TWI445746B - Polyester film for forming - Google Patents

Description

Molding film for molding

The present invention relates to a polyester film for molding. In particular, a polyester film for molding is excellent in appearance and decorative property particularly when it is used as a plating substitute, that is, when it is mirror-finished.

Various materials are used in the production of a molded article such as an exterior decorative member. For example, the outer surface of a molded body of an automobile part such as a moul or a pillar is plated or coated with a resin material. Incidentally, in the manufacture of exterior parts or interior parts of automobiles, generally, a method of coating or plating after surface treatment is employed, and recently, a document has been proposed as a coating film. Instead of or plating, instead of performing a method of decorating the molded body (Patent Document 1).

Such a resin sheet material for molding has conventionally used a polyvinyl chloride film. However, when a film is burned, toxic gas and overflow plasticizer are generated, which may cause problems in environmental suitability. Therefore, as a material excellent in environmental suitability, an unstretched sheet containing a polyester, a polycarbonate, or an acrylic resin has been used in a wide range of fields. For example, in the case of Patent Document 2, a polyester film for molding which exhibits excellent moldability is proposed.

On the other hand, there have been various proposals for improving the adhesion of the polyester film. For example, Patent Document 3 discusses the use of a copolymerized polyester, and Patent Document 4 discusses a method of using a copolymerized polyester and a water-soluble polyurethane resin as an easy-adhesion layer. The polyester film for molding proposed in the above Patent Documents 3 and 4 can be suitably used for various molding purposes because it has good adhesion and can be appropriately decorated by vapor deposition, printing, or the like.

[Previous Technical Literature] [

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-297569

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-30475

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-290354

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-131767

In the plating-containing film containing polyester, in order to exhibit adhesion to various functional layers such as a decorative layer, an easy-adhesion layer is provided on the surface of the film. In the case of plating, a thinner film is often used instead of the decorative film, and when the film is wound into a roll, wrinkles or streaks are likely to occur. Then, by adding particles to the surface of the film, particularly in the easy-adhesion layer, the surface is provided with a concavo-convex structure, and the smoothness necessary for the production step or the processing step is imparted.

On the other hand, instead of metal plating, a mirror-like metallic luster treatment is performed by metal vapor deposition or the like, and the surface is desired to be smooth in order to exhibit a high-grade appearance. However, there are cases where the surface of the film has irregularities and the surface texture is damaged. In particular, plating may be used instead of the film to be used, and a film having excellent moldability and having a soft elasticity and a thin film thickness can be used. Therefore, in the case of being wound into a roll shape, the surface of the film is easily pressed and deformed. For example, when a thin film having a thin film is wound into a roll, even if such a fine uneven structure that cannot be visually recognized from the film itself is subjected to a metallic gloss treatment, the fine uneven structure causes scattering of reflected light to cause reflection. The image on the mirror is skewed.

Further, a molding system in which the plating is integrally molded (insert molding) instead of the decorative film is used as an automobile, a home appliance, a mobile phone, or a member for building materials, and is used outdoors and indoors. It is predicted that in such a use environment, the molded body will be exposed to high temperature or humidity for a long period of time. Therefore, it is preferable to maintain good adhesion to the decorative layer such as the vapor deposition layer or the printing layer even after the molding in a hot and humid environment.

An object of the present invention is to solve the above problems. That is, a polyester film for molding is provided which has good adhesion to a decorative layer such as a vapor deposition layer or a printing layer, and exhibits a mirror-like appearance when used as a plating instead of a use. Further, it is preferable to provide a polyester film for molding, which is excellent in adhesion in a hot and humid environment in addition to the above. More preferably, it is a polyester film for insert molding which has moldability suitable for insert molding.

The polyester film for molding of the present invention which can solve the above problems includes the following constitution:

The first invention is a polyester film for molding which has an easy-adhesion layer on at least one side of the polyester film, and the easy-adhesion layer contains a polyester resin, a polyurethane resin, and at least one type of particles. The particle size distribution (d75/d25) is 1.1 to 1.5, the average particle diameter is 0.04 to 1.2 μm, and the ratio (d/t) of the average particle diameter d of the particles to the thickness t of the easily-adhered layer is 1 or more and 100 or less.

The second invention is the polyester film for molding described above, wherein the polyester film is a copolymerized polyester or a copolymerized polyester and a homopolyester.

According to a third aspect of the invention, the polyester film for molding, wherein the polyester resin is a polyester-based graft copolymer obtained by grafting a polymerizable unsaturated monomer onto a hydrophobic copolymerized polyester resin, and the polymerizable unsaturated polymer is unsaturated. The monomer contains at least one acid anhydride having a double bond.

According to a fourth aspect of the invention, the polyester film for molding, wherein the polyurethane resin is a polycarbonate-based polyurethane resin.

According to a fifth aspect of the invention, the polyester film for molding includes 0.01 to 3% by mass of the particles in the easy-adhesion layer, a haze of 2.0% or less, a static friction coefficient of 0.9 or less, and a dynamic friction coefficient of 0.8 or less. The air escape index is less than 200 seconds.

According to a sixth aspect of the invention, there is provided the polyester film for molding, wherein the film thickness is 15 to 100 μm.

According to a seventh aspect of the invention, in the polyester film for molding, the flatness test apparatus has a reflection intensity (Wa) of 4.0 or less in a region of a wavelength of 0.1 mm to 0.3 mm measured on the surface of the film.

According to a eighth aspect of the invention, there is provided a plating replacement processing method, characterized in that after the metal deposition layer is provided on one surface of the polyester film for molding, the substrate is integrally molded.

A ninth invention is a polyester film for insert molding, which has an easy-adhesive layer on at least one side of the polyester film, a polyester film-based copolymerized polyester, or a copolymerized polyester and a homo-polyester, and a poly The thickness of the ester film was 15 to 100 μm, and the reflection intensity (Wa) in the region of 0.1 mm to 0.3 mm measured on the surface of the film using a flatness tester was 4.0 or less.

According to a tenth aspect of the invention, the polyester film for insert molding, wherein the easy-adhesion layer contains a polyester resin, a polyurethane resin, and at least one type of particles.

According to a eleventh aspect of the invention, the polyester film for insert molding, wherein the particle size distribution (d75/d25) of the particles is 1.1 to 1.5, the average particle diameter d is 0.04 to 1.2 μm, and the average particle diameter d of the particles and the easy-to-layer layer The ratio (d/t) of the thickness t is 1 or more and 100 or less.

According to a twelfth aspect, the polyester film for insert molding, wherein the easy-adhesion layer contains a polyester resin and a polyurethane resin, and the polyester resin is graft-polymerizable unsaturated on the hydrophobic copolymerized polyester resin. A monomer-based polyester-based graft copolymer containing at least one acid anhydride having a double bond.

According to a thirteenth aspect of the invention, the polyester film for insert molding, wherein the polyurethane resin is a polycarbonate-based polyurethane resin.

According to a fourteenth aspect of the invention, the polyester film for insert molding, wherein the easy-to-adhere layer contains 0.01 to 3% by mass of the particles, the film has a haze of 2.0% or less, a static friction coefficient of 0.9 or less, and a dynamic friction coefficient of 0.8 or less. The air removal index is less than 200 seconds.

According to a fifteenth aspect of the invention, there is provided a plating film instead of a decorative film which has a metal deposition layer on one surface of the polyester film for insert molding.

In the molding of the present invention (including the meaning of insert molding, the same applies hereinafter), the polyester film has an easy-to-adhere layer in which a specific resin composition and a specific particle are laminated. In addition, both moldability and surface smoothness are excellent. Therefore, it is suitable for forming a mirror-like decorative layer which is excellent in adhesion and excellent in surface texture. Therefore, in the case of a decorative member for decoration, such as a decorative material for a vehicle interior or exterior, a home appliance membrane switch, a base material for a mobile phone, and a member for building materials, it is integrally molded with the molding substrate (insert molding). ), and can be applied as a plating instead of a treatment method.

Further, the present invention can be suitably used for outdoor use even if it has good adhesion under moist heat.

[Formation for implementing the invention] (easy to layer)

The easy-adhesion layer of the present invention comprises a polyester resin and a polyurethane resin and at least one specific particle. Thereby, an appropriate adhesion to a decorative layer such as printing or vapor deposition is exhibited, and a mirror-like suitable surface texture can be exhibited at the time of metal vapor deposition.

Hereinafter, each configuration of the easy-adhesion layer of the present invention will be described in detail.

(polyester resin)

A polyester resin is contained in the easy-adhesion layer. In order to improve the adhesion to the base film and the printed layer, a polyester resin is required. When the polyester resin is not contained, it is easy to cause minute adhesion of the adhesive layer, and as a result, the adhesion is lowered.

The polyester resin contained in the easy-adhesion layer can impart adhesion to the base polyester film and the easy-adhesion layer. Therefore, it is preferably blended in a range of 5 to 90% by mass based on the entire solid content of the easily-adhesive layer. Preferably, it is 30 to 80% by mass.

From the viewpoint of adhesion, the polyester resin is preferably a copolymerized polyester in which a copolymerization component is introduced to lower the glass transition temperature. From the viewpoint of coatability, the copolymerized polyester is preferably water-soluble or water-dispersible. The copolymerized polyester is a copolymerized polyester (hereinafter referred to as a copolymerized polyester containing a sulfonic acid group) bonded to at least one group selected from the group consisting of a sulfonic acid group or an alkali metal salt group thereof. It is better.

The copolymerized polyester having a sulfonic acid group herein means that a part of the dicarboxylic acid component or the diol component is bonded to at least one group selected from the group consisting of a sulfonic acid group or an alkali metal salt group thereof. a polyester in which an aromatic dicarboxylic acid containing at least one group selected from the group consisting of a sulfonic acid group or an alkali metal salt group thereof is used in a ratio of 2 to 10 mol% with respect to the entire acid component. The copolymerized polyester prepared by the acid component is preferred.

An example of such a dicarboxylic acid is 5-sodium sulfoisophthalic acid. In this case, examples of other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, p-β-ethoxyethoxybenzoic acid, 2,6-naphthalene dicarboxylic acid, and 4,4′-dicarboxyl group. Diphenyl, 4,4'-dicarboxydiphenyl ketone, bis(4-carboxyphenyl)ethane, adipic acid, sebacic acid, cyclohexane-1,4-dicarboxylic acid, and the like.

In addition, in order to improve the surface hardness and maintain good blocking resistance, it is preferable to set 96 to 90 mol% of all acidic components to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. It is more preferable that at least one group selected from the group consisting of the above-mentioned sulfonic acid group or an alkali metal salt group thereof is contained in 4 to 10 mol% of the aromatic dicarboxylic acid.

A glycol component for producing a copolymerized polyester containing a sulfonic acid group, mainly using ethylene glycol, and other propylene glycol, butanediol diol, neopentyl glycol, diethylene glycol, cyclohexane Methanol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

(Polyester-based graft copolymer)

The polyester resin used in the easy-adhesion layer is also suitable as a polyester-based graft copolymer. The polyester-based graft copolymer can form a highly self-crosslinking structure, and thus can exhibit a good effect in terms of heat and humidity resistance. The polyester-based graft copolymer is a polymerizable unsaturated monomer which is grafted on the hydrophobic copolymerized polyester resin to contain at least one acid anhydride having a double bond, from the viewpoint of moisture-heat resistance of the easily-adhesive layer. It is better. The following description is directed to a suitable polyester-based graft copolymer.

"Grafting" means introducing a graft polymer into a main polymer backbone, the graft polymer comprising a polymer different from the main chain. In the present invention, a polymerizable unsaturated single sheet containing at least one acid anhydride having a double bond is used in a state where the hydrophobic copolymerizable polyester resin is dissolved in an organic solvent by using a radical initiator. The bulk reaction is preferably carried out by graft polymerization. The reaction product after completion of the grafting reaction contains a graft copolymer of a desired hydrophobic copolymerizable polyester and a polymerizable unsaturated monomer, and also contains a non-grafted hydrophobic copolymerization. A polyester resin, and a polymer of the above unsaturated monomer which is not grafted to the hydrophobic copolymerizable polyester. The polyester-based graft copolymer used in the present invention is not limited to the above-mentioned polyester-based graft copolymer, but also includes a hydrophobic copolymerizable polyester which is not reacted therewith, and a non-grafted unsaturated monomer. A reaction mixture of a polymer or the like.

The acid-based graft copolymer obtained by graft-polymerizing a polymerizable unsaturated monomer onto a hydrophobic copolymerizable polyester resin preferably has an acid value of 600 eq/10 ⁶ g or more. It is preferably 1200 eq/10 ⁶ g or more. When the acid value of the graft copolymer is 600 eq/10 ⁶ g or more, the adhesion to the base film is good.

Further, in order to obtain a graft copolymer, the mass ratio of the hydrophobic copolymerizable polyester resin to the polymerizable unsaturated monomer is desirably in the range of polyester/polymerizable unsaturated monomer = 40/60 to 95/5, I hope that in the 55/45~93/7, I hope that I will be in the range of 60/40~90/10. When the mass ratio of the hydrophobic copolymerizable polyester resin is less than 40% by mass, the glass transition point (Tig) of the obtained easily-adhesive layer is increased, the conformability during molding is lowered, and the heat-resistant environment is resistant. The situation of subsequent decline. On the other hand, when the mass ratio of the hydrophobic copolymerizable polyester resin is more than 95% by mass, the blocking phenomenon tends to occur.

The graft copolymer is in the form of a solution or dispersion of an organic solvent or a solution or dispersion of an aqueous solvent. From the viewpoint of the working environment and the coating property, it is particularly preferable that the dispersion of the aqueous solvent, that is, the form of the water-dispersible resin. Such a water-dispersible resin can be obtained by graft-polymerizing at least one hydrophilic polymerizable unsaturated monomer to the above-mentioned hydrophobic copolymerizable polyester resin in an organic solvent, followed by hydrogenation, and organic solvent. It is obtained by distillation.

The glass transition point (Tig) of the graft copolymer is preferably 70 ° C or lower, preferably 50 ° C or lower. When the glass transition point (Tig) is 70° C. or less, the followability at the time of molding processing after the decoration is good, and excellent adhesion is easily obtained even in a moist heat-resistant environment.

(hydrophobic copolymerized polyester resin)

In the present invention, the hydrophobic copolymerizable polyester resin means a substance which is not inherently dispersed or dissolved in water and which is substantially water-insoluble. When a polyester resin which can be dispersed or dissolved in water is used for graft polymerization, there is a case where the adhesion in a hot and humid environment is deteriorated. The composition of the dicarboxylic acid component of the hydrophobic copolymerized polyester resin is 60 to 99.5 mol% of the aromatic dicarboxylic acid, 0 to 40 mol of the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid. %, preferably 0.5 to 10 mol% of the dicarboxylic acid containing a polymerizable unsaturated double bond. When the aromatic dicarboxylic acid is less than 60 mol% or when the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid exceeds 40 mol%, the adhesion may be lowered.

Further, when the dicarboxylic acid containing a polymerizable unsaturated double bond is less than 0.5 mol%, the grafting of the hydrophobic copolymerizable polyester resin to the hydrophobic copolymerizable polyester resin is not easily performed efficiently, and conversely In the case of more than 10 mol%, the viscosity of the grafting reaction increases, which hinders the uniform progress of the reaction, which is not preferable. Preferably, the aromatic dicarboxylic acid is 70 to 98 mol%, the aliphatic dicarboxylic acid and/or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid having a polymerizable unsaturated double bond is used. The acid is 2 to 7 mol%.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, and biphenyl dicarboxylic acid. The hydrophilic group-containing dicarboxylic acid such as 5-sodium sulfonate isophthalic acid lowers the anti-blocking property of the object of the present invention, and therefore it is preferably not used. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedione acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexane. A carboxylic acid, 1-3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, an acid anhydride, etc. As an example of the dicarboxylic acid containing a polymerizable unsaturated double bond, the α,β-unsaturated dicarboxylic acid may, for example, be fumaric acid, maleic acid, maleic anhydride, itaconic acid or citraconic acid; Examples of the alicyclic dicarboxylic acid having a saturated double bond include 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like. From the viewpoint of polymerizability, fumaric acid, maleic acid, and 2,5-northene dicarboxylic acid are preferred.

On the other hand, the diol component may, for example, be an aliphatic diol having 2 to 10 carbon atoms and/or an alicyclic diol having 6 to 12 carbon atoms and/or a glycol having an ether bond. Examples of the aliphatic diol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and neopentyl glycol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and the like. Examples of the alicyclic diol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol.

The glycol containing an ether bond may, for example, be diethylene glycol, triethylene glycol, dipropylene glycol, or even a binary obtained by adding two phenolic hydroxyl groups of bisphenol to ethylene oxide or propylene oxide. Alcohols such as 2,2-bis(4-hydroxyethoxyphenyl)propane and the like. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may also be used as necessary.

0 to 5 mol% of a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol may be copolymerized in the hydrophobic copolymerizable polyester resin, and (anhydrous) trimellitic acid may be used as the trifunctional or higher polycarboxylic acid. , (anhydrous) pyrophoric acid, (anhydrous) diphenyl ketone tetracarboxylic acid, trimesic acid, ethylene glycol bis(hydrogen trimellitate), glycerin (hydrogenated trimellitate) and the like. On the other hand, as the trifunctional or higher polyhydric alcohol, glycerin, trimethylolethane, trimethylolpropane, neopentylol or the like can be used. The polyvalent carboxylic acid and/or the polyhydric alcohol having a trifunctional or higher functional group is copolymerized in a range of 0 to 5 mol% with respect to all the acid components or all of the diol components, and is desirably in the range of 0 to 3 mol%. On the other hand, if it exceeds 5 mol%, gelation tends to occur during polymerization, which is not preferable. Further, the molecular weight of the hydrophobic copolymerizable polyester resin is preferably from 5,000 to 50,000 in terms of weight average. When the molecular weight is less than 5,000, the adhesion of the printed layer may be lowered. Conversely, if it exceeds 50,000, there is a problem that colloidalization occurs during polymerization.

(Grafting site of polyester-based graft copolymer)

The polymerizable unsaturated monomer which can be grafted on the hydrophobic copolymerizable polyester resin means a hydrophilic radical polymerizable monomer, and has a hydrophilic group or a group which can later become a hydrophilic group, and is free Base polymerized monomer. Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, a decylamino group, a 4- toluyl base, and the like. On the other hand, examples of the group which can be changed into a hydrophilic group include an acid anhydride group, a glycidyl group, a chlorine group and the like. From the viewpoint of water dispersibility and an increase in the acid value of the graft copolymer, a carboxyl group is preferred among the groups. Therefore, the polymerizable unsaturated monomer desirably contains at least one acid anhydride having a double bond.

a monoester or diester of fumaric acid of a polymerizable unsaturated monomer such as fumaric acid, monoethyl fumarate, diethyl fumarate or dibutyl fumarate; maleic acid and its anhydrate, Monoester or diester of maleic acid such as monoethyl maleate, diethyl maleate or dibutyl maleate; itaconic acid and its anhydride, monoester or diester of itaconic acid; benzene Maleic imine or the like of carbamazepine, etc.; styrene derivative of styrene, α-methylstyrene, t-butylstyrene, chloromethylstyrene, etc.; vinyl toluene, divinyl Base benzene and the like. Further, examples of the acrylic polymerizable monomer which is one of the polymerizable unsaturated monomers include alkyl acrylate and alkyl methacrylate (alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, phenyl, benzyl, phenethyl, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy acrylate A hydroxy-containing acrylic monomer of propyl ester or 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methyl acrylamide, N-hydroxyl Methyl acrylamide, N-methylol methacrylamide, N,N-dimethylol decylamine, N-methoxymethyl propylene decylamine, N-methoxymethyl methacryl Amidoxime-containing acrylic monomer of decylamine, N-phenylacrylamide; amine N,N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate Acrylic monomer; glycidyl acrylate, glycidyl methacrylate epoxy group-containing acrylic monomer; acrylic acid, methacrylic acid and the salts (sodium, potassium, ammonium) An acrylic monomer containing a carboxyl group or a salt thereof. The polymerizable unsaturated monomer may be used alone or in combination of two or more kinds, and it is desirable to contain at least one acid anhydride having a double bond. Among the above monomers, an acid anhydride having a double bond is preferably used. Other polymerizable unsaturated monomers combined with maleic anhydride are preferred. It may also contain esters of such anhydrides.

(polymerization initiator and other additives)

As the graft polymerization initiator which can be used in the present invention, organic peroxides or organic azo compounds which are well known in the art can be used. Examples of the organic peroxide include benzammonium peroxide, tert-butyl peroxypivalate, and organic azo compounds, and 2,2'-azobisisobutyronitrile and 2,2'-azo double are exemplified. (2,4-Dimethylvaleronitrile) and the like. The amount of the polymerization initiator used for the graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more based on the polymerizable unsaturated monomer. In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the graft polymer such as octyl mercaptan, hydrazine ethanol, 3-tert-butyl-4-hydroxyanisole or the like may be used as necessary. In this case, it is desirable to add in the range of 0 to 5% by mass based on the polymerizable unsaturated monomer.

In other aspects, the copolymerization component of the copolymerized polyester may further contain a dicarboxylic acid component or a glycol component containing a small amount of a guanamine bond, an urethane bond, an ether bond, a carbonate bond or the like. Further, in order to increase the surface hardness of the obtained coating film, it is also possible to use trimellitic acid, trimesic acid, pyromic acid, trimellitic anhydride, pyromellite in a ratio of 5 mol% or less. A monomer containing a plurality of carboxyl groups such as an acid anhydride is used as a copolymerization component of the above polyester. When the monomer having a plurality of carboxyl groups exceeds 5 mol%, the obtained graft copolymer is thermally unstable and easily colloidal, which is not preferable.

(polyurethane)

In the present invention, polyurethane is added in order to impart flexibility and excellent formability to the easy-adhesion layer. The polyurethane resin can be roughly classified into a polyester-based polyurethane resin, a polyether-based polyurethane resin, and a polycarbonate-based polyurethane resin. From the viewpoint of adhesion, any of them can be applied, and from the viewpoint of blocking resistance or heat and humidity resistance, it is preferred to use a polycarbonate-based polyurethane. Since the polyester-based polyurethane resin is easily hydrolyzed in a hot and humid environment, and the polyether-based polyurethane resin has high hygroscopicity, the film strength of the easily-adhesive layer is likely to be lowered, and the adhesion is insufficient. On the other hand, since the polycarbonate urethane resin has a polycarbonate structure as a hard segment, it has excellent heat and humidity resistance and is suitable.

As the polycarbonate-based polyurethane resin, a polycarbonate diol, an aliphatic and/or alicyclic diisocyanate, and a polymer which adds a chain extender as necessary may be used. Further, the constituent components of the urethanes can be determined by nuclear magnetic resonance analysis or the like.

The polycarbonate diol is represented by the following general formula.

HO-[-RO-COO-] _n -R-OH

(R is an aliphatic or alicyclic substituent)

The polycarbonate diol is, for example, one or more compounds selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate, and diols and/or polyether polyols. The class reaction is obtained.

Examples of the alkylene carbonate include ethyl carbonate, 1,2-propyl propyl carbonate, 1,2-butyl butyl carbonate, and the like.

Examples of the diaryl carbonate include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, and 4 -propyl diphenyl carbonate, 4,4'-dimethyldiphenyl carbonate, 4,4'-diethyldiphenyl carbonate, 4,4,-dipropyldiphenyl carbonate Wait.

Examples of the dialkyl carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, and Third butyl carbonate, di-n-pentyl carbonate, diisoamyl carbonate, and the like.

Examples of the carbonate-based co-reacting materials include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-butylene. Glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-methylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexyl Glycol, 2,3,5-trimethylpentanediol, and the like.

Further, examples of the polyether polyols include, for example, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and alkylene oxide adducts of glycols. Examples of the diol used herein include, for example, ethylene glycol, 1,2-propylene glycol, 1-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, and isomer pentanediol. Classes, isomers of hexanediols or octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis(hydroxymethyl)-cyclohexanone, 1,3-double ( Hydroxymethyl)-cyclohexanone, 1,4-bis(hydroxymethyl)-cyclohexanone, trimethylolpropane, glycerin, etc., examples of the alkylene oxides include ethylene oxide, propylene oxide, and 1 Further, 2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, benzene oxide, or epichlorohydrin may be used in combination of two or more kinds.

The above-mentioned diols and polyether polyols may be used singly or in combination of two or more kinds thereof. Any of these may be reacted by a known method with one or more compounds selected from the group consisting of alkyl carbonate, diaryl carbonate, and dialkyl carbonate described above to form a poly Carbonate diol.

In the present invention, the composition molar ratio of the polycarbonate polyol which is a constituent component of the urethane ethyl ester is 3 to 100 m in the case where the polyisocyanate component of all the urethane groups is 100 mol%. % is better, 5 to 50 mol% is better, and 6 to 20 mol% is better. If the compositional molar ratio is low, there is a case where the moist heat resistance improvement effect cannot be obtained. Further, in the case where the composition Moh ratio is high, the adhesion may be lowered.

The polyisocyanate which is a constituent component of the urethane ethyl ester of the present invention may, for example, be an isomer of toluene diisocyanate, an aromatic diisocyanate such as 4,4-diphenylmethane diisocyanate or aroma of xylene diisocyanate. Aliphatic diisocyanates, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, etc., alicyclic diisocyanate, Liu Ya An aliphatic diisocyanate such as methyl diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate or an addition of a single or a plurality of such compounds to trimethylolpropane or the like in advance Polyisocyanates.

Examples of the chain extender include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol, glycerin, and trimethylolpropane. And polyvalent alcohols such as pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine, and piperazine, amine alcohols such as monoethanolamine and diethanolamine, and thiodiethylene glycol. Sulphur diethylene glycol, or water.

The easy-adhesion layer of the present invention is preferably provided by a wire coating method which will be described later by using an aqueous coating liquid. Therefore, the urethane resin of the present invention is desirably water-soluble. Further, the above "water-soluble" means that it is dissolved in water or an aqueous solution containing less than 50% by mass of the 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 may be introduced into the urethane molecular skeleton (copolymerization). The sulfonic acid (salt) group is strongly acidic, and it is difficult to maintain moisture resistance due to its hygroscopic property. Therefore, it is suitable to introduce a weakly acidic carboxylic acid (salt) group.

In order to introduce a carboxylic acid (salt) group into the urethane resin, a polyol compound having a carboxyl group such as dimethylolpropionic acid or dimethylolbutyric acid as a polyol component is introduced as a copolymerization component, and Neutralized by a salt forming agent. Specific examples of the salt forming agent include trialkylamines such as ammonia, trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, and tri-n-butylamine, N-methylmorpholine, and N-ethyl. An N-dialkylalkanolamine such as an N-alkylmorpholine such as a phenyl group, N-dimethylethanolamine or N-diethylethanolamine. These may be used alone or in combination of two or more.

In the case where a polyol compound having a carboxylic acid (salt) group is used as a copolymerization component in order to impart water solubility, when all the polyisocyanate components of the urethane resin are set to 100 mol%, ethyl urethane is used. The composition of the polyol compound having a carboxylic acid (salt) group in the resin is preferably from 3 to 60 mol%, more preferably from 10 to 40 mol%. When the aforementioned composition molar ratio is less than 3 mol%, water dispersibility may be difficult.

In the present invention, it is preferred to control the glass transition point (Tig) of the polyurethane resin to a specific range. That is, the lower limit of the glass transition point (Tig) of the polyurethane of the present invention is 40 ° C, preferably 50 ° C, and the upper limit is 100 ° C, preferably 90 ° C. When the glass transition point (Tig) of the polyurethane resin is less than 40 ° C, the blocking resistance may be lowered. On the other hand, when it exceeds 100 ° C, the flexibility and adhesion of the adhesive layer may be lowered. In order to control the glass transition point (Tig) of the polyurethane to the above range, it can be carried out by appropriately selecting and adjusting the molecular weight of the following polyol component or polyurethane.

In the present invention, in order to more reliably balance the flexibility and adhesion of the easy-to-adhere layer, the blending ratio of the aforementioned copolymerized polyester to the aforementioned polyurethane is used to copolymerize the polyester/polyurethane ( Mass ratio) = 80/20~30/70 is preferred. The aforementioned blending ratio is preferably 75/25 to 40/60.

When the copolymerized polyester/polyurethane (mass ratio) = 100/0 to 90/10, the flexibility of the easy-to-layer layer is lowered, and at 20/80 to 0/100, there is resistance to blocking and The situation of subsequent decline.

The main component of the easy-adhesion layer of the present invention is a polyester which exhibits appropriate adhesion to a base film containing polyester, and a polyurethane having high compatibility with a decorative layer, and thus exhibits excellent properties. Initial adhesion. Further, in order to improve the heat and humidity resistance, a polyester-based graft copolymer having a high degree of self-crosslinkability is preferably used as the polyester, and a polycarbonate-based polyurethane which is not easily hydrolyzed is preferably used as the polyurethane. The combination of the polyester-based graft copolymer and the polycarbonate-based polyurethane is particularly suitable for imparting moist heat resistance, and the present inventors have considered the following. That is, the polyester-based graft copolymer of the present invention has a side chain having an acid anhydride as a constituent component. In another aspect, the polyurethane of the present invention has a carbonate group. It is considered that these side chains and the carbonate group exhibit a hydrogen bond-like interaction, and the durability as an easy-adhesion layer can be exhibited more highly.

The lower limit of the glass transition point (Tig) of the easy-adhesion layer of the present invention is 30 ° C, preferably 35 ° C, and the upper limit is 55 ° C, preferably 50 ° C. When the glass transition point (Tig) of the easy-adhesion layer is less than 35 ° C, there is a case where sufficient heat and humidity resistance cannot be obtained, and even a case where the blocking resistance is lowered. If the glass transition point (Tig) of the easy-adhesion layer exceeds 55 ° C, the flexibility of the easily-adhesive layer may be lowered. In order to smoothly achieve both moist heat resistance and moldability, it is preferable to set the glass transition point (Tig) of the easy-adhesion layer to such a range. Even if the glass transition point (Tig) of the polyester component and the polyurethane component is within the above range, in the case where an easy-adhesion layer having a crosslinked structure is laminated in the film forming step together with the crosslinking agent, There will be a case where the glass transfer point (Tig) exceeds 38 °C. In addition, in order to maintain the glass transition point (Tig) when having a crosslinked structure, an appropriate crosslinking agent blending amount, a blending amount of polyurethane and a polyester-based graft copolymer blending amount, and The mass ratio of the hydrophobic copolymerizable polyester resin to the polymerizable unsaturated monomer is preferably in the above range. Further, the above-mentioned glass transfer point means a polyester-based graft copolymer and a polycarbonate-based polyamine in a state in which it is laminated as an easy-to-attach layer in the film forming step. The extrapolation glass transition start temperature (Tig) measured in accordance with the method of JIS-K7121 in the state in which the acid ester is crosslinked.

(particle)

The easy-adhesion layer of the present invention is characterized in that it contains at least particles having a particle size distribution (d75/d25) of 1.1 to 1.5 and an average particle diameter of 0.04 to 1.2 μm.

If the surface of the film is smooth, when the film is wound into a roll shape, the air that is caught between the films cannot be completely removed, and the film is likely to cause wrinkles due to the entrapped air portion. In the case where a film having such a disadvantage is used as a plating instead, it may become an appearance defect and a suitable mirror appearance cannot be obtained. Such a defect in appearance, such as a film having a film thickness of 100 μm or less and even a film thickness of 80 μm or less, is likely to occur easily. Thus, the easy-adhesion layer of the present invention contains particles having an average particle diameter of 0.04 to 1.2 μm. The average particle diameter of the particles is preferably from 0.05 to 1.0 μm, more preferably from 0.06 to 0.90 μm. When the lower limit of the average particle diameter is at least the above, an effective protrusion is formed on the surface of the easy-adhesion layer to improve the air escape property, and a film having no defect in appearance can be obtained smoothly. Further, when the average particle diameter of the particles is at most the above upper limit, a smooth surface texture of the film surface can be obtained.

The average particle diameter of the particles can be measured by an image observed by a scanning microscope on the surface of the film easily adhered to the surface of the film, or an image observed by an electron microscope of the film which is easily laminated, or by a Kod counter method. Among them, the particle diameter of the particles which are exposed on the surface of the easy-adhesion layer can be measured by an image observed by a scanning microscope on the surface of the film-adhesive layer, and the particle average particle diameter can be suitably determined. Further, the reflection intensity (Wa) of the surface of the film to be described later can be controlled to a specific range by using the above particles.

In the case where the thickness of the easy-adhesion layer is set to t (μm) and the average particle diameter of the particles is set to d (μm), the ratio (d/t) is from 1 to 100, preferably from 2 to 50. More preferably 5~20. When (d/t) is at least the above lower limit, surface protrusions which contribute to air removal are easily formed on the surface of the easy-adhesion layer. Further, when (d/t) is equal to or less than the above upper limit, the particles are less likely to be detached (the particles are detached from the easily-adhesive layer), and a stable friction coefficient can be easily obtained at the time of processing.

From the above relationship, the thickness of the easily-adhesive layer of the present invention is preferably 0.02 to 0.50 μm, more preferably 0.03 to 0.10 μm, still more preferably 0.04 to 0.08 μm.

Since the easy-adhesion layer of the present invention has the above configuration, it has good air-removability.

Specifically, the air removal index measured by the method described later is preferably 350 seconds or less, preferably less than 200 seconds, more preferably less than 50 seconds. Since the air removal index of the film of the present invention is not more than the above upper limit, even if the film of the present invention is wound around a roll in the film forming step, the air can be well removed and stored in the form of a film. In the case, it is not easy to produce wrinkles. On the other hand, the lower limit of the air removal index is preferably 30 seconds or more, and more preferably 35 seconds or more. When the air removal index is at least the above lower limit, the powder falling of the particle protrusions can be more smoothly suppressed.

The film of the present invention desirably exhibits good appearance when the vapor deposition and the decorative surface are the back surface. Therefore, the content of the particles in the easy-adhesion layer is preferably 0.01 to 3% by mass, more preferably 0.05 to 2.5% by mass, still more preferably 0.10 to 2.0% by mass. When the particle content is at least the above lower limit, the air repellent property can be favorably maintained when wound into a film. In addition, when the particle content is equal to or less than the above upper limit, it is possible to more smoothly suppress powder falling of the particle protrusions, and it is also possible to easily obtain appropriate transparency.

Since the particle concentration in the easy-adhesion layer is in the above range, the film of the present invention has high transparency. Specifically, the film of the present invention preferably has a haze of 2.0% or less, preferably 1.5% or less, more preferably 1.2% or less, particularly preferably 1.0% or less, and most preferably 0.8% or less. Since the film of the present invention has excellent transparency as described above, even if a vapor deposition layer is provided on the back surface of the film and molded integrally with the substrate (insert molding), a mirror-like good surface appearance can be obtained. Further, in order to make the transparency of the film within the above range, it is preferable to set the film to contain only particles in the easy-adhesion layer, and it is preferable that the polyester film as the substrate contains substantially no particles. Further, "substantially free of particles in the base film" means that, for example, in the case of inorganic particles, when the amount of the inorganic element is quantified by fluorescent X-ray analysis, the content is below the detection limit. This is because even if particles are not intentionally added to the base film, contamination components such as foreign matter may be mixed.

When a vapor-deposited layer having a metallic luster is provided on the surface of the film to achieve a very high degree of mirror surface, even if the fine surface unevenness shape which cannot be visually recognized in the film state is caused, the scattering caused by the reflected light causes the image reflected on the mirror surface. Skew occurs, and the appearance defects can be visually discerned. Although the image skew is not observed when the film is mirror-finished at the time of film formation, it is clearly observed when a film wound into a roll shape is used. As a result of the intensive review of the occurrence mechanism of such image skew, it was found that the main cause is the unevenness of the particle shape of the particles added to impart air-removing property. That is, in the case where the particle shape is not uniform, the fine unevenness on the surface of the film is locally unevenly distributed, and it is known that in the case of forming a film into a film and synthesizing the film layer into a plurality of layers, the distribution of the uneven shape is not Both of them aggregate to produce a fine film surface uneven structure called orange peel. The fine concavo-convex structure on the surface of the film formed as described above has a structure which is finer than the concavo-convex structure which exhibits a felt shape or the like, and which is larger than the surface protrusion structure represented by three-dimensional surface roughness (SRa) or the like. In other words, it is a fine surface uneven shape which can be visually discriminated when the mirror surface treatment is not visually recognized from the film itself. The uneven distribution of the uneven shape of the particles is considered to be likely to occur when the film elasticity is reduced as in the case of a film having a film thickness of 100 μm or less and even 80 μm or less.

In order to solve the above problems, a good specular appearance is exhibited, and it is important to set the particle size distribution (d75/d25) of the particles contained in the easy-adhesion layer of the present invention to 1.1 to 1.5. The particle size distribution (d75/d25) of the particles is preferably 1.4 or less, more preferably 1.3 or less. When the particle size distribution of the particles is not more than the above upper limit, uneven distribution of unevenness on the surface of the film is small, and even if a thin film is wound into a roll, the orange peel phenomenon is less likely to occur. Further, the particle size distribution of the particles is preferably about 1, and from the viewpoint of industrial productivity, 1.1 is the lower limit. The means for controlling the particle size distribution of the particles in the above range is not particularly limited, and may be, for example, filtration by a filter or the like, or removal of coarse particles by a particle falling speed, a blowing device, an electrostatic device, or the like, and selecting particles which are less likely to cause particle agglomeration. The type uses organic particles that are easy to obtain a narrow particle size distribution. The organic particles can appropriately control the particle size distribution by adjusting the concentration of the surfactant added at the time of preparation. In particular, the crosslinked organic particles obtained by emulsion polymerization can be easily obtained by obtaining a narrow particle size distribution. The particle size distribution can be measured by an image observed by a scanning microscope on the surface of the film, or by an electron microscope observed by an electron microscopy of the film, or by a Coulter Counter method. . Among them, the particle size of the particles on the surface of the easy-adhesion layer was measured by an image observed by a scanning microscope on the surface of the film-adhesive layer, and the particle size distribution can be suitably determined.

Since the easy-adhesion layer of the present invention has the above-described configuration, even when a thin film is wound into a roll shape, the orange peel phenomenon is less likely to occur, and a clear image can be obtained by the mirror surface treatment. Image skew is caused by the uneven structure of the shiny surface of the metal, which causes the reflection of light to be different, and can be visually observed by humans. The film surface unevenness structure which is the main cause of image skew can be evaluated by microwave scanning (manufactured by Gardner Co., Ltd.) for optical measurement of a light-dark pattern of wavelength. The flatness tester irradiates the laser light with a laser point source at an oblique angle of 60° with respect to a perpendicular to the surface of the film, and detects the reflected light at the same angle on the opposite side with respect to the perpendicular line by a detector. The device can detect the optical contour of the surface of the film by moving and scanning the laser point source on the surface of the film to measure the brightness of the reflected light at a predetermined interval.

The detected optical profile is spectrally resolved by a frequency filter, and the structure of the surface can be resolved. The characteristic spectrum of this device is as follows. Du: wavelength 0.1mm or less, Wa: wavelength 0.1~0.3mm, Wb: wavelength 0.3~1mm, Wc: wavelength 1~3mm, Wd: wavelength 3~10mm, We: wavelength 10~30mm, SW: wavelength 0.3~1.2mm LW: The wavelength is 1.2~12mm. Among these, it is known that the reflection intensity (Wa) in the region of the wavelength of 0.1 to 0.3 mm can be utilized as the contour generated by the fine surface uneven structure of the present invention.

When the surface of the film of the present invention is measured by a flatness tester, the reflection intensity (Wa) in the region of 0.1 to 0.3 mm is preferably 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less. When the reflection intensity is not more than the above upper limit, the surface of the film is smooth, and when used as a plating instead, it exhibits a good mirror appearance.

The aforementioned particles contained in the easy-adhesion layer in the present invention may, for example, be titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, cerium oxide, aluminum oxide, talc, kaolin, clay, or the like, or a mixture thereof, or even Other inorganic particles, such as inorganic particles such as calcium phosphate, mica, hectorite, zirconium, tungsten oxide, lithium fluoride, calcium fluoride, or the like; or styrene, acrylic, melamine, benzoguanamine, An organic polymer-based particle such as a polysiloxane or the like. Among them, organic polymer-based particles such as styrene-based or acrylic-based particles which can easily obtain particles having a narrow particle size distribution are preferred.

In the present invention, at least one type of particles is preferred to satisfy the above requirements. Further, in addition to the above particles, it is also one of suitable forms to combine a plurality of kinds of inorganic particles having different average particle diameters for the purpose of blocking resistance or scratch resistance. The other particles used at this time are desirably smaller than the aforementioned particles, and even more desirably smaller than the thickness of the easily-adhesive layer. By adding such smaller other particles, the hardness of the surface of the easily-adhesive layer can be imparted, and the blocking resistance can be improved.

The average particle diameter of the particles having a small average particle diameter (hereinafter referred to as particles B, and the particles being referred to as particles A and distinguishing the two) is preferably 20 to 150 nm. 30 to 100 nm is preferred, and 40 to 80 nm is more preferred. When the average particle diameter of the particles B is set to dB and the thickness of the easy-to-layer layer is set to t, the ratio (dB/t) is preferably 1.5 to 0.1, and preferably 1.2 to 0.3. By using the particles smaller than the particle A and further equal to the thickness of the easily-adhesive layer as the particles B, the anti-blocking property can be improved without impairing the texture of the film surface. When the particles B are added, the solid content concentration in the easily-adhesive layer is preferably 30% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less. By setting the addition concentration of the particles B to the above upper limit or less, the transparency of the film can be maintained. Further, as for the particle A, the average particle diameter of the particles B can be obtained by measuring the particle diameter of the particles which are exposed on the surface of the easy-adhesion layer by an image observed by a scanning microscope on the surface of the film.

Further, since the easy-adhesion layer of the present invention has the above-described constitution, it has excellent blocking resistance. Specifically, the static friction coefficient of the easy-adhesion layer measured by the method described later is preferably 0.9 or less, more preferably 0.8 or less, still more preferably 0.7 or less. Further, the dynamic friction coefficient is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.6 or less. Since the static friction coefficient and/or the dynamic friction coefficient are not more than the above upper limit, the film of the present invention has appropriate workability in various molding processes.

(crosslinking agent)

From the viewpoint of anti-blocking, it is preferred to contain a crosslinking agent in the easy-adhesion layer of the present invention. Thereby, an appropriate crosslinked structure can be formed in the easy-adhesion layer, and therefore the addition of the crosslinking agent is suitable for imparting heat and humidity resistance. The blending ratio of the crosslinking agent is preferably 5 to 40 parts by mass, more preferably 8 to 25 parts by mass, per 100 parts by mass of the total of the polyester resin and the polyurethane resin. When the blending ratio of the crosslinking agent is less than 5 parts by mass based on 100 parts by mass of the total of the polyester resin and the polyurethane resin, the blocking resistance is lowered and the adhesion is lowered. Therefore, it is not good. On the other hand, when it exceeds 40 mass parts, the softness required for the moldability may fall.

The above crosslinking agent may be a phenol formaldehyde resin which is a condensate of formaldehyde, such as an alkylated phenol or a cresol; and an adduct of formaldehyde, such as urea, melamine, benzoguanamine, etc., containing this adduct and a carbon atom. An amine-based resin such as an alkyl ether compound of 1 to 6; a polyfunctional epoxy compound; a polyfunctional isocyanate compound; a blocked isocyanate compound; a polyfunctional aziridine compound; An oxazoline compound or the like.

Examples of the phenol formaldehyde resin include phenol which is alkylated (methyl, ethyl, propyl, isopropyl or butyl), p-third amyl phenol, 4,4'-second butylene phenol, and the like. Tributyl phenol; o-, m-, p-cresol; p-cyclohexyl phenol, 4,4'-isopropylidene phenol, p-nonyl phenol, p-octyl phenol, 3-pentadecyl phenol, phenol, benzene A condensate of a phenol such as o-cresol, p-phenylphenol or xylenol with formaldehyde.

The amine-based resin may, for example, be methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methoxylated methylol dicyanamide, methoxylated methylol melamine , methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated hydroxymethyl benzoguanamine, and the like, and methoxymethylol melamine, butyl Oxylated methylol melamine, and methylolated benzoguanamine.

Examples of the polyfunctional epoxy compound include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A, oligomers thereof, diglycidyl phthalate, and isophthalic acid. Diglycidyl dicarboxylate, diglycidyl terephthalate, diglycidyl hydroxybenzoate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, Diglycidyl succinate, diglycidyl adipate, diglycidyl sebacate, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl Ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ether, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-two Glycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol alkylene oxide adduct triglycidyl ether Wait.

As the polyfunctional isocyanate compound, a low molecular or high molecular aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. The polyisocyanate has tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, isophorone II. The isocyanate and the three isomers of the isocyanate compounds. Further, a low molecular weight active hydrogen compound such as an excessive amount of the isocyanate compound and ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine or triethanolamine, or A compound having an isocyanate group at the terminal obtained by the reaction of a polymer active hydrogen compound such as a polyester polyol, a polyether polyol or a polydecylamine.

Among the crosslinking agents, the crosslinking agent used in the present invention is preferably a blocked isocyanate crosslinking agent. By adding a blocked isocyanate-based crosslinking agent, it is possible to reliably achieve both adhesion and blocking resistance.

The blocked isocyanate crosslinking agent can be prepared by subjecting the above isocyanate compound to a blocking agent by an appropriate method known in the art. Examples of the isocyanate blocking agent include phenols such as phenol, cresol, xylenol, resorcin, nitrophenol, and chlorophenol; sulfur phenols such as thiophenol and methylthiophenol; acetone oxime and methyl ethyl ketone; Anthraquinones such as ketone oxime and cyclohexanone oxime; alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as chlorohydrin and 1,3-dichloro-2-propanol; Tertiary alcohols such as butanol and third pentanol; indoleamines such as ε-caprolactam, δ-valeroguanamine, γ-butyrolactam, and β-propionamide; aromatic Amines; quinone imines; active methylene compounds such as acetamidineacetone, acetamidine acetate, ethyl malonate; thiols; imines; ureas; diaryl compounds; sodium bisulfite .

In the coating liquid of the present invention, well-known additives such as an antioxidant, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, an organic slip agent, a pigment, a dye, and the like may be added within a range not inhibiting the effects of the present invention. Organic or inorganic particles, antistatic agents, nucleating agents, and the like.

(substrate polyester film)

The polyester film as a substrate mainly contains a polyester resin. The polyester resin constituting the base film is suitably polyethylene terephthalate, polyethylene 2,6 naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, or The constituent components of these resins are copolymers of main components. From the viewpoint of moldability, in particular, a copolymerized polyester or a polyester film comprising a copolymerized polyester and a homopolyester is preferred.

In the case where the plating instead of the film is integrally molded (insert molding) with the molded substrate, it is preferable that the film has a thin film thickness. The thickness of the film of the present invention is preferably 15 to 100 μm, more preferably 80 μm or less, still more preferably 75 μm or less, particularly preferably 60 μm or less, and most preferably 50 μm or less. Further, from the viewpoint of the strength of the film, the lower limit of the film thickness is 15 μm or more, more preferably 20 μm or more, and still more preferably 25 μm or more. Since the easy-adhesion layer of the present invention has the above-described form, even a thin film exhibits an appearance suitable for use as a plating instead.

The measure of the formability of the film is evaluated as stress (F100) at 100% elongation. The reason why F100 is closely related to the moldability of the film is that, for example, in the case of insert molding, the film may locally extend to 100% or more in the vicinity of the corner of the mold. Among the F100 high films, such locally elongated portions partially generate extremely high stress, and it is considered that the film is broken due to the concentration of the stress, and the formability is lowered. On the other hand, in the film in which F100 is too small, although the moldability is good, only a portion which is uniformly elongated in a metal mold such as a flat portion can generate extremely weak tension, and it is considered that the film in this portion may not be uniformly elongated.

In the present invention, the physical properties relating to the moldability corresponding to the temperature at the time of insert molding are stresses (F100 ₁₀₀ ) at 100% elongation at 100 °C. Further, when the insert molding is performed using a metal mold having irregularities or low ridges, the physical properties relating to the moldability for insert molding the film before molding in advance along the molds are 100% elongation at 25 ° C. Stress (F100 ₂₅ ).

Regarding the above physical properties, the film of the present invention is particularly preferably used in the case of insert molding, and the stress (F100 ₂₅ ) at 100% stretching at 25 ° C is preferably 40 to 300 MPa. The lower limit is preferably 50 MPa, more preferably 60 MPa, still more preferably 70 MPa. Further, the upper limit is preferably 250 MPa, more preferably 200 MPa, still more preferably 150 MPa. When the F100 _{25 is} less than 40 MPa, when the roll-shaped film is stretched and starts to be entangled, the film may be stretched or broken, and workability may be deteriorated. On the other hand, when F100 ₂₅ exceeds 300 MPa, moldability may deteriorate. In particular, when molding is performed using a metal mold having irregularities or low entanglements, the film before molding may be molded slightly along the molds in advance. In such a case, the film may not be easily molded, and the pattern of the finished product may be deteriorated.

Further, in the case where the film of the present invention is used for insert molding, the stress (F100 ₁₀₀ ) at 100% stretching at 100 ° C is preferably 1 to 100 MPa. From the viewpoint of moldability, the upper limit of F100 ₁₀₀ is preferably 90 MPa, preferably 80 MPa, and particularly preferably 70 MPa. On the other hand, from the viewpoint of elasticity or form stability in the case of using a molded article, the lower limit of F100 ₁₀₀ is preferably 5 MPa, more preferably 10 MPa, still more preferably 20 MPa, and particularly preferably more than 35 MPa.

(copolymerized polyester)

The copolymerized polyester is suitably (a) a copolymerized polyester comprising an aromatic dicarboxylic acid component; and a glycol component containing ethylene glycol, a branched aliphatic diol or an alicyclic diol, or (b) A copolymerized polyester comprising an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol. Further, from the viewpoint of improving moldability, the polyester having a biaxially oriented polyester film preferably contains a 1,3-propanediol unit or a 1,4-butanediol unit as a glycol component. When the copolymerized polyester used in the present invention is the above (a), the copolymerization is carried out so that the proportion of ethylene glycol in all the glycol components is 20 mol% to 95 mol%. The ingredients are good. Further, the lower limit of the ratio of the ethylene glycol to all the glycol components is preferably 30 mol%, preferably 40 mol%, and the upper limit is preferably 90 mol%, preferably 80 mol%, more preferably It is 70% by mole. Further, in the case where the copolymerized polyester used in the present invention is the above (b), the ratio of terephthalic acid to all the aromatic dicarboxylic acid components is 50% by mole to 95% by mole. The way to add copolymerization is divided into good. Further, the lower limit of the ratio of terephthalic acid in all of the above aromatic dicarboxylic acid components is preferably 60 mol%, preferably 70 mol%, and the upper limit is preferably 90 mol%.

As the film raw material, any method in which a copolymerized polyester is used alone, a combination of one or more kinds of homopolyesters or copolymerized polyesters, or a combination of a homopolyester and a copolymerized polyester can be used. From the standpoint of suppressing the decrease in the melting point, it is suitable to incorporate the same.

In the case where the copolymerized polyester is a copolymerized polyester comprising an aromatic dicarboxylic acid component: and a glycol component containing ethylene glycol, a branched aliphatic diol or an alicyclic diol, the aromatic diol is used. The carboxylic acid component is suitable for terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or such ester-forming derivatives, and the amount of terephthalic acid and/or naphthalene dicarboxylic acid component relative to all dicarboxylic acid components. It is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, more preferably 100 mol%.

Further, as the branched aliphatic diol, for example, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol or the like can be exemplified. The alicyclic diol can be exemplified by 1,4-cyclohexanedimethanol, dimethylol tricyclodecane or the like.

Among these, neopentyl glycol or 1,4-cyclohexane dimethanol is particularly preferred. Further, in the present invention, in addition to the above-described glycol component, 1,3-propanediol or 1,4-butanediol is also a suitable embodiment. It is suitable to use these diols as a copolymerization component, and to provide the above-mentioned characteristics, and it is also suitable from the viewpoint of being excellent in transparency and heat resistance, and improving adhesion with an easy-adhesion layer.

Further, when a copolymerized polyester composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a glycol component containing ethylene glycol is used as the copolymerized polyester, The amount of ethylene glycol is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, and more preferably 100 mol%, based on the total diol component. The diol component other than ethylene glycol is preferably a branched aliphatic diol, an alicyclic diol, or diethylene glycol.

As the catalyst used in the production of the above-mentioned copolymerized polyester, for example, an alkaline earth metal compound, a manganese compound, a cobalt compound, an aluminum compound, a ruthenium compound, a titanium compound, a titanium/ruthenium composite oxide, a ruthenium compound or the like can be used. From the viewpoint of catalyst activity, among these, a titanium compound, a ruthenium compound, a ruthenium compound, or an aluminum compound is preferred.

In the production of the aforementioned copolymerized polyester, it is preferred to add a phosphorus compound as a thermal stabilizer. The phosphorus compound is preferably, for example, phosphoric acid, phosphorous acid or the like.

The intrinsic viscosity of the copolymerized polyester is preferably 0.50 dl/g or more, more preferably 0.55 dl/g or more, and particularly preferably 0.60 dl/g or more, from the viewpoints of moldability, adhesion, and film stability. . When the intrinsic viscosity is less than 0.50 dl/g, the moldability tends to be lowered. Further, in the case where a filter for removing foreign matter is provided in the fusion line, the upper limit of the intrinsic viscosity is preferably 1.0 dl/g from the viewpoint of extrusion stability at the time of extruding the molten resin.

(Polyester resin as a film material)

In the present invention, by using one or more kinds of homopolyesters or copolymerized polyesters as a film raw material, by blending these films to form a film, it is possible to maintain the same flexibility as in the case of using only a copolymerized polyester. At the same time, transparency and high melting point (heat resistance) can be achieved. Further, compared with the case of using only a high melting point homopolyester (for example, polyethylene terephthalate), it is possible to maintain high transparency while achieving flexibility and practically no problem in melting point (heat resistance). ).

Further, from the viewpoint of moldability, a homopolyester (for example, polytetramethylene terephthalate or polybutylene terephthalate) other than the above-mentioned copolymerized polyester and polyethylene terephthalate is blended. It is also more preferable to use at least one of the diesters as a raw material of the polyester resin film of the present invention.

In the present invention, a polyester resin or a polyester resin in which one or more kinds of homopolyesters or copolymerized polyesters are blended alone is used as a film raw material. The polyester resin used in the present invention preferably contains 5 to 50% by mass of the copolymerization component.

The polyester resin preferably has a melting point of 180 to 250 ° C from the viewpoint of heat resistance and moldability. Further, by controlling the film formation conditions within the above-mentioned melting point range by the type or composition of the polymer to be used, the moldability and the completeness are balanced, and a high-quality molded article can be economically produced. Here, the melting point refers to the endothermic peak temperature at the time of melting detected by the so-called differential scanning calorimetry (DSC). This melting point was determined by a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Co., Ltd.) at a temperature elevation rate of 20 ° C/min. The lower limit of the melting point is preferably 190 ° C, more preferably 200 ° C, and particularly preferably 210 ° C. If the melting point is less than 180 ° C, the heat resistance tends to deteriorate. Therefore, when molding or when using a molded article, problems may occur when exposed to high temperatures.

From the viewpoint of heat resistance, the higher the upper limit of the melting point, the higher the better, and the case where the film having a melting point of more than 250 ° C is deteriorated in the form of a polyethylene terephthalate unit. tendency. In addition, there is a tendency for transparency to deteriorate. Further, in order to obtain high moldability or transparency, it is preferred to control the upper limit of the melting point to 250 °C.

The polyester resin film of the present invention is a biaxially stretched film. In the present invention, the disadvantage of unstretched sheets is improved by the molecular alignment produced by biaxial stretching: solvent resistance or dimensional stability. That is, it is possible to maintain good moldability of the unstretched sheet while improving solvent resistance or heat resistance of the disadvantage of the unstretched sheet.

In order to obtain good transparency and stable workability (especially surface friction characteristics), a suitable embodiment of the present invention may also use a film having a multilayer structure and a polyester film containing only fine particles in the surface layer. Such a base film is preferably a polyester film having a multilayer structure (a/b/a) which is a surface containing inactive particles on both sides of a center layer (b layer) by a co-extrusion method. The layers (layers a) are laminated. The layers constituting the surface layer on the front and back sides may be of the same type or different types, and in order to maintain the planarity of the base film, it is desirable to set the polyester resin of the front and back surface layers to have the same configuration.

(Production method)

The polyester film for molding of the present invention is desirably a biaxially oriented laminated polyester obtained by sequential biaxial stretching or simultaneous biaxial stretching. The following is a description of the successive biaxial stretching method that is most suitable for use.

The raw material pellets are first dried under sufficient vacuum. Next, the extruder is melted at a temperature above the melting point by an extruder, and the polyester sheet is extruded into a layer by a co-extrusion method to be adhered to the rotary cooling roll to obtain an unstretched polyester. film. A known electrostatic adhesion method, an air knife method, a gas chamber method, or the like can be used as a method of adhering to the rotary cooling roll. In addition, air may be blown off by the opposite side of the rotary cooling roll as necessary. The unstretched polyester film was introduced into a roll type longitudinal stretcher, heated to 80 to 125 ° C, and then extended by 2.5 to 5.0 times in the longitudinal direction by the difference in rotation speed of the rolls to obtain a uniaxially stretched film. Longitudinal extensions can be implemented in a single stage or in multiple stages.

Then, the uniaxially stretched polyester film is introduced into a jig-type horizontal stretcher, and after heating to 80 to 180 ° C, it is extended 2.5 to 5.0 times in the transverse direction, and then after heat setting treatment at 200 to 240 ° C, it is necessary to A 1 to 10% relaxation treatment is performed in the longitudinal direction and/or the transverse direction, and then wound up by a winder to obtain a biaxially stretched polyester film.

The step of coating the easy-adhesion layer may be any one of a method of coating before stretching of the film, a method of coating after stretching in the longitudinal direction, a method of coating the surface of the film after completion of the alignment treatment, and the like, wherein the wire coating method is based on the method. It is a suitable method that the coating of the polyester film is applied before the end of the crystal alignment, and then the film is aligned in at least one direction to complete the crystal alignment of the polyester film, and the effect of the present invention can be remarkably exhibited.

A method of providing an easy-adhesion layer can be applied to a commonly used method such as gravure coating, conformal coating, dipping, spray coating, curtain coating, air knife coating, knife coating, and reverse roll coating.

(molded body)

The polyester film for molding of the present invention can be suitably used as a plating instead. A metal-tone decorative layer is applied to either side of the polyester film for molding of the present invention. The metal-tone decorative layer can be formed by physical vapor deposition using a metal, an alloy, a metal oxide, or, if necessary, adding ruthenium or the like as an evaporation material. The physical vapor deposition method is a method of forming a film by vaporizing an evaporation material in any manner in a vacuum vessel and accumulating the vaporized evaporation material on a substrate placed nearby. According to the evaporation method of the evaporation material, it is divided into an evaporation system and a sputtering system. Evaporation systems include EB vapor deposition, ion plating, pulsed laser evaporation, etc. Sputter systems include RF (high frequency) sputtering, magnetron sputtering, counter target magnetron sputtering, and ECR sputtering. Wait.

The vapor deposition material may be any one or more selected from the group consisting of tin, indium, aluminum, zinc, gold, silver, copper, titanium, nickel, or an alloy based on any of them. Specifically, what should be selected can be selected in accordance with the type of metallic luster desired. Among them, indium is excellent in stretchability, and thus it is suitable for the formable plating in the present invention instead of the film.

The thickness of the metal deposition layer is preferably 5 nm or more and 80 nm or less. When it is 5 nm or more, a suitable metallic luster can be easily obtained, and when it is 80 nm or less, cracking at the time of molding can be suitably suppressed.

In addition to physical vapor deposition, it may be provided by coating or printing with a mirror ink or the like, and the surface to be decorated may be either an easy-to-layer layer or a non-adhesive layer. By integrally molding (insert molding) the film on which the decoration is applied and the molded substrate, it is possible to exhibit a surface texture that is plated.

As the substrate, a sheet or a film having moldability can be used. The constituent material of the substrate is not particularly limited, and a polymer resin is suitably used. As the polymer resin, for example, an acrylic resin such as a polyurethane resin or a polymethyl methacrylate resin, an acrylonitrile-butadiene-styrene resin (ABS resin), a polycarbonate resin, or a polyterephthalic acid can be used. A polyester resin such as ethylene glycol ester, an olefin resin such as polypropylene, a polyethylene resin, or a fluororesin. The base material and the polyester film for molding may be laminated directly, or may be laminated via an adhesive layer, a heat seal layer or the like.

The method of integrally molding (insert molding) the obtained laminate is not particularly limited, and can be integrally molded (insert molding) by vacuum molding, pressure molding, metal mold molding, or the like.

The obtained molded body is suitable as, for example, a decorative material for interior or exterior use for automobiles, a home appliance product such as a television, a refrigerator, a washing machine, an audio, a portable electric appliance, a mirror product such as a powder box mirror for makeup, an automobile, or the like. Inscriptions (including display panels and panels) used in vehicles, ships, airplanes, buildings, racing equipment (ski goggles, etc.), recreational facilities, and various other mechanical devices. In particular, it is more suitable for use in high temperature and damp heat (bath, washstand, kitchen, health care, etc., toiletries, toiletries, building materials, exteriors, solar panels, and other outdoor products, car interiors, eaves, etc.).

[Examples]

Examples and comparative examples of the invention are disclosed below. First, the measurement and evaluation methods used in the present invention are disclosed below.

(1) Glass transfer point (Tig)

The measurement of the glass transition point (Tig) of the easy-to-layer layer was carried out by simply removing the easy-adhesion layer from the easy-adhesion film.

The glass transition start temperature (Tig) was determined from the DSC curve using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Co., Ltd.) in accordance with JIS K7121.

Measuring condition

(a) Measurement temperature range: 0~200°C

(b) Heating rate: 20 ° C / min

(c) using a nitrogen stream

(2) Intrinsic viscosity

0.1 g of a sample of the fine scale was dissolved in 25 ml of a mixed solvent of phenol/tetrachloroethane = 6/4 (mass ratio), and measured at 30 ° C using an Oswald viscometer. Further, the measurement was performed 3 times and the average value thereof was determined.

(3) Haze

According to JIS K7105, an integrating sphere type light transmittance measuring apparatus (manufactured by Nippon Denshoku Industries Co., Ltd.) was used for evaluation.

(4) Easy adhesion layer thickness

The cross-section of the film was taken by a transmission electron microscope (TEM) at a right angle to the film surface at a right angle to the film surface, and the thickness of the easy-adhesion layer was measured by this photograph. The same measurement was performed 10 times at the changing place, and the average of the measured values was defined as the thickness of the easy-to-layer layer (μm).

(5) Appearance 1 (flatness tester method)

The obtained film having a length of about 100 m was wound into a film shape, and after standing at room temperature for about 12 hours, the film was cut and taken out, and a black sheet (GA Borad FS Black 26) was placed on the surface opposite to the easy-to-back layer. The flatness tester (manufactured by BYK Gardner Co., Ltd.) was used to measure the easy adhesion layer of the film. The value of the reflection intensity Wa in the region of 0.1 to 0.3 mm of the displayed wavelength was evaluated. The reflection intensity Wa in the region of the wavelength of 0.1 to 0.3 mm is an index of the amplitude of the surface roughness, and the amplitude of the fine concavo-convex shape like the orange peel on the surface of the film can be evaluated. The smaller the value, the higher the smoothness of the surface.

(6) Appearance 2 (visual evaluation)

The obtained film having a length of about 100 m was wound into a film shape, and after standing at room temperature for about 12 hours, about 100 was applied to the film. The thickness of the metal (In) is evaporated, the image of the fluorescent lamp is reflected on the surface thereof, and the image state of the fluorescent lamp is visually observed, and the following four stages are evaluated.

1: There is no observed skew of the image at all.

2: Observed a number of unclear image skews, can be used

3: Observed quite a lot of unclear image skewing, can be used

4: A comprehensive observation of significant image skew is unusable

(7) Particle size distribution of particle A

The particle size distribution was measured by a photographic method performed by an S3500 scanning electron microscope (magnification: 800 times) manufactured by Hitachi, Ltd., and the particles exposed on the surface of the easy-adhesion layer were measured and converted into equivalent spheres.

The particle size distribution measures the particle size of about 500 particles and accumulates the volume from the smaller side of the particles. The particle diameter when the cumulative ratio with respect to the total volume was 25% was set to d25, and the particle diameter when the cumulative ratio was 75% was set to d75, and the ratio (d75/d25) indicates the sharpness of the particle size distribution. The closer this value is to 1, the sharper it is. Further, in the case where the particles B coexist, the particle group having a large particle diameter is used as a parent group, and the measurement is performed by the above method.

(8) Average particle size of particles

The average particle diameter of the particles is obtained by the same method as the above-described particle size distribution, and is expressed as a particle diameter d50 when the cumulative ratio with respect to the total volume is 50%. Further, when the particles B coexist, the particle group having a large particle diameter is divided into a parent group and a parent group having a small particle diameter, and the particle diameter of the particle having a large particle diameter is defined as particle A, and the particle diameter is small as particle B. , measured by the above method.

(9) Friction evaluation (μs‧μd)

From the obtained film, a sample film having an area of 8 cm × 5 cm was cut out. This was fixed to the bottom surface of a metal cube having a bottom surface of 6 cm × 5 cm and a weight of 4.4 kg in such a manner that the layer was easily formed inside. At this time, the 5 cm width direction of the sample film was aligned with the 5 cm width direction of the metal cube, and the side of the sample film in the longitudinal direction was folded up, and was fixed to the side surface of the metal cube with an adhesive tape.

Next, a sample film having an area of 20 cm × 10 cm was cut out from the same base film, and the end portion in the longitudinal direction was fixed to the flat metal plate with the adhesive tape facing the upper side. The metal cube to which the sample film was attached was placed thereon in such a manner as to measure the surface contact, and the static friction coefficient (μs) and the dynamic friction coefficient (μd) were measured under the conditions of a pulling speed of 200 mm/min, 23 ° C, and 65 RH. The measurement was performed using RTM-100 manufactured by Toyo BALDWIN Co., Ltd., and the static friction coefficient (μs) and the dynamic friction coefficient (μd) were calculated in accordance with JIS K7125.

(10) Air removal index

As shown in Fig. 1, the film 4 is placed on the pedestal 1 with the side opposite to the easy-to-back layer facing upward. Then, the film is fixed by applying the film pressing member 2 on the film 4 and fixing it while fixing the film 4. Next, the film 5 is placed on the film pressing member 2 with the easy-to-back layer facing downward. Then, the film pressing member 8 is placed on the film 5, and the film pressing members 8, 2 and the pedestal 1 are further fixed by the screws 3. Next, the cavity 2a provided in the film pressing member 2 is transmitted through the pores 2c and the tube member 7 provided in the film pressing member 2, and is connected to the vacuum pump 6. Then, when the vacuum pump 6 is driven, the film 5 is applied with tension due to being adsorbed to the cavity 2a. At the same time, the surface on which the film 4 and the film 5 overlap each other is also permeable to the pores 2d which are circumferentially provided in the film pressing member 2, and the surface on which the film 4 and the film 5 overlap each other is adhered to the outer peripheral portion. The closeness can be easily seen by observing the interference pattern from the upper part of the coincident side. Next, an interference pattern is generated from the outer peripheral portion of the polymerization surface of the film 4 and the film 5, and the time (seconds) until the interference pattern is spread to the front side of the overlapping surface and the movement is stopped is measured. ) is defined as the air removal index. Further, the measurement was carried out by repeating five times in two films, and the average value was calculated as an air removal index. The smaller the value of the air removal index, that is, the shorter the time (seconds), the better the winding characteristics of the film.

The winding property was evaluated using the following criteria.

◎: Air removal index is less than 50 seconds

○: Air removal index of 50 seconds or more and less than 200 seconds

△: Air removal index is more than 200 seconds and less than 350 seconds

╳: Air removal index is more than 350 seconds

(11) Adhesiveness

UV-curable ink (UVA710 Black, manufactured by Seiko Advance Co., Ltd.) was printed on the surface of the film by a Tetoron Screen (#300 mesh) (after being provided with an easy-adhesion layer, the surface of the easy-adhesion layer) was 500 mJ/cm. ² UV exposure.

By the dicing blade, the printed layer (ink surface) after hardening is subjected to a cross-cut of 100 squares and a square length of 2 mm, and the Cellotape is attached thereto so as not to allow air bubbles to enter (registered trademark, manufactured by Nichiban Co., Ltd., CT- 24), further rubbing on it to make it sufficiently close. Then, the front and rear ends of the ink surface and the Cellotape are not pressed by hand, and the cross-cut surface is rapidly peeled off in the 90° direction.

The ink surface after peeling was observed, and the ink residual ratio of 100 grids (only a part of the lattice in which peeling occurred was regarded as the number of peeling) was evaluated by the following four-stage standard, and ◎ and ○ were determined to pass. Further, the so-called easy adhesion of the present invention is defined as having an ink residual ratio of 90% or more when the above evaluation is performed.

◎: Residual rate 100% (no peeling at all)

○: The residual rate is 90% or more and less than 100% (there is no problem in practical use)

△: The residual ratio is 70% or more and less than 90% (the adhesion is slightly weak, and there is a possibility that a problem may occur in practice)

╳: The residual rate is less than 70% (subsequent bad)

(12) Adhesion after damp heat

The oxidized polymerization ink (manufactured by Shijo Chemical Co., Ltd., black) and the dilution solvent (Tetoron, manufactured by Shijo Co., Ltd.) were diluted with ink: diluted solvent: 4:1 by Tetoron Screen (#250 mesh). After the surface of the film (in the case where the easy-to-adhere layer was provided as the surface of the easy-adhesion layer), it was dried in a Geer oven at 65 ° C for 15 minutes.

Next, the film printed with this ink was placed in hot water at 80 ° C for 2 minutes. After taking out, the water was wiped off, and it was air-dried for more than 3 hours. Next, a cross-cut of 100 squares of 2 mm squares was performed on the printing surface by a dicing blade, and Cellotape (registered trademark, manufactured by Nichiban Co., Ltd., CT-24) was attached thereto so as not to allow air bubbles to enter. , further rubbing on it to make it fully sealed. Then, the front and rear ends of the ink surface of the above-mentioned ink surface were not pressed by hand, and the cross-cut surface was rapidly peeled off in the 90° direction.

The ink surface after the peeling was observed, and the ink residual ratio of 100 grids (only a part of the lattice in which peeling occurred was regarded as the number of peeling) was evaluated by the following four-stage standard, and ◎ and ○ were determined to be acceptable. Further, the so-called easy adhesion of the present invention is defined as having an ink residual ratio of 90% or more when the above evaluation is performed.

◎: Residual rate 100% (no peeling at all)

○: The residual rate is 90% or more and less than 100% (there is no problem in practical use)

△: The residual ratio is 70% or more and less than 90% (the adhesion is slightly weak, and there is a possibility that a problem may occur in practice)

╳: The residual rate is less than 70% (following the problem)

(13) Formability

A polyurethane resin (Takenate (registered trademark) A-975, manufactured by Mitsui Chemicals, Inc.) was applied to the reverse vapor-deposited layer of the film of the metal vapor-deposited layer obtained in (6), and an adhesive layer was provided. The metal vapor-deposited surface was protected by a separator made of polyethylene terephthalate having a thickness of 38 μm, and an acrylic film having a thickness of 100 μm was laminated on the side opposite to the vapor-deposited surface to be heated to 100 to 140 ° C for hot plate contact. After heating for 4 seconds, calender molding was carried out at a metal mold temperature of 30 to 70 ° C and a pressure holding time of 5 seconds. The metal mold was used in the shape of a cup, the diameter of the opening was 50 mm, the diameter of the bottom portion was 40 mm, and the depth was 20 mm, and a mold having a diameter of 0.5 mm was applied to all the corners. The obtained molded article was evaluated by the following criteria.

◎: The corner portion is well formed, and there is no wrinkle or a defective appearance of the image, and a high gloss of metallic tone is exhibited.

○: Although wrinkles were observed in a part, there was no image skew, and a high gloss feeling of a metallic hue was exhibited.

△: Wrinkles or image skew were observed in a part.

╳: Wrinkles or image distortion are observed comprehensively, or rupture is observed in the molded article.

(14) Melting point (Tm) of raw material (object)

Using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Co., Ltd.), about 7 mg of the film sample was placed in the sample pan, the lid of the pan was capped, and the temperature was raised at room temperature of 20 ° C / min under a nitrogen atmosphere. The temperature was raised to 300 ° C for measurement. The melting point is determined from the aforementioned melting peak temperature.

(15) Stress at 100% stretching

A strip-shaped sample having a length of 180 mm and a width of 10 mm was cut out in the longitudinal direction and the width direction of the film obtained by (F100) by a single-blade razor. Next, a thin strip sample was stretched using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress (MPa) when 100% was stretched in each direction was obtained from the obtained stress-strain curve.

Further, the stress at 100% stretching at 25 ° C was measured in an environment of 25 ° C with an initial length (distance between the lines) of 40 mm, a distance between the jigs of 100 mm, a crosshead speed of 100 mm/min, and a recorder. The graph speed was 200 mm/min and the load cell was 25 kgf. In addition, this measurement used an average value of 10 times.

Further, the measurement of the stress at 100% stretching at 100 ° C was also carried out under the same conditions as above. At this time, the sample was measured in an environment of 100 ° C for 30 seconds and then measured. Further, the average value of the measurement was performed 10 times.

Example 1 (Preparation of hydrophobic polymerized polyester resin)

218 parts by weight of dimethyl terephthalate, 194 parts by weight of dimethyl isononate, and 488 parts by weight of ethylene glycol were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser. 200 parts by weight of neopentyl glycol and 0.5 parts by weight of tetra-N-butyl titanium were heated from 160 ° C to 220 ° C for 4 hours to carry out a transesterification reaction. Then, 13 parts by weight of fumaric acid and 51 parts by weight of sebacic acid were added, and the temperature was raised from 200 ° C to 220 ° C for 1 hour to carry out an esterification reaction. Subsequently, the temperature was raised to 255 ° C, and the reaction system was gradually reduced in pressure, and then reacted under reduced pressure of 0.22 mmHg for 1 hour and 30 minutes to obtain a hydrophobic copolymerized polyester resin. The resulting hydrophobic copolymerized polyester was light yellow transparent.

(Preparation of polyester-based graft copolymer dispersed in water)

75 parts by mass of a hydrophobic copolymerized polyester, 56 parts by mass of methyl ethyl ketone, and 19 parts by mass of isopropyl alcohol were added to a reactor equipped with a stirrer, a thermometer, a reflux device, and a metering device, and heated at 65 ° C. Stir to dissolve the resin. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Next, 12 parts by mass of a solution of 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile dissolved in methyl ethyl ketone was dropped into the polyester solution at 0.1 ml/min, and stirring was further continued. hour. After sampling for analysis by the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution, followed by stirring for 1 hour and a half. Then, the internal temperature of the reactor was raised to 100 ° C, and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a polyester-based graft copolymer dispersed in water. The obtained polyester-based graft copolymer was light yellow transparent, and the glass transition point was 40 °C. This resin was designated as a polyester-based graft copolymer (a1).

(Synthesis of polycarbonate urethane resin)

In a four-necked flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 73.0 parts by mass of 1,3-cyclohexane bis(methyl isocyanate) as a polyisocyanate and a number average molecular weight of 2000 were added. 112.7 parts by mass of the alcohol carbonate, 11.7 parts by mass of neopentyl glycol, 12.6 parts by mass of dimethylolpropionic acid, 60 parts by mass of acetonitrile as an organic solvent, and 30 parts by mass of N-methylpyrrolidone, the reaction was carried out under a nitrogen atmosphere. The liquid temperature was adjusted to 75 to 78 ° C, and 0.06 parts by mass of stannous octoate as a reaction catalyst was added, and the reaction was carried out for 7 hours until the reaction rate was 99% or more. It was then cooled to 30 ° C to give an isocyanate-terminated prepolymer. Next, 450 g of water was added to a reaction vessel equipped with a homogenizer (Homo Disper) which can be stirred at a high speed, and adjusted to 25 ° C, and stirred and mixed at 2000 min-1, and an isocyanate-terminated prepolymer was added thereto to disperse it in water. Then, by removing acetonitrile and a part of water under reduced pressure, an aqueous solution (b1) of a water-dispersible polycarbonate-based urethane resin having a solid content of 35% was prepared. The glass transfer point (Tig) was 86 °C.

(modulation of coating liquid A)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and the mixture was mixed with water/isopropyl alcohol with 1.0% by mass of polymethyl methacrylate particles having an average particle diameter of 0.04 μm as particles. The solvent (=65/35; mass ratio) was diluted to prepare an aqueous coating agent.

(Manufacture of film raw materials)

100 parts by mole of terephthalic acid unit as an aromatic dicarboxylic acid component, 40% by mole of ethylene glycol unit as a diol component, and 60% by mole of neopentyl glycol unit, respectively, as a constituent component and intrinsic viscosity The chips (A) of the copolymerized polyester of 0.69 dl/g were dried with the chips (B) having an intrinsic viscosity of 0.69 dl/g of polyethylene terephthalate. Further, the chips (A) and the chips (B) were mixed in such a manner that the mass ratio was 25:75.

(Manufacturing of laminated film)

Next, the pieces of the mixture were melt-extruded from the slit of the T-die by an extruder at 270 ° C, and quenched and solidified on a cooling roll having a surface temperature of 40 ° C while being adhered by electrostatic application. On the chill roll, an amorphous unstretched sheet is obtained.

Between the heating roller and the cooling roller, the obtained unstretched sheet was extended to a longitudinal direction of 3.3 times at 90 °C.

Next, the aqueous coating liquid A shown above was applied to one surface of the film by a roll coating method on the obtained uniaxially stretched film, and dried at 130 ° C for 3 seconds to remove water.

Then, the end portion is clamped by the clip, and is continuously guided to the tenter, heated at a setting of 100 ° C, extended laterally by 3.8 times, the web is fixed, and heat treatment is performed at 230 ° C for 5 seconds, further This was allowed to relax at 5% in the width direction of 205 ° C, thereby obtaining a polyester film for molding having a film thickness of 25 μm and an easy adhesion layer thickness of 0.05 μm.

The evaluation results of the obtained polyester film for molding are disclosed in Table 1.

(modulation of coating liquid B)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that A mixed solvent of water/isopropyl alcohol (========================================================================================= 65/35; mass ratio) diluted to prepare an aqueous coating agent.

Example 2

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid B in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid C)

The ratio of the solid content of the polyester-based graft copolymer (a1) and the water-dispersible polycarbonate-based urethane resin (b1) obtained above is a polyester-based graft copolymer/polyurethane resin. (mass ratio) = 95/5, and the blocked isocyanate compound is mixed in such a manner that it is 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and The solid content of the resin is 2.8% by mass, and 1.0% by mass of cerium oxide particles having an average particle diameter of 0.13 μm is contained for all the resins, and cerium oxide having an average particle diameter of 0.06 μm is contained for all the resins. The form of 7.3 mass% of the particles was diluted with a mixed solvent of water/isopropanol (=65/35; mass ratio) to prepare an aqueous coating agent.

Example 3

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid C in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid D)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin is 2.8% by mass, and 0.02% by mass of the styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm with respect to all the resins, and the average of all the resins. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 4

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid D in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the easy-adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid E)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and the styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were 0.05% by mass based on the total resin, and the average of the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 5

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid E in the first embodiment, a polyester film for molding having a film thickness of 0.05 μm and a coating thickness of the adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid F)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in such a manner that it is 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and The total solid content of the resin is 0.56% by mass, and 1.0% by mass of the styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm is contained in all the resins, and is contained in all the resins. An aqueous coating agent was prepared by diluting a 7.3 mass% of cerium oxide particles having an average particle diameter of 0.06 μm in a mixed solvent of water/isopropanol (=65/35; mass ratio).

Example 6

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.01 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid F in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid G)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 1.12% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 7

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.02 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid G in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid H)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 8

A molding polyester having a film thickness of 25 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid H in the same manner as in Example 1. film. The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid I)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 5.04% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 9

A molding polyester film having a film thickness of 25 μm and a coating thickness of an easy-adhesion layer of 0.09 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid I in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid J)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 5.60% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 10

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.10 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid J in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid K)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and the content of the styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm was 3.0% by mass based on the total resin, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 11

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid K in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid L)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and the styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in an amount of 5.0% by mass based on the total resin. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 12

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid L in the first embodiment, a polyester film for molding having a film thickness of 0.05 μm and a coating thickness of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid M)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.47 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 13

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid M in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the easy-adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

Example 14

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid M in the first embodiment, the film thickness after the film formation was 75 μm, and the coating thickness of the easy-adhesion layer was 0.05 μm. Polyester film. The characteristics and evaluation results of the obtained film are disclosed in Table 1.

Example 15

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid M in the first embodiment, the film thickness after film formation was 20 μm, and the coating thickness of the easy-adhesion layer was 0.05 μm. Polyester film. The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(Modulation of coating liquid N)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the isocyanate compound is blocked so as to be mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin. The total solid content of the resin is 2.8% by mass, and the amount of the cerium oxide particles having an average particle diameter of 1.12 μm is 1.7% by mass for all the resins, and the average particle diameter is 0.06 μm for all the resins. The cerium oxide particles were diluted with a mixed solvent of water/isopropyl alcohol (=65/35; mass ratio) in an amount of 7.3 mass% to prepare an aqueous coating agent.

Example 16

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid N in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid O)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed with 20 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin in an amount of 20 parts by mass. The total solid content of the resin was 2.8% by mass, and 1.0% by mass of benzoguanamine-formaldehyde crosslinked particles having an average particle diameter of 1.86 μm were contained in all the resins, and the average particles were contained for all the resins. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) in a manner of 7.3% by mass of cerium oxide particles having a diameter of 0.06 μm.

Comparative example 1

A molding polyester film having a film thickness of 25 μm and a coating thickness of 0.05 μm in an easy-contact layer was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid O in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid P)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and 1.0% by mass of the melamine-formaldehyde crosslinked particles having an average particle diameter of 0.9 μm were contained in all the resins, and the average particle diameter was 0.06 μm with respect to all the resins. An aqueous coating agent was prepared by diluting a 7.3 mass% of cerium oxide particles in a mixed solvent of water/isopropanol (=65/35; mass ratio).

Comparative example 2

A molding polyester film having a film thickness of 25 μm and a coating thickness of 0.05 μm in an easy-contact layer was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid P in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid Q)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 95/5, and the blocked isocyanate compound is mixed with 20 parts by mass of 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, and all the resins are mixed. The solid content concentration is 2.8% by mass, and 1.0% by mass of cerium oxide particles having an average particle diameter of 1.58 μm is contained for all the resins, and cerium oxide particles having an average particle diameter of 0.06 μm are contained for all the resins. The 7.3 mass% method was diluted with a mixed solvent of water/isopropanol (=65/35; mass ratio) to prepare an aqueous coating agent.

Comparative example 3

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was replaced with the coating liquid Q in Example 1. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid R)

The ratio of the solid content of the polyester-based graft copolymer (a1) obtained above and the water-dispersible polycarbonate-based urethane resin (b1) is a polyester-based graft copolymer/polyaminecarboxylic acid. The ester resin (mass ratio) is 80/20, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the polyester-based graft copolymer and the polyurethane resin, so that The total solid content of the resin was 2.8% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm were contained in all the resins, and the average of all the resins was included. An aqueous coating agent was prepared by diluting a water/isopropanol mixed solvent (=65/35; mass ratio) of 7.3 mass% of cerium oxide particles having a particle diameter of 0.06 μm.

Example 17

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid R in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid S)

The ratio of the solid content of the copolymerized polyester resin liquid (a1) obtained above and the water-dispersible polycarbonate urethane resin (b1) is a copolymerized polyester resin/polyurethane resin ( The mass ratio is 40/60, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, so that all the resin solid components are obtained. The concentration is 2.8% by mass, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm are contained in all the resins, and an average particle diameter of 0.06 μm is contained for all the resins. An aqueous coating agent was prepared by diluting 7.3 mass% of cerium oxide particles in a mixed solvent of water/isopropanol (=65/35; mass ratio).

Example 18

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid S in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid T)

The ratio of the solid content of the copolymerized polyester resin liquid (a1) obtained above and the water-dispersible polycarbonate urethane resin (b1) is a copolymerized polyester resin/polyurethane resin ( (mass ratio) = 80/20, and the blocked isocyanate compound is mixed in a manner of 40 parts by mass based on 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, so that all the resin solid components are obtained. The concentration is 2.8 mass%, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm are contained in all the resins, and an average particle diameter of 0.06 μm is contained for all the resins. An aqueous coating agent was prepared by diluting 7.3 mass% of cerium oxide particles in a mixed solvent of water/isopropanol (=65/35; mass ratio).

Example 19

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid T in the first embodiment, a molding polycondensation having a film thickness of 25 μm and an easy adhesion layer thickness of 0.05 μm was obtained. Ester film. The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid U)

The ratio of the solid content of the copolymerized polyester resin liquid (a1) obtained above and the water-dispersible polycarbonate urethane resin (b1) is a copolymerized polyester resin/polyurethane resin ( The mass ratio is 80/20, and the blocked isocyanate compound is mixed in an amount of 8 parts by mass based on 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin, so that all the resin solid components are obtained. The concentration is 2.8 mass%, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm are contained in all the resins, and an average particle diameter of 0.06 μm is contained for all the resins. An aqueous coating agent was prepared by diluting 7.3 mass% of cerium oxide particles in a mixed solvent of water/isopropanol (=65/35: mass ratio).

Example 20

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid U in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the easy-adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid V)

The ratio of the above-mentioned copolymerized polyester resin liquid (a1) and a polyurethane resin having a glass transition point of 35 ° C (type number) (made by Mitsui Chemical Co., Ltd.: Takelac (registered trademark) W511) becomes copolymerization. The polyester resin/polyurethane resin (mass ratio) is 80/20, and the blocked isocyanate compound is 20 parts by mass based on 100 parts by mass of the total amount of the copolymerized polyester resin and the polyurethane resin. By mixing, the total solid content of the resin is 2.8 mass%, and 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm with respect to all the resins. The resin was diluted with a mixed solvent of water/isopropanol (=65/35; mass ratio) in a manner of containing 7.3% by mass of cerium oxide particles having an average particle diameter of 0.06 μm to prepare an aqueous coating agent.

Example 21

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid V in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the adhesive layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

(modulation of coating liquid W)

An ether-based polyurethane resin (manufactured by Mitsui Chemicals Co., Ltd.: Takelac (registered trademark) W6020), which has a polyester-based graft copolymer (a1) and a glass transition point of 90 ° C (type-recorded value). The ratio of the solid content is a polyester-based graft copolymer/polyurethane resin (mass ratio) = 80/20, and the blocked isocyanate compound is compared with the polyester-based graft copolymer and the polyurethane resin. When the total amount of the resin solid content is 2.8% by mass, and the styrene-diethylene having an average particle diameter of 0.83 μm is contained with respect to all the resins, the total amount of the resin solid content is 2.8 mass%. 1.0% by mass of the benzene-based crosslinked particles, and a mixed solvent of water/isopropyl alcohol (=65/35; mass ratio) in which the cerium oxide particles having an average particle diameter of 0.06 μm are contained in an amount of 7.3% by mass based on the entire resin. Dilute to prepare an aqueous coating agent.

Example 22

In the same manner as in Example 1, except that the coating liquid A was changed to the coating liquid W in the first embodiment, a polyester film for molding having a film thickness of 25 μm and a coating thickness of the easy-adhesion layer of 0.05 μm was obtained. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

Example 23

In the production of the coating liquid H, the blocked isocyanate compound was changed to a coating obtained by making a melamine compound (a Beckamine (registered trademark) M-3 solid content concentration of 60%) a solid content of 16.7% by mass. A laminated polyester film having a coating thickness of 0.05 nm in an easy-adhesion layer was obtained in the same manner as in Example 8 except for the liquid (X). The properties and evaluation results of the obtained single-layer film are disclosed in Table 1.

Example 24

A layer having an easy-adhesion layer of 0.05 nm was obtained in the same manner as in Example 4 except that only the polyethylene terephthalate (B) having an intrinsic viscosity of 0.69 dl/g was used as the film material. Polyester film. The properties and evaluation results of the obtained single-layer film are disclosed in Table 1.

(Modulation of coating liquid Y)

The ratio of the solid content of the copolymerized polyester resin liquid (a1) obtained above and the water-dispersible polycarbonate urethane resin (b1) is a copolymerized polyester resin/polyurethane resin ( The mass ratio is =0/100, and the blocked isocyanate compound is mixed in an amount of 20 parts by mass based on 100 parts by mass of the copolymerized polyester resin, so that the total resin solid content concentration is 2.8% by mass, and All the resins contain 1.0% by mass of styrene-divinylbenzene crosslinked particles having an average particle diameter of 0.83 μm, and 7.3% by mass of cerium oxide particles having an average particle diameter of 0.06 μm with respect to all the resins. The water/isopropyl alcohol mixed solvent (=65/35; mass ratio) was diluted to prepare an aqueous coating agent.

Comparative example 4

A molding polyester film having a film thickness of 25 μm and an easy-adhesion layer coating thickness of 0.05 μm was obtained in the same manner as in Example 1 except that the coating liquid A was changed to the coating liquid Y in the first embodiment. . The characteristics and evaluation results of the obtained film are disclosed in Table 1.

[Industrial availability]

The polyester film for molding of the present invention has good adhesion and is suitable for forming a mirror-like decorative layer having excellent surface texture. Therefore, it is suitable for a decorative member for interior decoration or exterior decoration of a vehicle, a home appliance membrane switch, a base material for a mobile phone, a member for building materials, and the like, and is integrally molded with a molding substrate at the same time. It is suitable for plating instead of processing.

1. . . Pedestal

2, 8. . . Film pressing member

2a. . . Empty hole

2c. . . hole

2d. . . Fine hole

3. . . Screw

4, 5. . . film

6. . . Vacuum pump

7. . . Pipe fittings

X. . . Film overlap

Fig. 1 is a cross-sectional explanatory view showing an apparatus for measuring the air removal rate of a film.

Claims (12)

A polyester film for molding which has an easy-adhesive layer on at least one side of a polyester film, and the easy-adhesion layer contains a polyester resin, a polyurethane resin, and at least one type of particles, and the polyurethane resin A polycarbonate-based polyurethane resin having a particle size distribution (d75/d25) of 1.1 to 1.5, an average particle diameter d of 0.04 to 1.2 μm, and an average particle diameter d of the particles and an easy-to-layer thickness t The ratio (d/t) is 1 or more and 100 or less. The polyester film for molding according to claim 1, wherein the polyester film is a copolymerized polyester or a copolymerized polyester and a homopolyester. The polyester film for molding according to claim 1 or 2, wherein the polyester resin is a polyester-based graft copolymer obtained by grafting a polymerizable unsaturated monomer onto a hydrophobic copolymerized polyester resin. The polymerizable unsaturated monomer contains at least one acid anhydride having a double bond. The polyester film for molding according to the first or second aspect of the invention, wherein the easy-to-adhere layer contains 0.01 to 3% by mass of the particles, the haze of the film is 2.0% or less, the static friction coefficient is 0.9 or less, and the dynamic friction coefficient is The system is below 0.8, and the air escape index is 200 seconds or less. The polyester film for molding according to claim 1 or 2, wherein the film thickness is 15 to 100 μm or less. The polyester film for molding according to claim 1 or 2, wherein the reflection intensity (Wg) of the region using a flatness tester (Wave-scan) at a wavelength of 0.1 mm to 0.3 mm measured on the surface of the film is 4.0. the following. A plating instead of a processing method, characterized in that a metal vapor-deposited layer is provided on one surface of a polyester film for molding according to any one of claims 1 to 6, and then integrally molded with a substrate. A polyester film for insert molding, which has an easy-adhesion layer on at least one side of a polyester film, and the easy-adhesion layer contains a polyester resin, a polyurethane resin, and at least one kind of particles, and the polyamine The ester resin is a polycarbonate-based polyurethane resin, the polyester film is a copolymerized polyester, or a copolymerized polyester and a homopolymer polyester, and the thickness of the polyester film is 15 to 100 μm, and a flatness test device is used. The reflection intensity (Wa) in the region of the wavelength of 0.1 mm to 0.3 mm measured on the surface of the film is 4.0 or less. The polyester film for insert molding according to Item 8 of the patent application, wherein the particle size distribution (d75/d25) of the particles is 1.1 to 1.5, the average particle diameter d is 0.04 to 1.2 μm, and the average particle diameter d of the particles is The ratio (d/t) of the easy-to-layer thickness t is 1 or more and 100 or less. The polyester film for insert molding according to claim 8 or 9, wherein the polyester resin is a polyester-based graft copolymer obtained by grafting a polymerizable unsaturated monomer onto a hydrophobic copolymerized polyester resin. Property The unsaturated monomer contains at least one acid anhydride having a double bond. The polyester film for insert molding according to the eighth or ninth aspect of the invention, wherein the easy-to-adhere layer contains 0.01 to 3% by mass of the particles, the haze of the film is 2.0% or less, and the static friction coefficient is 0.9 or less. The dynamic friction coefficient is 0.8 or less, and the air removal index is 200 seconds or less. A plating instead of a decorative film, which has a metal deposition layer on one side of the polyester film for insert molding according to any one of claims 8 to 11.