JP2011156687A - Resin sheet and molding using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated polyester film which has high selective reflection performance, is excellent in high temperature high humidity molding processability, prevents the occurrence of peeling in an adhesive surface, and is free from blocking and reduces the generation of an oligomer, the rise of haze, and the fouling of a mold during molding processing. <P>SOLUTION: A resin sheet includes a structure in which at least 50 layers (layers A) made of a polyester resin A and at least 50 layers (layers B) made of a polyester resin B are laminated alternately. A layer made of the reactant of a coating agent containing at least an acrylic-urethane copolymer resin, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent is formed on at least one side of a laminated film having at least one reflection band wherein a relative reflectance is at least 30%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin sheet suitable for imparting design properties to a molded body and its use.

  Conventionally, an optical interference multilayer that selectively removes light of a specific wavelength by utilizing a light interference phenomenon that is manifested by alternately laminating two or more materials having different refractive indexes at a layer thickness of the wavelength of light. Membranes are known. Such a multilayer film can be provided with various performances by setting the refractive index, the number of layers, and the thickness of each layer to a desired optical design, and is thus commercially available for various optical applications. ing. For example, a cold mirror, a half mirror, a laser mirror, a dichroic filter, a heat ray reflective film, a near-infrared cut filter, a monochromatic filter, a polarizing reflective film, and the like can be given.

  When such a multilayer film is obtained by melt extrusion, polyethylene terephthalate is used for one resin and the other resin for reasons such as transparency, heat resistance, weather resistance, chemical resistance, and strength and dimensional stability. Furthermore, it is known that it is a multilayer film using a low refractive index copolymer polyester (Patent Documents 1 and 2).

  However, the polyester resin is not necessarily satisfactory in molding followability and adhesiveness with other resins, and improvement thereof has been desired. The adhesion of the film surface is essential when various layers are provided on the polyester film. In order to improve the adhesiveness of the film, surface treatments such as corona treatment, frame treatment, and chemical treatment are known but insufficient.

  Also known is a method of forming a primer layer (hereinafter also referred to as an easy-adhesion layer) by applying an easy-adhesive coating agent to the film surface. However, the conventionally known film with an easy-adhesion layer is subjected to in-mold molding and the like, and when exposed to high temperature and high humidity for a long time, the adhesiveness at the interface between the film surface and the easy-adhesion layer decreases, and the surface layer In the case where a hard coat layer, an adhesive layer, or the like is provided, a problem that peeling occurs has been pointed out, and in particular, the above-described multilayer film has been desired to be solved.

  It has been proposed to apply a hydrophobic resin together with an organic solvent as a means to increase the high temperature and humidity resistance of the easy-adhesion layer. However, as long as the hydrophobic resin is used, the organic solvent must be used. There are immeasurable adverse effects.

  On the other hand, coating films using water-dispersible resins are superior in terms of cost and environment, and Patent Documents 3 and 4 disclose examples aimed at improving high-temperature and humidity resistance. However, since these methods cannot prevent cracks caused by molding, essential improvements cannot be made. In addition, these methods have not solved the problem of mold contamination that impairs the appearance of the molded body due to oligomer precipitation and the problem of contamination of the mold.

JP 2005-059332 A Japanese Patent Laid-Open No. 2004-249687 JP 2005-343118 A Japanese Patent Laid-Open No. 7-214738

  The present inventors have made extensive studies on the above problems and have found that the phenomenon of delamination under high temperature and high humidity is caused by a slight crack generated in the easy-adhesive layer during molding pressurization and moisture entering. It has also been found that this tendency becomes more prominent as deep drawing.

  Therefore, in view of the above-mentioned problems of the prior art, the present invention is a laminated polyester film that has high selective reflection performance, is excellent in high-temperature and high-humidity molding processability, does not peel off on the adhesive surface, and has no blocking. It is an issue to provide. It is another object of the present invention to provide a resin sheet that can reduce haze rise and mold contamination.

In order to solve the above problems, the present invention provides:
(1) It includes a structure in which 50 layers or more of layers made of polyester resin A (A layer) and layers of polyester resin B (B layer) are alternately laminated, and at least a reflection band having a relative reflectance of 30% or more A resin sheet characterized in that a layer made of a reaction product of a coating containing at least an acrylic / urethane copolymer resin, an oxazoline-based crosslinking agent, and a carbodiimide crosslinking agent is provided on one or both sides of a laminated film having one,
(2) The resin sheet according to (1), wherein the haze increase rate before and after heating at 150 ° C. for 30 minutes is 2% or less,
(3) A printing layer is provided on the resin sheet of the coating agent, and insert molding is performed under the conditions of a film temperature of 120 ° C., a resin temperature of 250 ° C., a mold temperature of 60 ° C., and an injection speed of 240 mm / s. The adhesive according to (1) or (2) above, wherein the adhesion between the resin sheet and the printed layer after being carried out and then allowed to stand for 168 hours in an atmosphere of 65 ° C. and 95% humidity is good Resin sheet,
(4) A molded body using the resin sheet according to any one of (1) to (3),
This is the purpose.

  The present invention has excellent selective reflection performance, excellent high-temperature and high-humidity molding processability, no peeling on the adhesive surface, and no blocking. In addition, generation of oligomers and an increase in film haze, that is, mold contamination during molding can be reduced.

  Hereinafter, embodiments of the present invention will be described in detail.

  In the laminated polyester film of the present invention, 50 layers or more of layers made of polyester resin A (A layer) and layers of polyester resin B (B layer) are alternately laminated, and at least a reflection band having a relative reflectance of 30% or more is provided. I have one.

  The polyester used in the present invention is typically a homopolyester or a copolyester that is a polycondensate of a dicarboxylic acid component skeleton and a diol component skeleton. Here, the homopolyester refers to a polyester composed of one kind of oxycarboxylic acid unit, or a polyester composed of one kind of dicarboxylic acid unit and a diol unit. For example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene Typical examples include -2,6-naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, and polyethylene diphenylate. In particular, polyethylene terephthalate is preferable because it is inexpensive and can be used in a wide variety of applications. On the other hand, a copolyester is a polyester comprising two or more oxycarboxylic acid units, a polyester comprising two or more dicarboxylic acid units or diol units, or an oxycarboxylic acid unit, a dicarboxylic acid unit and a diol unit. The polycondensate comprising at least three or more components selected from the following components having a dicarboxylic acid skeleton and components having a diol skeleton is typical. Examples of compounds that give dicarboxylic acid units include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid. 4,4′-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexanedicarboxylic acid and ester derivatives thereof. Examples of diol units are ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2,2-bis. (4′-β-hydroxyethoxyphenyl) propane, isosorbate, 1,4-cyclohexanedimethanol, spiroglycol and the like can be mentioned.

  In the present invention, two kinds of polyester resins are used, and the absolute value of the difference in SP value between the two kinds of polyester resins is preferably 1.0 or less. When the absolute value of the difference in SP value is 1.0 or less, delamination hardly occurs. As means for realizing such a range, it is preferable that the polyester resin A and the polyester resin B have the same basic skeleton. Here, the basic skeleton is a repeating unit constituting the resin. For example, when one resin is polyethylene terephthalate, ethylene terephthalate is the basic skeleton, and the polyester having the same basic skeleton as polyethylene terephthalate is, for example, Copolyesters containing an ethylene terephthalate skeleton such as isophthalic acid copolymerized polyethylene terephthalate and butylene glycol copolymerized polyethylene terephthalate.

  A preferred polyester resin combination is a polyester using polyethylene terephthalate and spiroglycol as diol units. The polyester using spiroglycol as a diol unit refers to a copolyester obtained by copolymerizing spiroglycol, a homopolyester using spiroglycol, or a polyester obtained by blending them. Polyester using spiroglycol as the diol unit can be a polyester with a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, so it is difficult to overstretch during film formation by using such polyester, and delamination Is less likely to occur. More preferably, the polyester resin A is a polyester using polyethylene terephthalate or polyethylene naphthalate, and the polyester resin B is a polyester in which spiroglycol and cyclohexanedicarboxylic acid are used as polymerization components. Polyesters using spiroglycol and cyclohexanedicarboxylic acid as polymerization components have a large in-plane refractive index difference from polyethylene terephthalate or polyethylene naphthalate, and thus high reflectance is easily obtained. Further, since the glass transition temperature difference between polyethylene terephthalate and polyethylene naphthalate is small, it is difficult to be over-stretched during molding, and is also difficult to delaminate.

  The resin sheet of the present invention has a structure in which 50 layers or more of layers made of polyester resin A (A layer) and layers made of polyester resin B (B layer) are alternately laminated. The alternately laminated structure means a state in which A layers and B layers are alternately laminated in the thickness direction. The number of A layers and B layers stacked alternately is preferably 200 layers or more, more preferably 600 layers or more. If the structure in which 50 layers or more of the A layer and the B layer are laminated is not included, a film having poor reflection performance such as a narrow reflection band or low reflectance is obtained. Further, if it is 200 layers or more, it becomes easy to widen the reflection band, and if it is 600 layers or more, it is possible to obtain a resin sheet having a wide reflection band of 300 to 600 nm having a reflectance of 50% or more. Become. When the reflection band is in the range of 300 nm to 600 nm, the appearance of the resin sheet can be made metallic, and the higher the reflectance, the higher the degree. The upper limit of the number of layers is not particularly limited, but considering the decrease in wavelength selectivity due to the decrease in stacking accuracy due to the increase in the size of the stacking device and the increase in the number of layers, the number of layers is 1500 or less, respectively. It is preferable. In addition, if the resin sheet of the present invention has a structure in which 50 layers or more of the A layer and the B layer are alternately laminated, the other layer is laminated outside the structure in which the 50 layers or more are laminated. It may be.

  The resin sheet of the present invention has one or more reflection bands having a reflectance of 30% or more in a wavelength region of 380 to 2500 nm. The reflection band refers to a wavelength range (width) having a width of 20 nm or more showing a reflectance of 30% or more, preferably the width is 50 nm or more, more preferably 30% in a section of 380 to 1400 nm. That's it. In order to obtain such a resin sheet, the thickness of each layer in the feed block used during film formation is designed to gradually increase from the surface side to the opposite surface side, and the layers are alternately laminated in the thickness direction composed of the A layer and the B layer. This can be achieved by using a structured structure.

  In the present invention, the difference between the in-plane average refractive index of the A layer and the in-plane average refractive index of the B layer is preferably 0.03 or more. More preferably, it is 0.05 or more, More preferably, it is 0.1 or more. When the refractive index difference is smaller than 0.03, it is difficult to obtain a sufficient reflectance. By using one polyester resin as an amorphous polyester resin, the in-plane average refractive index of the A layer and the B layer can be reduced by causing orientation relaxation of the B layer in the heat treatment in the tenter after being formed into a sheet shape. The difference can be increased.

  The resin sheet of the present invention preferably has a stress (F-100 value) at 100% elongation at 150 ° C. in the range of 10 to 70 MPa. By adopting such a configuration, the moldability can be improved, and even if the applied pressure is small, it becomes possible to remove the tension and the crease, so that the cracks in the easy adhesion layer are reduced. A more preferable range of the F-100 value is 20 to 60 MPa, and the moldability is further improved. In order to set the F-100 value to 70 MPa or less, it is easy to include amorphous polyester in the range of 20 to 80% by weight of the resin sheet serving as the base material. More preferably, it is the range of 40 to 60 weight%. Although the detailed reason is unknown, it seems to be related to the reduction of the tensile stress of the resin sheet.

  The resin sheet of the present invention comprises an acrylic / urethane copolymer resin, an oxazoline-based crosslinking agent, and a carbodiimide crosslinking agent on one or both sides of a laminated film including a structure in which 50 layers or more of the A layer and B layer are alternately laminated. It is necessary that at least a layer made of a reaction product of the coating agent to be included (hereinafter also referred to as the present coating layer) is provided. When the surface roughness (Ra) of the coating layer is 8 to 30 nm and the thickness is 10 to 1000 nm, the adhesiveness is good, which is desirable. The coating agent preferably further contains at least one of an isocyanate compound, a melamine compound, and an organometallic compound. Further, for example, an epoxy compound, an aziridine compound, an amide epoxy compound, a methylolated or alkylolized urea compound, an acrylamide compound, and the like can be arbitrarily used.

  The resin sheet of the present invention has an F-100 value of 10 to 70 MPa, and a surface roughness of a layer comprising a reaction product of a coating agent containing at least the acrylic / urethane copolymer resin, an oxazoline-based crosslinking agent, and a carbodiimide crosslinking agent. When the thickness (Ra) is 8 to 30 nm and the thickness is 10 to 1000 nm, the effect of the present invention becomes more remarkable.

  Next, the coating agent used for formation of this coating film layer is demonstrated.

(1) Acrylic / urethane copolymer resin (A)
In the present invention, those obtained by copolymerizing acrylic and urethane are used from the viewpoints of adhesion and UV resistance (adhesion after UV irradiation). The acrylic / urethane copolymer resin (A) is not particularly limited as long as it is a resin in which an acrylic component and a urethane component are copolymerized, but in particular, an acrylic / urethane copolymer resin having acrylic as a skin layer and urethane as a core layer is used. preferable. At this time, it is preferable that the core layer is not completely encased by the skin layer but has a form in which a part of the core layer is exposed. That is, when the core layer is completely encased by the skin layer, when the resin is applied and dried to form a film, the surface state has only acrylic characteristics, and the characteristics of the urethane derived from the core layer It becomes difficult to obtain the surface state possessed. On the other hand, the state in which the core layer is not encapsulated by the skin layer, that is, the state in which the core layer is separated is simply a mixture of acrylic and urethane. In order to selectively coordinate to the side, when the resin is applied and dried to form a film, the film has a surface state having only acrylic characteristics. For example, the acrylic / urethane copolymer resin having a core / skin structure is firstly subjected to first-stage emulsion polymerization using a monomer, an emulsifier, a polymerization initiator, and a water that form the core portion of the polymer resin. After the completion, it can be obtained by adding a monomer for forming the shell portion and a polymerization initiator and performing second-stage emulsion polymerization. At this time, since the copolymer resin to be produced has a two-layer structure, the emulsifier is not added in the second-stage emulsion polymerization, or even if added, the amount is such that a new core is not formed. It is effective to allow the polymerization to proceed on the surface of the copolymer resin core formed in (1). In particular, the core layer, which is a preferred embodiment of the present invention, is not completely encased by the skin layer, but the form in which the core layer is exposed is adjusted, for example, in the above-mentioned production method, with the amount of emulsifier charged during the second stage emulsion polymerization. Or a portion corresponding to the skin layer to be subjected to the second-stage emulsion polymerization is polymerized separately, and the second-stage emulsion polymerization is further performed on the core surface. The above-mentioned acrylic / urethane copolymer resin (A) is obtained by, for example, copolymerizing an acrylic monomer constituting acrylic in the presence of aqueous urethane, or by using aqueous urethane and aqueous acrylic, particularly aqueous acrylic having a crosslinkable functional group. It can be obtained by copolymerization or copolymerization of water-based urethane and water-based acrylic with the crosslinkable functional group of each resin. These water-based urethanes are functional groups that increase the affinity for water to ordinary urethane resins, for example, anionic functional groups such as carboxylic acid groups, sulfonic acid groups, sulfuric acid half ester bases, and cationic functional groups such as quaternary ammonium bases. The thing which introduce | transduced group can be illustrated. Among these functional groups, anionic functional groups are preferable from the viewpoint of dispersibility in water and ease of reaction control during synthesis, and carboxylate groups and sulfonate groups are more preferable. For example, the introduction of a carboxylic acid group may be performed by using a carboxylic acid group-containing polyhydroxy compound as one component of a polyhydroxy compound used as a raw material during urethane copolymerization, or by adding a hydroxyl group-containing carboxylic acid to the isocyanate group of a urethane having an unreacted isocyanate group. The reaction can be carried out by reacting the amino group-containing carboxylic acid, and then adding the reaction product to an alkaline aqueous solution with high-speed stirring and neutralizing.

  In addition, introduction of a sulfonate group or a sulfuric acid half ester base, for example, forms a prepolymer from a polyhydroxy compound, a polyisocyanate, and a chain extender, and an amino group or a hydroxyl group that can react with a terminal isocyanate group and a sulfonate group. Alternatively, a compound having a sulfuric acid half ester base in the molecule is added and reacted to finally obtain an aqueous urethane having a sulfonate group or a sulfuric acid half ester base in the molecule.

In that case, it is preferable to perform a production | generation reaction in an organic solvent, and then remove this organic solvent after adding water. As another method, a compound having a sulfonic acid group is used as one of raw materials to polymerize a urethane having a sulfonic acid group, and then the urethane is added to an alkaline aqueous solution with high-speed stirring, followed by neutralization. And a method of introducing a sulfonic acid alkali salt (for example, sulfonated sodium base) in the presence of an alkali into the primary or secondary amino group of the main chain or side chain of urethane. As the alkaline aqueous solution, it is preferable to use an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, alkylamine, etc., particularly ammonia that does not leave the alkali in the coating film after coating and drying, amine that volatilizes under dry solid conditions, etc. preferable. The amount of a base such as a carboxylic acid base, a sulfonic acid base, or a sulfuric acid half ester base is preferably 0.5 × 10 ^{−4 to} 20 × 10 ⁻⁴ equivalent / g, and more preferably 1 × 10 ⁻⁴ to 10 × 10 ^−4. Equivalent / g is preferred. If the proportion of the base is too small, the affinity of urethane for water is insufficient, making it difficult to prepare an aqueous dispersion, and if it is too large, the original properties of urethane are impaired. Of course, the water-based urethane forms a stable aqueous dispersion or forms an aqueous solution by using a dispersion aid as required.

  Examples of the polyhydroxy compound used in the synthesis of urethane include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, poly Caprolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, glycerin, and the like can be used.

  In particular, in the present invention, those using polycaprolactone or polycarbonate diol are preferable as the polyhydroxy compound. In this case, the coating appearance is particularly excellent when applied on a film.

  Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, an adduct of tolylene diisocyanate and trimethylol propane, an adduct of hexamethylene diisocyanate and trimethylol ethane, and the like.

  Examples of the carboxylic acid group-containing polyhydroxy compound include dimethylolpropionic acid, dimethylolbutyric acid, dimethylolvaleric acid, trimellitic acid bis (ethylene glycol) ester, and the like. As the amino group-containing carboxylic acid, for example, β-aminopropionic acid, γ-aminobutyric acid, p-aminobenzoic acid and the like can be used. As the hydroxyl group-containing carboxylic acid, for example, 3-hydroxypropionic acid, γ-hydroxybutyric acid, p- (2-hydroxyethyl) benzoic acid, malic acid and the like can be used.

  Examples of the compound having an amino group or a hydroxyl group and a sulfone group that can react with a terminal isocyanate group include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 2-amino-5-methylbenzene-2-sulfonic acid, and β-hydroxy. Sodium ethanesulfonate, a propane sultone of an aliphatic diprimary amine compound, a butane sultone addition product, and the like can be used, and a propane sultone adduct of an aliphatic primary amine compound is preferable.

  Furthermore, examples of the compound containing an amino group or a hydroxyl group capable of reacting with a terminal isocyanate group and a sulfuric acid half ester include aminoethanol sulfate, ethylenediamineethanol sulfate, aminobutanol sulfate, hydroxyethanol sulfate, γ-hydroxypropanol sulfate, α-hydroxy. Butanol sulfate or the like can be used.

  Polymerization of urethane using these compounds can be performed by a conventionally used method.

  Examples of acrylic monomers used in the acrylic / urethane copolymer resin (A) include alkyl acrylates (alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.) Alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Hydroxyl group-containing monomers such as acrylate and 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolacrylamide, Amide group-containing monomers such as methylol methacrylamide, N, N-dimethylol acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-phenyl acrylamide, N, N-diethylaminoethyl acrylate Amino group-containing monomers such as N, N-diethylaminoethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, carboxyl such as acrylic acid, methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) A monomer containing a group or a salt thereof can be used. In the present invention, it is preferable to copolymerize a crosslinkable functional group, and it is particularly preferable to copolymerize N-methylolacrylamide in terms of improving the self-crosslinking property and the crosslinking density. The copolymerization ratio of N-methylolacrylamide is preferably from 0.5 to 5% by weight in terms of copolymerizability and the degree of crosslinking, and more preferably from 1 to 3% by weight in view of the coating appearance. When the amount is less than 0.5% by weight, for example, moisture-resistant adhesion tends to be inferior, and when it exceeds 5% by weight, for example, the stability of the aqueous dispersion of the resin tends to be inferior, and the coating appearance tends to be deteriorated.

  These acrylic monomers can be used in combination with other monomers. Examples of other kinds of monomers include glycidyl group-containing monomers such as allyl glycidyl ether, sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or salts thereof. Monomers, monomers containing carboxyl groups such as crotonic acid, itaconic acid, maleic acid, fumaric acid and their salts (sodium salt, potassium salt, ammonium, etc.) or acid anhydrides such as maleic anhydride and itaconic anhydride Monomer containing functional groups, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, acrylonitrile , Methacrylonitrile, alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride, etc. can be used vinylpyrrolidone.

  Acrylic monomers are polymerized using one or more kinds, but when other monomers are used in combination, the proportion of acrylic monomers in all monomers may be 50% by weight or more, and even 70% by weight or more. preferable.

The glass transition temperature (Tg) of the acrylic resin constituting the acrylic / urethane copolymer resin (A) is preferably 20 ° C. or higher, more preferably 40 ° C. or higher. When this glass transition temperature is less than 20 ° C., the heat resistance is insufficient, and for example, blocking tends to occur easily even at room temperature.
The ratio of “acrylic / urethane” in the acrylic / urethane copolymer resin (A) is preferably “10/90” to “70/30”, more preferably “20/80” to “50” in terms of weight ratio. / 50 ". If the ratio using an acrylic monomer is less than 10/90, the adhesiveness of the laminate obtained after coating and drying tends to deteriorate, and if it exceeds 70/30, the surface of the laminate is covered with acrylic. Since the ratio increases, the initial adhesiveness tends to deteriorate. The weight ratio of “acrylic / urethane” can be set to a desired value by adjusting the blending amount of the raw materials during the production of the acrylic / urethane copolymer resin (A).

  As a method for producing the acrylic / urethane copolymer resin (A), for example, a small amount of a dispersant and a polymerization initiator are added to the aqueous dispersion of the aqueous urethane described above, and the acrylic monomer is stirred while maintaining a constant temperature. While gradually adding, then raise the temperature as necessary, continue the reaction for a certain period of time to complete the polymerization of the acrylic monomer, and obtain a water dispersion of acrylic-urethane copolymer resin, etc. It is not limited to this.

  By using the acrylic / urethane copolymer resin (A), not only can the resin sheet be given good transparency, but also adhesiveness can be given.

(2) Oxazoline compound (B)
The oxazoline compound used in the present invention is not particularly limited as long as it has at least one oxazoline group or oxazine group per molecule, but the addition-polymerizable oxazoline group-containing monomer is polymerized alone or polymerized with other monomers. The polymer type is preferred. By using a polymer type oxazoline compound, the flexibility, toughness, water resistance, and solvent resistance of the resin sheet can be improved.

  As addition-polymerizable oxazoline group-containing monomers, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline. These may be used alone or in a mixture of two or more. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer, such as alkyl acrylate, alkyl methacrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (Meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group), acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.), unsaturated nitriles such as acrylonitrile, methacrylonitrile; acrylamide, methacrylamide, N-alkylacrylamide N-alkyl methacrylamide N, N-dialkylacrylamide, N, N-dialkylmethacrylate (as alkyl groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group) , Cyclohexyl groups, etc.), vinyl esters such as vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid with polyalkylene oxide added to the ester moiety, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, etc. , Α-olefins such as ethylene and propylene, halogen-containing α and β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride, α and β-unsaturated aromatics such as styrene and α-methylstyrene Group monomers and the like, one or more of these It may be used monomers.

  By using the oxazoline compound (B), it is possible to impart wet heat resistance, which will be described later, to the resin sheet.

(3) Carbodiimide compound (C)
The carbodiimide compound used in the present invention is not particularly limited as long as it has at least one carbodiimide structure represented by the following general formula (1) per molecule, but in terms of moisture and heat resistance, Polycarbodiimide compounds having two or more in one molecule are particularly preferred. In particular, when a polymer type isocyanate compound having a plurality of carbodiimide groups is used at the terminal or side chain of a polymer such as a polyester resin or an acrylic resin, the flexibility and toughness of the resin sheet is preferably increased. it can.
-N = C = N- (1)
The polycarbodiimide compound can be obtained by known means, and is generally obtained by polycondensation of a diisocyanate compound in the presence of a catalyst. As the diisocyanate compound that is a starting material of the polycarbodiimide compound, aromatic, aliphatic, and alicyclic diisocyanates can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane. Diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used. Furthermore, in order to improve the water solubility and water dispersibility of the polycarbodiimide compound within the range not losing the effect of the present invention, a surfactant is added, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, hydroxy A hydrophilic monomer such as an alkyl sulfonate may be added or used.

  By using the said carbodiimide compound (C), the heat-and-moisture resistant adhesiveness mentioned later can be provided to a laminated body. Further, when used in combination with the oxazoline compound (B), the resin sheet can be provided with a synergistic moisture and heat-resistant adhesive property that is more than expected from when the oxazoline compound (B) or the carbodiimide compound (C) is used. .

(4) Isocyanate compound (D)
Examples of the isocyanate compound that can be used in the present invention include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, and tolylene diene. Addition product of isocyanate and hexanetriol, addition product of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate 3,3′-vitrylene-4,4 ′ diisocyanate, 3,3′dimethyldiphenylmethane-4,4′-diisocyanate, metaphenylene diisocyanate Anate etc. are mentioned. In particular, when a polymer type isocyanate compound having a plurality of isocyanate groups is used at the terminal or side chain of a polymer such as a polyester resin or an acrylic resin, the flexibility and toughness of the resin sheet is preferably increased. it can.

  Furthermore, in the case of using a coating composition, for example, a blocked isocyanate compound in which the isocyanate group is masked with a blocking agent or the like is preferably used from the viewpoint of easy reaction of the isocyanate group with the water and pot life of the coating agent. be able to. A typical example of the blocking agent is a system in which the blocking agent is volatilized by heating after coating and heat in the drying process, and an isocyanate group is exposed to cause a crosslinking reaction. The isocyanate group may be either a monofunctional type or a polyfunctional type, but a polyfunctional type block polyisocyanate compound can be suitably used in that the crosslinking density can be easily increased. Examples of low-molecular or high-molecular compounds having two or more blocked isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane 3-mole adduct, polyvinyl isocyanate, vinyl isocyanate copolymer, polyurethane-terminated diisocyanate. , A methyl ethyl ketone oxime block of tolylene diisocyanate, a sodium hyposulfite block of hexamethylene diisocyanate, a methyl ethyl ketone oxime block of a polyurethane-terminated diisocyanate, a phenol block of trimethylolpropane to a tolylene diisocyanate 3 mol adduct, and the like. it can.

  By using the isocyanate compound (B), a tough resin sheet can be formed, and the adhesiveness can be further improved.

(5) Melamine compound (E)
The melamine compound that can be used in the present invention is not particularly limited as long as it has a melamine structure, but a methyl alcohol melamine derivative obtained by condensing melamine and formaldehyde in terms of hydrophilicity is used as a lower alcohol. And compounds obtained by etherification by dehydration condensation reaction of methyl alcohol, ethyl alcohol, isopropyl alcohol and the like.

  Examples of methylolated melamine derivatives include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.

  By using the melamine compound (E), the moisture and heat resistance can be further improved on the resin sheet.

(6) Organometallic compound (F)
The organometallic compound that can be used in the present invention contains a metal atom, and generally has a catalytic action that promotes an addition reaction, a polymerization reaction, and a crosslinking reaction such as an isocyanate group, a hydroxyl group, a carboxyl group, and an amino group. Although it will not specifically limit if it is a compound which has, It is preferable that the metal atom contained is chosen from the organometallic compound which consists of tin, bismuth, zirconium, aluminum, titanium, iron, and zinc. In particular, a tin-based compound and a zirconium-based compound having a high reaction promoting effect are preferable.

  By using the organometallic compound (F), whitening can be significantly suppressed even when the resin sheet is heated. More specifically, the haze increase rate after heating the laminated body at 150 ° C. for 30 minutes is 2% or less, and the oligomer content having a molecular weight of 60 to 700 in the layer composed of acrylic / urethane copolymer resin and two or more crosslinking agents is 0. .7% by weight or less.

These coating agents (A), (B), (C), (D), (E), and (F) are mixed so as not to be aggregated and uniformly applied by a # 4 bar coater. It is formed. At the time of mixing, the blending ratio (parts by weight) of these coating agents is preferably set in the following range.
(A) / (B) / (C) / (D) / (E) / (F) = 38-50 / 20-40 / 20-40 / 50-62 / 1-20 / 0.1-1
In the resin sheet of the present invention, it is preferable that both outermost layers of the laminated film as a substrate are composed of polyethylene terephthalate having a thickness of 2 to 10 μm. The outermost polyethylene terephthalate layer is effective in suppressing oligomer bleed out. It should be noted that even if it is larger than 10 μm, there is no particular problem, but a large difference in effect is not observed. The outermost layer can be achieved by appropriately increasing the slit width for forming thick film layers located at both ends of the slit plate in the laminating apparatus. Alternatively, it can also be achieved by forming a multilayer film with a laminating apparatus and then merging and laminating polyethylene terephthalate to both surface layers with a third extruder.

  Dissolve or disperse these materials in a solvent such as water, and add and mix additives such as leveling agents, foam inhibitors, viscosity modifiers, stabilizers, preservatives, etc., as necessary. The

  Further, it is preferable that IV (intrinsic viscosity) of the polyethylene terephthalate of both surface layers is 0.55 to 0.7 and the oligomer content is 0.1 to 0.7% by weight. Here, the oligomer will be briefly described. The oligomer is usually an organic substance having a molecular weight of 60 to 700, and has a solid property at room temperature (25 ° C.). Many of them are melt-decomposed products and unreacted products of polyester. Examples include terephthalic acid, 2-bishydroxyethyl terephthalic acid, cyclic trimer, 4-carboxybenzaldehyde and the like, and most of them have the structure of polyester dicarboxylic acid or diol. In particular, it tends to increase when a component easily oxidized and deteriorated is contained in the molecular chain of the polyester. The polyester used in the present invention preferably has an oligomer content of 0.1 to 0.7% by weight. Therefore, solid phase polymerization is performed before forming a laminated film, or a known oxidative degradation inhibitor is added to the polyester. On the other hand, it is preferably employed to contain it at a ratio of 0.1 to 5% by weight.

  The oligomer content is measured by GPC (gel permeation chromatography). The apparatus is HPLC 8120 series manufactured by Tosoh Corporation, the column is TSKgel superHM-H H4000 / H3000 / H2000 (7.8 mm diameter, 150 mm × 3), eluent THF (tetrahydrofuran), flow rate 1 ml / min, sample concentration 0.1%, The injection amount is 20 μL, the detector RI, the measurement temperature is 40 ° C., and the measurement pretreatment is performed on the resin component obtained by dissolving the film in THF and filtering with a 0.45 μm filter to remove additives such as silica. The column was stabilized in a heat chamber at 40 ° C., THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the concentration of the resin component was adjusted to 0.05 to 0.6% by weight. Measurement is performed by injecting 50 to 200 μl of the sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the prepared calibration curve and the number of counts using several types of monodisperse polystyrene standard samples. From this, the area ratio of the peak with a molecular weight of less than 700 to the whole can be calculated.

  Next, the method for obtaining the resin sheet of the present invention will be described in detail with reference to examples. Two types of polyester resin A and polyester resin B are prepared in the form of pellets. The pellets are dried in hot air or under vacuum as necessary, and then supplied to a separate extruder. In the extruder, the resin that has been heated and melted to the melting point or higher is made uniform in the extrusion amount of the resin by a gear pump or the like, and foreign matter or denatured resin is removed through a filter or the like.

  Polyester resin A and polyester resin B sent out from different flow paths using these two or more extruders are then fed into the multilayer laminating apparatus. As the multilayer stacking apparatus, a multi-manifold die or a field block can be used. Moreover, you may combine these arbitrarily. The structure of the feed block has at least one member in a comb-shaped slit plate having a large number of fine slits, and resin A and resin B extruded from two extruders pass through each manifold, Introduced into the slit plate. Here, since the resin A and the resin B selectively flow alternately into the slit through the introduction plate, finally, a multilayer film such as A / B / A / B / A... Can be formed. . In addition, the number of layers can be increased by further overlapping the slit plates.

Further, since the reflection wavelength can be obtained by the following equation 1, the order of the reflection wavelength can be arbitrarily adjusted by the thickness of each layer. The reflectance is controlled by the difference in refractive index between the A layer and the B layer and the number of layers of the A layer and the B layer.
2 × (na · da + nb · db) = λ Equation 1
na: In-plane average refractive index of the A layer nb: In-plane average refractive index of the B layer da: Layer thickness (nm) of the A layer
db: Layer thickness of layer B (nm)
λ: main reflection wavelength (primary reflection wavelength)
The melt laminated in this way is extruded into a sheet form from a slit-shaped die, adhered to the casting drum by a method such as electrostatic application, cooled and solidified into an unstretched sheet, and then stretched in two directions. It is preferable to heat-treat. Moreover, in order to give functions, such as runnability (easiness of slipperiness), a weather resistance, and heat resistance, to a film, it is good also as what added particle | grains to the resin layer which comprises a surface layer part. Examples of such particles include organic particulates such as polyimide, polyamideimide, polymethylmethacrylate, formaldehyde resin, phenolic resin, crosslinked polystyrene, as well as wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate. Inorganic fine particles such as barium sulfate, alumina, mica, kaolin, and clay can be used. As the stretching method, techniques such as a sequential biaxial stretching method of stretching in the width direction after stretching in the longitudinal direction and a simultaneous biaxial stretching method of stretching the longitudinal direction and the width direction almost simultaneously are used. The preheating temperature before stretching and the stretching temperature are 60 ° C. to 130 ° C., the stretching ratio is 2.0 to 5.0 times, and if necessary, heat treatment from 140 ° C. to 240 ° C. is performed after stretching.

  The laminated film used in the present invention preferably has heat resistance, mechanical strength and dimensional stability that can withstand higher order processes. If the thickness of the laminated film is 10 μm or less, the thermal and mechanical stability will be insufficient, and if it is 250 μm or more, the rigidity will be too high and the handleability will be lowered, and the roll length will be physically long. 14 to 250 μm is preferable, and 38 to 188 μm is more preferable.

  As a preferable method for forming this coating film layer, it is convenient to install a coating means for a coating agent during the production process during the production of the laminated film, and to apply and dry it. At this time, it can be stretched together with the film. For example, the method of applying before introducing into the tenter and drying and curing in the transverse stretching step / heat treatment step is a suitable method. Various coating methods such as reverse coating method, gravure coating method, rod coating method, bar coating method, Mayer bar coating method, die coating method, spray coating method and the like can be used as the coating method. In consideration of the uniformity of coating film application and adhesiveness, it is preferable to subject the film surface to corona discharge before coating. Moreover, it is also possible to provide this coating film layer using a well-known method after formation of a laminated film.

  The resin sheet thus obtained has excellent high-temperature molding processability, and also has excellent adhesion under heat and humidity resistance. In various moldings such as pressure molding, in-mold molding, insert molding, cold molding, and press molding, molding can be performed without problems such as peeling.

  The resin sheet of the present invention includes a hard coat layer, an antistatic layer, an abrasion resistant layer, an antireflection layer, a color correction layer, an ultraviolet absorption layer, a printed layer, a metal layer, a transparent conductive layer, a gas barrier layer, and a hologram layer. Functional layers such as a release layer, an adhesive layer, an emboss layer, and an adhesive layer may be further formed.

  An evaluation method of physical property values used in the present invention will be described.

(Method for evaluating physical properties)
(1) Relative reflectance, reflection performance A 60-sphere integrating sphere 130-0632 (Hitachi Ltd.) and a 10 ° inclined spacer were attached to a spectrophotometer (U-3410 Spectrophotometer) manufactured by Hitachi, Ltd., and the reflectance was measured. The band parameter was set to 2 / servo, the gain was set to 3, and the range from 380 nm to 2500 nm was measured at a detection speed of 120 nm / min. In order to standardize the reflectance, an attached Al ₂ O ₃ plate was used as a standard reflecting plate.

  In addition, in the wavelength range of 380 nm to 2500 nm, the reflection performance is ○ that has a reflection band with a half width of 20 nm or more and a reflectance of 30% or more, and a reflection band with a half width of 50 nm or more and a reflectance of 60% or more. It was evaluated as ◎, having a half-value width of 20 nm or more, but having a reflectance of less than 30%, Δ, and having no reflection band at all, evaluated as ×.

(2) Number of layers, thickness of layered film The layer structure of the film was determined by observation with an electron microscope for a sample cut out of a cross section using a microtome. That is, using a transmission electron microscope H-7100FA type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified 40000 times at an acceleration voltage of 75 kV, a cross-sectional photograph was taken, and the layer configuration and each layer thickness were measured. In some cases, in order to obtain high contrast, a staining technique using a known RuO ₄ or OsO ₄ may be used.

  A specific method for obtaining the laminated structure will be described. About 40,000 times as many TEM photographic images were captured with CanonScan D123U at an image size of 720 dpi. The image is saved in the JPEG format, and then image processing software Image-Pro Plus ver. 4 (sales company Planetron Co., Ltd.) was used to open this JPG file and perform image analysis. In the image analysis process, the relationship between the thickness in the thickness direction and the average brightness of the area sandwiched between the two lines in the width direction was read as numerical data in the vertical thick profile mode. Using the spreadsheet software (Excel2000), the position (nm) and brightness data were subjected to numerical processing of sampling step 6 (decimation 6) and 3-point moving average. Furthermore, the data obtained by periodically changing the brightness is differentiated, and the maximum value and the minimum value of the differential curve are read by a VBA (Visual Basic For Applications) program. The layer thickness was calculated as the layer thickness of one layer.

(3) Adhesive A printed layer is provided on the side of the resin sheet where the coating layer is provided, and insert molding is performed under the conditions of a film temperature of 120 ° C., a resin temperature of 250 ° C., a mold temperature of 60 ° C., and an injection speed of 240 mm / s. 100 pieces of 1 mm ² crosscuts were put on the surface carried out in, and a cellophane tape made by Nichiban Co., Ltd. was applied thereon, pressed with a load of 1.5 kg / cm ² , and then peeled in the direction of 90 °. Four-stage evaluation (◎: 100, ○: 80 to 99, Δ: 50 to 79, x: 0 to 49) was performed according to the number of remaining pieces. (◎) is considered to have good adhesion.

(4) A printing layer is provided on the side of the wet heat and heat resistant resin sheet on which the coating layer is provided, and insert molding is performed at a film temperature of 120 ° C, a resin temperature of 250 ° C, a mold temperature of 60 ° C, and an injection speed of 240 mm / s. After that, after being left for 168 hours in an atmosphere of 65 ° C. and 95% humidity, 100 pieces of 1 mm ² crosscuts were put on the surface on which insert molding was performed, and cellophane tape made by Nichiban Co., Ltd. was used. Affixed on it, pressed with a load of 1.5 kg / cm ² , peeled in the direction of 90 °, and evaluated according to the four-stage evaluation (◎: 100, ○: 80-99, Δ: 50-79, X: 0 to 49). (◎, ○) is considered to have good adhesion.

(5) Measurement of haze haze is carried out using a fully automatic direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. after leaving the resin sheet sample in an atmosphere of 23 ° C. and 65% relative humidity for 2 hours. It was. The average value measured three times was used as the haze value of the sample.

(6) Haze after heating Instead of placing in an atmosphere of 23 ° C. and relative humidity of 65% for 2 hours, the resin sheet sample was heated at 150 ° C. for 30 minutes, and the haze of (5) above was measured.

(7) Blocking The surfaces of the two sheets of the easy-adhesion layer and the surface without the easy-adhesion layer were overlapped, and a pressure of 1.5 kg / cm ² was applied to the film for 65 hours in an atmosphere of 60 ° C. × 80% RH. Post-peeling and evaluation is performed based on the peeling force (g number per 5 cm overlap width). In addition, evaluation is performed on the following reference | standard from peeling force. (◎) and (○) were considered good.
A: Less than 2 g O: 2 g or more and less than 5 g x: 5 g or more, or the film is broken.

(8) Mold dirt The upper and lower press plates of the press machine are washed smoothly, and a 200 mm x 200 mm film is sandwiched between them. Pressurization is performed at 190 ° C and 30 kg / cm ² , and the state is maintained for 30 minutes. did. Thereafter, a new film was sandwiched and held under pressure in the same manner. When this was repeated 10 times, the mold contamination was visually judged by the appearance of the first film and the tenth film.

◎: There is almost no difference in transparency compared to when the first film was pressed. ○: A slight decrease in transparency was observed compared to when the first film was pressed. △: A decrease in transparency is observed compared to when the first film is pressed. ×: A significant decrease in transparency is observed compared to when the first film is pressed.

(9) Intrinsic viscosity Calculated from the solution viscosity measured at 25 ° C in orthochlorophenol. The solution viscosity was measured using an Ostwald viscometer. The unit is [dl / g]. The n number was 3, and the average value was adopted.

Example 1
Polyethylene terephthalate (PET) [Toray F20S] having an intrinsic viscosity of 0.65 as polyester resin A, 20 mol% of cyclohexanedicarboxylic acid with respect to terephthalic acid as polyester resin B, and 15 mol% of spiroglycol with ethylene glycol The copolymerized polyester (copolymerized PET1) was used. In addition, this resin B had an intrinsic viscosity of 0.67 and was an amorphous resin. Polyester resin A is dried with a rotary vacuum dryer (180 ° C., 3 hours), and polyester resin B is dried with an absolutely dry air circulation dryer (70 ° C., 5 hours). Supplied to the machine.

  Polyester resin A and polyester resin B are each melted at 280 ° C. by an extruder, and after passing through a gear pump and a filter, are alternately laminated in a 51-layer feed block at a discharge ratio of 1.1 / 1. To join. After forming into a sheet shape, it was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application.

The obtained cast film was heated in a roll group set at 75 ° C., and then stretched 3.3 times in the longitudinal direction while rapidly heating from both sides of the film with a radiation heater between 100 mm in the stretch section length, and then temporarily Cooled down. Subsequently, corona discharge treatment was performed in air on both surfaces of this uniaxially stretched film, the wetting tension of the base film was 55 mN / m, and the following materials A, B, C, and D were not aggregated on the treated surface. Thus, the coating composition 1 was prepared and uniformly coated with a # 4 bar coater to form an easy adhesion layer.
"Coating composition 1"
Acrylic / urethane copolymer resin (A):
Acrylic / urethane copolymer resin anionic water dispersion ("Sannaron" WG-353 (prototype) manufactured by Shannan Synthetic Chemical Co., Ltd.). An acrylic resin component / urethane resin component (polycarbonate-based) having a solid content weight ratio of 12/23 and an aqueous dispersion using 2 parts by weight of triethylamine.
Oxazoline compound (B):
Oxazoline-containing polymer aqueous dispersion (“Epocross” WS-500, manufactured by Nippon Shokubai Co., Ltd.)
Carbodiimide compound (C):
Carbodiimide aqueous crosslinking agent (Nisshinbo Chemical Co., Ltd. “Carbodilite” V-04)
Isocyanate compound (D):
Polyisocyanate aqueous dispersion (“Bernock” DNW-500, manufactured by DIC Corporation)
Solid content weight ratio:
(A) / (B) / (C) / (D) = 40 parts by weight / 30 parts by weight / 30 parts by weight / 60 parts by weight This uniaxially stretched film is led to a tenter, preheated with hot air at 100 ° C., and then 110 ° C. The film was stretched 3.5 times in the transverse direction at a temperature of. The stretched film was directly heat-treated with hot air at 230 ° C. in a tenter, subsequently subjected to a relaxation treatment of 5% in the width direction at the same temperature, and then gradually cooled to room temperature and wound up. Table 1 shows the characteristics and the like of the obtained resin sheet.

(Example 2)
Using the polyester resin used in Example 1, the laminating apparatus was changed from a 51-layer feed block to a 801-layer feed block and merged. In addition, said feed block consists of three slit members which have 267 slits. The joined polyester resin A and polyester resin B are changed so that the thickness of each layer gradually increases from the surface side to the opposite surface side in the feed block. The polyester resin A is 401 layers and the polyester resin B is 400 layers. It was set as the structure laminated | stacked alternately in the thickness direction which consists of layers. Moreover, the slit shape was designed so that both surface layer parts might become the polyester resin A, and the layer thickness of the adjacent A layer and B layer became substantially the same. In this design, a reflection band exists between 400 nm and 1200 nm. The thus obtained laminate composed of a total of 801 layers was supplied to a multi-manifold die and formed into a sheet shape, and then rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application. This was formed by the same film forming method as in Example 1. Table 1 shows characteristics and the like of the obtained resin sheet.

(Example 3)
Except that (A) to (D) used in Example 1 were mixed and adjusted at a solid content weight ratio of (A) / (B) / (C) / (D) = 50/30/30/50. A coating composition 2 was prepared in the same manner as in Example 1.

  A resin sheet was obtained in the same manner as in Example 2 except that the coating composition 2 was used. Table 1 shows characteristics and the like of the obtained resin sheet.

Example 4
Except that (A) to (D) used in Example 1 were mixed and adjusted at a solid content weight ratio of (A) / (B) / (C) / (D) = 38/30/30/62. A coating composition 3 was prepared in the same manner as in Example 1.

  A resin sheet was obtained in the same manner as in Example 2 except that the coating composition 3 was used. Table 1 shows characteristics and the like of the obtained resin sheet.

(Example 5)
In addition to (A) to (D) used in Example 1, the melamine compound (E) in terms of solids weight ratio (A) / (B) / (C) / (D) / (E) = 40 / A coating composition 4 was prepared in the same manner as in Example 1, except that the mixture was adjusted at 30/30/60/10.
Melamine compound (E): Melamine resin water sol (DIC Corporation "WATERSOL" S-695)
A resin sheet was obtained in the same manner as in Example 2 except that the coating composition 4 was used. Table 1 shows characteristics and the like of the obtained resin sheet.

(Example 6)
In addition to (A) to (D) used in Example 1, the organometallic compound (F) in terms of solid content weight ratio was (A) / (B) / (C) / (D) / (F) = Coating composition 5 was prepared in the same manner as in Example 1 except that mixing was carried out at 40/30/30/60 / 0.6.

Organometallic compound (F): organozirconium compound ("Orgachix" ZB-126, manufactured by Matsumoto Fine Chemical Co., Ltd.)
A resin sheet was obtained in the same manner as in Example 2 except that the coating composition 5 was used. Table 1 shows characteristics and the like of the obtained resin sheet.

(Example 7)
In addition to (A) to (D) used in Example 1, the melamine compound (E) used in Example 5 and the organometallic compound (F) used in Example 6 are in a solid weight ratio (A ) / (B) / (C) / (D) / (E) / (F) = 40/30/30/60/10 / 0.6 Coating composition 6 was prepared.
A resin sheet was obtained in the same manner as in Example 2 except that the coating composition 6 was used. Table 1 shows characteristics and the like of the obtained resin sheet.

(Comparative Example 1)
Film formation was performed under the same conditions as in Example 2. However, the layer by the coating composition 1 is not formed. Table 1 shows the characteristics and the like of the obtained laminated film.

(Comparative Example 2)
A film was formed and applied under the same conditions as in Example 2 except that the coating composition 1 was changed to the coating composition 7 shown below.
"Coating composition 7"
A ′: Water-dispersed alkyl acrylate (acid group 2.8 mg / g)
B ′: methylolated melamine (diluent: isopropyl alcohol / water)
C ′: Colloidal silica (average particle size 80 nm)
D ': Perfluorobutyl sulfonate (diluent: water)
Solid content weight ratio: (A ′) / (B ′) / (C ′) / (D ′) = 100 parts by weight / 25 parts by weight / 3 parts by weight / 0.2 parts by weight Properties of the obtained resin sheet, etc. Is shown in Table 1.

(Comparative Example 3)
A resin sheet was obtained in the same manner as in Example 1, except that a 33-layer feed block was used instead of the 51-layer feed block. Table 1 shows characteristics and the like of the obtained resin sheet.

(Comparative Example 4)
PET pellets (extreme viscosity 0.63 dl / g) substantially free of particles are sufficiently vacuum dried, then supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T-shaped die, and electrostatically applied Using a casting method, it was wound around a mirror casting drum having a surface temperature of 25 ° C. to be cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film. This film was subjected to corona discharge treatment in air.

  Next, the coating composition 1 was applied to the corona discharge-treated surface of the uniaxially stretched film using a bar coat. The both ends in the width direction of the uniaxially stretched film coated with the coating composition 1 are gripped with a clip and guided to a preheating zone. After setting the ambient temperature to 75 ° C, the ambient temperature is set to 110 ° C using a radiation heater, and then The coating liquid was dried at an atmospheric temperature of 90 ° C. Continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ° C., followed by heat treatment for 20 seconds in a heat treatment zone (heat setting zone) at 230 ° C. to complete the crystal orientation Got. In the obtained resin sheet, the thickness of the PET film portion was 100 μm. Table 1 shows characteristics and the like of the obtained resin sheet.

(Comparative Example 5)
A resin sheet was obtained under the same conditions as in Comparative Example 4 except that the coating composition 6 was used in place of the coating composition 1. Table 1 shows characteristics and the like of the obtained resin sheet.

(Comparative Example 6)
A resin sheet was obtained under the same conditions as in Comparative Example 4 except that the coating composition 7 was used in place of the coating composition 1. Table 1 shows characteristics and the like of the obtained resin sheet.

  INDUSTRIAL APPLICABILITY The present invention can be used as a design for interior and exterior of various molded products such as building materials, packaging, automobiles and mobile phones.

Claims (4)

It includes a structure in which 50 layers or more of layers made of polyester resin A (A layer) and layers of polyester resin B (B layer) are alternately laminated, and has at least one reflection band with a relative reflectance of 30% or more. A resin sheet, wherein a layer made of a reaction product of a coating agent containing at least an acrylic / urethane copolymer resin, an oxazoline-based crosslinking agent, and a carbodiimide crosslinking agent is provided on one side or both sides of a laminated film. The resin sheet according to claim 1, wherein a haze increase rate before and after heating at 150 ° C. for 30 minutes is 2% or less. A printed layer is provided on the resin sheet on the layer made of the reaction product of the coating agent, and insert molding is performed under the conditions of a film temperature of 120 ° C., a resin temperature of 250 ° C., a mold temperature of 60 ° C., and an injection speed of 240 mm / s. Then, after standing for 168 hours in an atmosphere of 65 ° C. and 95% humidity, 100 cross cuts of 1 mm ² were put on the surface on the printed layer side, and cellophane tape manufactured by Nichiban Co., Ltd. was pasted thereon. 3. The resin sheet according to claim 1, wherein the printed layer does not peel when peeled in a 90 ° direction after being pressed with a load of 5 kg / cm ² . The molded object using the resin sheet in any one of Claim 1 to 3.