or more functional groups and a monofunctional and / or bifunctional ionizing radiation curable compound. The content of the monofunctional and / or bifunctional ionizing radiation curable compound is 5% by mass or more and 95% by mass. The hard coat film for molding is less than or equal to. The hard coat film for molding according to claim 1, wherein the adhesive modification layer further contains a π-electron conjugated conductive polymer. The hard coat film for molding according to claim 2, wherein the π-electron conjugated conductive polymer contains thiophene or a thiophene derivative as a repeating unit. Wherein comprises a hard coat layer average particle diameter 10nm or 300nm or less of the particles during the according to claim 1, the content of the hard coat layer is not more than 5 wt% to 70 wt% of said particles Hard coat film for molding. The hard coat film for molding according to claim 1 , wherein at least one ionizing radiation curable compound contained in the coating solution is an ionizing radiation curable compound having an amino group. The hard coat layer contains an ionizing radiation curable silicone resin, and the content of the ionizing radiation curable silicone resin in the hard coat layer is 0.15 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable compound. The hard coat film for molding according to any one of claims 1 to 5 , wherein the hard coat film is not more than part by mass. The molded object formed by shape | molding the hard-coat film for shaping | molding in any one of Claims 1-6 .