JP2010070581A - Polyester film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester film satisfying all of transparency, solvent resistance (printing property), heat resistance, and moldability, and also excellent in cost performance. <P>SOLUTION: The polyester film has at least a polyester (A) layer in which full width at half maximum of 1730 cm<SP>-1</SP>of spectral band in a laser Raman method is <23 cm<SP>-1</SP>. The polyester (A) layer contains an expanding agent, in which stress at 400% elongation is in a range of 2-20 MPa under an atmosphere of 120°C, and haze is ≤10%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyester film excellent in solvent resistance, heat resistance and moldability.

  As a film for transfer foil used by printing and molding, a biaxially stretched polyester film (for example, see Patent Document 1 and Patent Document 2) has been used, and this biaxially stretched polyester film was used. The transfer foil is insufficient in terms of formability for transferring to a member having a large drawing ratio or a member having a complicated shape.

  Moreover, as a polyester film aiming at the improvement of a moldability, the transfer foil (for example, refer patent document 3) using the copolyester film whose molding stress is low compared with a biaxially stretched polyester film, and polyester are comprised. Polyester films for molding, processing, printing products and the like containing a specific glycol component such as butanediol as a glycol component have been proposed (for example, see Patent Document 4). Transfer foils using these polyester films are Although the moldability is good, the printability is not particularly considered, and it is easily whitened by the organic solvent contained in the printing ink, for example, ethyl acetate, methyl ethyl ketone, toluene, acetone, transparency, and smoothness of the film surface. Problems such as poor printability and easy printing defects. .

  Thus, a film excellent in solvent resistance to various solvents contained in the printing ink, that is, printability has been desired.

  In addition, the polyester unstretched film has better moldability than the biaxially stretched film, but when used for molding applications such as a transfer foil, a release layer, a top layer, and a printing layer are sequentially coated on the film. In order to form these layers, they are dissolved in a solvent such as ethyl acetate, methyl ethyl ketone, toluene, acetone, or a mixed solvent thereof, applied as a solution, and the solvent is dried to sequentially form each layer. The temperature at which the solvent is dried is near or above the boiling point of each solvent {ethyl acetate (boiling point: 77 ° C), methyl ethyl ketone (boiling point: 80 ° C), toluene (boiling point: 110 ° C), acetone (boiling point: 56 ° C)}. Heated and dried. However, polyester unstretched films are more likely to be wrinkled, stretched, shrunk, etc. when they are tensioned at the drying temperature, compared to biaxially stretched films. As a result, there is a problem that the heat resistance at 80 to 120 ° C. is insufficient due to molding defects.

Further, a molding polyester sheet in which a thermoplastic polyester having a melting point of 180 ° C. or higher and a crystallization parameter ΔTcg (crystallization temperature-glass transition temperature) of 50 ° C. or lower is laminated on both surfaces of another thermoplastic polyester has been proposed ( For example, see Patent Document 5). However, the crystallinity of the laminated surface was not taken into consideration, and the solvent resistance, heat resistance, and moldability were not all satisfied. Therefore, a film satisfying all of solvent resistance, heat resistance, and moldability is desired.
JP-A-6-210799 JP 2000-344909 A Japanese Patent No. 3090911 JP 2002-97261 A JP-A-4-070333

  An object of the present invention is to provide a film satisfying all of solvent resistance, heat resistance and moldability. Thereby, the film of this invention is used suitably for the use regarding printing and a shaping | molding process.

As a result of intensive studies to achieve the above object, the present inventors adopt the following means. That is:
[1] spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman has at least a polyester (A) layer is less than 23cm ^-1,
The polyester (A) layer contains an extender,
Under an atmosphere of 120 ° C., the stress at 400% elongation is in the range of 2 to 20 MPa,
A polyester film having a haze of 10% or less.
[2] polyester and polyester (A) layer spectral band full width at half maximum of 1730 cm ^-1 is less than 23cm ^-1 in the laser Raman method, the spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman method, which is 23cm ^-1 or more ( B) having at least a layer,
The polyester (A) layer and / or polyester (B) layer contains an extender,
Under an atmosphere of 120 ° C., the stress at 400% elongation is in the range of 2 to 20 MPa,
A polyester film having a haze of 10% or less.
[3] The extender is at least one selected from the group consisting of aliphatic carboxylic acid amides and N-substituted ureas,
[1] or [2], wherein the layer containing the extender further contains at least one selected from the group consisting of aliphatic alcohols, sorbitol compounds, amino acids, and polypeptides. The polyester film as described in.
[4] The polyester (A) that is the main component of the polyester (A) layer is a polyester composed of at least one selected from the group consisting of polypropylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and copolymers thereof. The polyester film according to any one of the above [1] to [3], wherein the polyester film is provided.
[5] Any of [2] to [4] above, wherein the polyester (B) as a main component of the polyester (B) layer is a polyester made of polyethylene terephthalate or a copolymer of polyethylene terephthalate. The polyester film of crab.
[6] The polyester film according to any one of [2] to [5], wherein the polyester (A) layer is provided on both sides of the polyester (B) layer.

  According to the present invention, a polyester film excellent in transparency, heat resistance, solvent resistance, and moldability can be obtained.

  More specifically, the polyester film of the present invention is excellent in solvent resistance against a solvent contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone, etc., so various printing inks can be used, and the printing property is excellent. .

Further, the spectral band full width at half maximum around 1730 cm ^-1 in the laser Raman polyester (A) layer surface be less than 23cm ^-1, by further addition of extenders, coater suitability (heat resistance) of drying the various solvents, It becomes possible to achieve both solvent resistance and moldability, and a film having particularly excellent moldability.

  The polyester film of the present invention is excellent in moldability such as molding that requires deep drawing and molding of complex shapes, so in-mold transfer foil used by printing and molding, automotive interior / exterior parts, bathroom panels, home appliances It is suitably used as a transfer foil for performing printing transfer processing of parts for products and packaging containers.

Polyester film of the present invention, having at least a polyester (A) layer spectral band full width at half maximum of 1730 cm ^-1 is less than 23cm ^-1 in the laser Raman method, the polyester (A) layer contains the extender, In a 120 ° C. atmosphere, the polyester film has a stress at 400% elongation of 2 to 20 MPa and a haze of 10% or less.

Another aspect of the polyester film of the present invention, the polyester (A) layer spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman method is less than 23cm ^-1, spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman At least a polyester (B) layer having a density of 23 cm ⁻¹ or more, and the polyester (A) layer and / or the polyester (B) layer contains an extender and is 400% stretched in an atmosphere of 120 ° C. The polyester film has a stress in the range of 2 to 20 MPa and a haze of 10% or less. Hereinafter, the polyester film of the present invention will be described in detail.

  The polyester film of the present invention needs to have at least a polyester (A) layer from the viewpoint of solvent resistance to the solvent contained in the printing ink, that is, printability.

  Moreover, it is also preferable that the polyester film of this invention makes it the laminated structure which has a polyester (A) layer and a polyester (B) layer at least. Particularly preferably, for example, the polyester (A) layer is provided on both sides of the polyester (B) layer from the viewpoint of suppressing the curling phenomenon of the film due to the difference in stretching stress of each layer due to temperature, humidity, etc. Although it is preferable to laminate | stack by the film structure of (polyester (A) layer / polyester (B) layer / polyester (A) layer), this invention is not limited to this film structure.

  The polyester (A) that is the main component of the polyester (A) layer of the polyester film of the present invention is preferably a polymer basically composed of a dicarboxylic acid component and a glycol component.

  In the following description, “main component” means the largest component in a total of 100% by mass of all components in a certain layer.

  Examples of the dicarboxylic acid component include isophthalic acid, terephthalic acid, diphenyl-4,4′-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, Diphenoxyethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, malonic acid, 1,1-dimethylmalonic acid, succinic acid, glutaric acid, Adipic acid, sebacic acid, decamethylene dicarboxylic acid and the like can be used.

  The polyester (A) as the main component of the polyester (A) layer of the polyester film of the present invention is preferably a polyester having a high crystallization rate or a polyester having a high glass transition temperature from the viewpoint of solvent resistance. Examples of the polyester having a high crystallization speed include polybutylene terephthalate, polypropylene terephthalate, and polyhexamethylene terephthalate. Among these, polybutylene terephthalate and polypropylene terephthalate are preferable, and polybutylene terephthalate is particularly preferable. Polyester having a high glass transition temperature includes polyethylene naphthalate, and is particularly preferably used.

  Therefore, the polyester (A) as the main component of the polyester (A) layer of the polyester film of the present invention is at least selected from the group consisting of polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, and copolymers thereof. One type of polyester is preferred.

The polyester (A) layer mainly composed of polyester (A) of the polyester film of the present invention, it spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface is less than 23cm ^-1 is important. The spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface, from the viewpoint of easily controlled below 23cm ^-1, the polypropylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and copolymers thereof Preferably, the polyester (A) layer contains at least one polyester (A) selected from the group consisting of 80% by mass and 100% by mass in a total of 100% by mass of all components of the polyester (A) layer. It is. More preferably, it is an embodiment in which the polyester (A) is contained in an amount of 90% by mass to 100% by mass in a total of 100% by mass of all components of the polyester (A) layer, and more preferably 100% by mass in total of all components of the polyester (A) layer %, The polyester (A) is contained in an amount of 95% by mass or more and 99.9% by mass or less.

Polyester film of the present invention, spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface, it is important that less than 23cm ^-1. It is said that the 1730 cm ⁻¹ spectral band of the Laser Raman method is due to the C═O bond band of the polyester. It was found that the smaller the full width at half maximum of the spectrum band of the C═O bond, the higher the crystallinity and the better the solvent resistance and heat resistance. Of the polyester film, the spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface not less than 23cm ^-1, solvent resistance, it is easily inferior heat resistance. Spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface, more preferably less than 22 cm ^-1, more preferably less than 21cm ^-1. The lower limit of the spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (A) layer surface, because not observed substantially less than 15cm ^-1, the lower limit of such a band full width at half maximum is 15cm ^-1 .

  The polyester film of the present invention preferably further has a polyester (B) layer. The polyester (B) as the main component of the polyester (B) layer is the same as the polyester (A) used in the polyester (A) layer. It is possible to use a dicarboxylic acid component and a glycol component.

  The polyester (B) is more preferably a polyester containing a naphthalenedicarboxylic acid component and / or a terephthalic acid component in the dicarboxylic acid component in an amount of 90 mol% to 100 mol% from the viewpoint of heat resistance and productivity. When a dicarboxylic acid component other than the naphthalenedicarboxylic acid component and terephthalic acid component is used, and if the naphthalenedicarboxylic acid component and / or terephthalic acid component in the dicarboxylic acid component is less than 90 mol%, heat resistance and productivity are reduced. This is not preferable because it is easy to do.

  Examples of the glycol component include ethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, aliphatic glycols such as 1,3-propanediol, alicyclic glycols such as cyclohexanedimethanol, bisphenol-A, A glycol component such as aromatic glycol such as bisphenol-S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-propylene glycol copolymer, or the like can be used.

  From the viewpoint of moldability and productivity, the ethylene glycol component is 100 mol% in the glycol component, or the ethylene glycol component is in the range of 60 to 98 mol% in the glycol component, and 1,3-propanediol and / or The 1,4-butanediol component preferably contains 2 to 40 mol%. When a glycol component other than the ethylene glycol component, 1,3-propanediol component, and 1,4-butanediol component is used, the ethylene glycol component is 100 mol%, or the ethylene glycol component is 60 to 98 mol%, In addition, if the composition ratio is other than 1 to 40 mol% of the 1,3-propanediol and / or 1,4-butanediol component, moldability and productivity are likely to be lowered, which is not preferable.

  The specific polymer used as the polyester (B) is preferably polyethylene terephthalate or a copolymer of polyethylene terephthalate from the viewpoint of glass transition temperature.

  The polyester (B), which is the main component of the polyester (B) layer of the polyester film of the present invention, is a polyester comprising the above-mentioned polyethylene terephthalate or a copolymer of polyethylene terephthalate because the glass transition temperature of the film is difficult to decrease. (B) is preferred. And the polyester (B) layer which contains 80 mass% or more and 100 mass% or less of polyester (B) which consists of a copolymer of a polyethylene terephthalate or a polyethylene terephthalate with respect to 100 mass% of all the components of a polyester (B) layer, It is preferable to do. More preferably, it is 90 mass% or more and 100 mass% or less with respect to 100 mass% of all the total components of a polyester (B) layer, More preferably, it is 95 mass% or more and 99.9 mass% or less.

Spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman polyester (B) layer surface of the polyester film of the present invention, it is important that 23cm ^-1 or more. When the half width is less than 23 cm ⁻¹ , the polyester film having a polyester (B) layer on the polyester (A) layer is excellent in heat resistance, but the moldability may be easily deteriorated, which is not preferable. The full width at half maximum of 1730 cm ⁻¹ in the laser Raman method on the surface of the polyester (B) layer is more preferably 24 cm ⁻¹ or more, and further preferably 25 cm ⁻¹ or more. Since the upper limit of the full width at half maximum of the spectrum band is not substantially 26 cm ⁻¹ or more, the upper limit of the full width at half maximum of the polyester (B) layer is 26 cm ⁻¹ .

  The polyester film of the present invention has a thickness of the polyester (A) layer mainly composed of the polyester (A) (thickness per layer of the polyester (A) layer) from the viewpoint of achieving both solvent resistance, heat resistance and moldability. ) Is 1 μm or more, and the total thickness of the polyester (A) layer mainly composed of the polyester (A) is preferably 5 to 50% of the total thickness of the film.

  If the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is less than 1 μm, the solvent resistance and heat resistance are likely to be inferior. More preferably, the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is 3 μm or more, and particularly preferably 4 μm or more. The upper limit of the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) varies depending on the thickness of the entire film, and the polyester (A) layer is compatible with both heat resistance and moldability described later. The total thickness is 50% of the thickness of the entire film. For example, when the thickness of the entire film is 20 μm, if the film configuration is an A / B / A configuration, the upper limit of the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is 5 μm, If the film configuration is an A / B configuration, the upper limit of the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is 10 μm. Moreover, when the thickness of the whole film is 500 μm, if the film configuration is an A / B / A configuration, the upper limit value of the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is 125 μm, If the film configuration is an A / B configuration, the upper limit value of the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) is 250 μm. If the thickness of the polyester (A) layer (thickness per layer of the polyester (A) layer) exceeds the upper limit, the solvent resistance and heat resistance are excellent, but the moldability tends to be inferior. Further, if the total thickness of the polyester (A) layer is less than 5% of the total thickness of the film, it is not preferable because the heat resistance such as the film stretches easily when the solvent is dried with a coater or the like. Conversely, if the total thickness of the polyester (A) layer exceeds 50% of the total thickness of the film, the heat resistance is excellent, but the moldability tends to be inferior. By setting the thickness of the polyester (A) layer (the thickness per layer of the polyester (A) layer) to 1 μm or more, solvent resistance can be obtained, and the total thickness of the polyester (A) layer is set to the total film thickness. By setting the thickness within the range of 5 to 50%, both heat resistance and moldability can be achieved.

  In the polyester film of the present invention, it is important that the polyester (A) layer and / or the polyester (B) layer contains an extender (when the polyester film does not have a polyester (B) layer, the polyester (A ) Layer contains an extender and, if the polyester film has both a polyester (A) layer and a polyester (B) layer, the polyester (A) layer and / or the polyester (B) layer. Is important to contain an extender). When the polyester (A) layer and / or the polyester (B) layer contains an extender, the haze value of the polyester film of the present invention is halved, the transparency is improved, and the overall breaking elongation is improved by 30% or more. It turns out that they do. This mechanism is not clear, but I think as follows. By containing an extender, it is considered that transparency is improved by suppressing the crystal growth of the polyester and making the crystal size smaller than visible light. In the tensile test, the molecules constituting the polyester crystal are unwound and stretched, the molecules are fully stretched, and the point at which the molecules are broken becomes the breaking elongation. It is believed that if the crystal size is reduced to the following size, the number of crystals increases, so that when the molecules constituting the crystal are unwound, the molecular entanglement increases and the breaking elongation of the film is improved. The improvement in the elongation at break leads to an improvement in formability such as deep drawing and complex shape.

  Examples of the extender having the characteristics of improving transparency and improving elongation at break include aliphatic carboxylic acid amides, N-substituted ureas, aliphatic carboxylates, aliphatic alcohols, aliphatic carboxylic acid esters, fats Aromatic / aromatic carboxylic acid hydrazides, sorbitol compounds, melamine compounds, phenylphosphonic acid metal salts, amino acids, polypeptides, and the like can be used. Among them, compounds selected from aliphatic carboxylic acid amides, N-substituted ureas, sorbitol compounds, amino acids, and polypeptides can be preferably used, and aliphatic carboxylic acid amides and N-substituted ureas are particularly preferable.

  Specific examples of the aliphatic carboxylic acid amide preferably used as the extender include lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide and hydroxystearic acid amide. Aliphatic monocarboxylic amides such as N-oleyl palmitic acid amide, N-oleyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid N-substituted aliphatic monocarboxylic amides such as amide, methylol stearic acid amide, methylol behenic acid amide, methylene bis stearic acid amide, ethylene bislauric acid amide, ethylene biscapric acid amide, ethylene bisoleic acid amide Acid amide, ethylene bis stearic acid amide, ethylene bis erucic acid amide, ethylene bis behenic acid amide, ethylene bis isostearic acid amide, ethylene bishydroxy stearic acid amide, butylene bis stearic acid amide, hexamethylene bis oleic acid amide, Fats such as hexamethylenebisstearic amide, hexamethylene bisbehenic amide, hexamethylene bishydroxystearic amide, m-xylylene bisstearic amide, m-xylylene bis-12-hydroxystearic amide Carboxylic bisamides, N, N′-dioleyl sebacic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide N-place like Listed are substituted aliphatic carboxylic acid bisamides. Among these, compounds selected from aliphatic monocarboxylic amides, N-substituted aliphatic monocarboxylic amides and aliphatic carboxylic bisamides are preferably used. An amide of an aliphatic carboxylic acid having 4 to 30 carbon atoms, more preferably 12 to 30 carbon atoms, and an amine selected from ammonia or an aliphatic / aromatic monoamine / diamine having 1 to 30 carbon atoms is preferable. Used. In particular, palmitic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, hydroxy stearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, ethylenebiscapric acid amide, ethylenebisolein A compound selected from acid amide, ethylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis erucic acid amide, m-xylylene bis stearic acid amide and m-xylylene bis-12-hydroxy stearic acid amide is preferably used. .

  Specific examples of the N-substituted urea preferably used as the extender include N-butyl-N′-stearyl urea, N-propyl-N′-stearyl urea, N-stearyl-N′-stearyl urea, N— Phenyl-N′-stearyl urea, xylylene bisstearyl urea, toluylene bisstearyl urea, hexamethylene bisstearyl urea, diphenylmethane bisstearyl urea, diphenylmethane bislauryl urea, and the like can be used.

  Moreover, as a preferable example of the aliphatic carboxylate preferably used as the extender, a metal salt of an aliphatic carboxylic acid having preferably 4 to 30 carbon atoms, more preferably 14 to 30 carbon atoms may be mentioned. Specific examples of the aliphatic carboxylic acid having 14 to 30 carbon atoms include lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, isostearic acid, behenic acid, and montanic acid. Examples of the metal include lithium, sodium, potassium, magnesium, calcium, barium, aluminum, zinc, silver, copper, lead, thallium, cobalt, nickel, and beryllium. In particular, a salt of stearic acid or a salt of montanic acid is preferably used, and in particular, a compound selected from sodium stearate, potassium stearate, zinc stearate and calcium montanate is preferably used.

  Moreover, as a preferable example of the aliphatic alcohol used preferably as an extending | stretching agent, C4-C30, More preferably, C15-C30 aliphatic alcohol is mentioned. Specifically, aliphatic monoalcohols such as pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, ceryl alcohol, melyl alcohol, 1,6-hexanediol, 1,7 -Aliphatic polyhydric alcohols such as heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, Examples include cyclic alcohols such as cyclohexane-1,4-diol. In particular, aliphatic monoalcohols are preferably used, and stearyl alcohol is particularly preferably used.

  Moreover, as a preferable example of the aliphatic carboxylic acid ester preferably used as the extender, preferably an aliphatic carboxylic acid having 4 to 30 carbon atoms, more preferably 12 to 30 carbon atoms, and an aliphatic having 1 to 30 carbon atoms. / Esters with alcohols selected from aromatic monools, diols and triols are preferably used. Specific examples include lauric acid cetyl ester, lauric acid phenacyl ester, myristic acid cetyl ester, myristic acid phenacyl ester, palmitic acid isopropyl ester, palmitic acid dodecyl ester, palmitic acid tetradecyl ester, palmitic acid pentadecyl ester, palmitic acid Aliphatic monocarboxylic esters such as acid octadecyl ester, palmitic acid cetyl ester, palmitic acid phenyl ester, palmitic acid phenacyl ester, stearic acid cetyl ester, behenic acid ethyl ester, monolauric acid glycol, monopalmitic acid glycol, monostearate Monoesters of ethylene glycol such as acid glycol, glycol dilaurate, glycol dipalmitate, glycostearate Diesters of ethylene glycol such as glycerol, monolauric acid glycerin ester, monomyristic acid glycerin ester, monopalmitic acid glycerin ester, monostearic acid glycerin ester and other glycerin monoesters, dilauric acid glycerin ester, dimyristic acid glycerin ester, Glycerin diesters such as glyceryl dipalmitate and glyceryl distearate, trilauric acid glycerin ester, trimyristic acid glycerin ester, tripalmitic acid glycerin ester, tristearic acid glycerin ester, palmitodiolein, palmitodistearin, oleodistearin And the like, and the like. Of these, ethylene glycol diesters are preferred, and ethylene glycol distearate is particularly preferred.

  Specific examples of the aliphatic / aromatic carboxylic acid hydrazide preferably used as the extender include sebacic acid dibenzoic acid hydrazide, and specific examples of sorbitol compounds include dibenzylidene sorbitol and bis (p-methylbenzylidene) sorbitol. Specific examples of bis (p-ethylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, and melamine compounds include melamine cyanurate and melamine polyborate and phenylphosphonic acid metal salts. A phosphonic acid zinc salt, a phenylphosphonic acid calcium salt, a phenylphosphonic acid magnesium salt, etc. can be used.

  Specific examples of amino acids that are preferably used as extenders include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, phenylglycine, tryptophan, and proline, which are constituents of proteins contained in living bodies. Specific examples of o-tyrosine, glutamic acid, aspartic acid, glutamine, asparagine, lysine, arginine, histidine, and polypeptide include leuprolide.

  These extenders may be used alone or in combination of two or more in each layer. When two or more types are used in combination, there may be cases where the respective synergistic effects are exhibited, and the increase in crystallization speed and the promotion of crystal refinement are more remarkable than in the case where each is used alone.

  Regarding the total content of these extenders, regarding the polyester (A) layer, transparency, extensibility, and the effect as an extender are saturated, and the appearance and physical properties do not change. It is preferable to contain the extending | stretching agent of the range of 0.1-5 mass% with respect to 100 mass% of total components. When the content of the extender is less than 0.1% by mass in the total mass of 100% by mass of all the components of the polyester (A) layer, the transparency and extensibility are likely to be inferior. On the other hand, if the content exceeds 5% by mass, bleeding is likely to occur and the appearance and physical properties are likely to change, such being undesirable. More preferably, in the polyester (A) layer 100% by mass, the content of the extender is 0.3 to 3% by mass, and more preferably 0.5 to 2% by mass.

  Moreover, regarding the polyester (B) layer, from the viewpoint of transparency, extensibility, and moldability, the extender is in the range of 0.05 to 3% by mass with respect to 100% by mass in total of all components of the polyester (B) layer. It is preferable to contain. When the content of the extender is less than 0.05% by mass in a total of 100% by mass of all the components of the polyester (B) layer, the transparency and extensibility are likely to be inferior. Conversely, if the content exceeds 3% by mass, the moldability tends to be poor, which is not preferable. More preferably, it is 0.08-2 mass%, More preferably, it is the range of 0.1-1.5 mass%.

  The polyester film of the present invention preferably further contains a compound having hydrogen bonding properties with the extender. The exemplified extenders are often self-associating, and in that case, the extender is added in an aggregated state in the resin, which may be inconvenient for crystal refinement. Therefore, by further mixing the extender and the compound having hydrogen bonding properties with the extender, the self-association of the extender may be released, and the extender may be further finely dispersed. In this case, crystal miniaturization becomes more effective.

  There is no particular limitation on the method of adding the compound having hydrogen bonding properties with the extender. The compound having hydrogen bonding property with the extender may be melted or mixed with the polyester or the extending agent at the same time, or the compound previously melted or solution mixed with the extending agent and the compound having hydrogen bonding property with the extender. You may add to polyester. Moreover, the method of producing a master pellet and diluting it may be used. Among these, from the viewpoint of solving the self-association of the extender, a method of adding a compound having a hydrogen bondability with the extender, previously melted or mixed with the extender, to the polyester is preferable.

In addition, the determination of whether the compound and the extender have hydrogen bonding can be analyzed by nuclear magnetic resonance (NMR). For example, the presence or absence of a hydrogen bond can be confirmed from the change in chemical shift of the ¹ H-NMR spectrum of a solution mixture of the compound and the extender compared to the case of each simple substance. For example, when an aliphatic carboxylic acid amide compound is used as the extender and a sorbitol compound is used as the compound having hydrogen bonding property with the extender, the solution mixture product has a low amide bond proton peak compared to each other. The magnetic field shifts, and the proton peak of the hydroxyl group of sorbitol is shifted by a high magnetic field, so that it can be confirmed that a hydrogen bond exists between them.

  As a specific example of the compound having hydrogen bonding property with the extender, when an aliphatic carboxylic acid amide or N-substituted urea is used as the extender, the compound having hydrogen bond property with the extender is an aliphatic alcohol, Sorbitol compounds, amino acids, polypeptides and the like can be used. Therefore, as the extender, at least one selected from the group consisting of aliphatic carboxylic acid amides and N-substituted ureas is used, and the layer containing the extender further includes aliphatic alcohols, sorbitol compounds, amino acids And at least one selected from the group consisting of polypeptides is particularly preferred.

  In the case of containing a compound having a hydrogen bonding property with the extender, the amount relationship with the extender is not particularly limited, but from the viewpoint of effectively releasing the self-association of the extender, the extender, the extender and the hydrogen bond The mass ratio of the compound having the property is preferably 1: 9 to 9: 1. More preferably, it is 1: 5 to 5: 1, and further preferably 1: 2 to 2: 1.

  From the viewpoint of releasing the above-described self-association of the extender and finely dispersing the extender in the resin, a method of dissolving only the extender once in a solvent and releasing the self-association is added to the polyester. Can also be used.

  The polyester film of the present invention preferably has a plane orientation coefficient fn in the range of 0.00 to 0.04 from the viewpoint of moldability. In order to obtain a film having a plane orientation coefficient fn of 0.00 to 0.04, a method of forming an unstretched film can be mentioned. Even if it is a non-stretched film, it may be drafted during film formation, and the film may be slightly oriented in the machine (longitudinal) direction. Even so, it is important to suppress the orientation. When the plane orientation coefficient fn exceeds 0.04, the formability in the machine (longitudinal) direction and the width direction may be different during molding, which is not preferable. More preferably, it is the range of 0.00-0.03, More preferably, it is the range of 0.00-0.02.

Here, the plane orientation coefficient (fn) is a value calculated from the refractive index (Nx, Ny, Nz, respectively) in the film longitudinal direction, width direction, and thickness direction measured using an Abbe refractometer or the like by the following equation. It is.
-Plane orientation coefficient: fn = {(Nx + Ny) / 2} -Nz
Here, when the longitudinal direction and the width direction of the film are not known, the direction having the maximum refractive index in the film plane is the longitudinal direction, the direction perpendicular to the longitudinal direction in the film plane is the width direction, and the film plane. The plane orientation coefficient (fn) can be obtained with the orthogonal direction as the thickness direction. The direction of the maximum refractive index in the film plane may be determined by measuring the refractive index in all directions in the plane with an Abbe refractometer, for example, with a phase difference measuring device (birefringence measuring device) or the like. You may obtain | require by determining an axial direction.

  In the polyester film of the present invention, it is important that the haze of the film is 10% or less. In general, when polyester is crystallized by heat treatment or the like in order to improve solvent resistance, the polyester crystal grows and becomes opaque as a film. By adding an extender to the polyester, excessive crystal growth of the polyester can be suppressed, the crystal can be refined, and transparency can be obtained. When the haze of the film exceeds 10%, for example, it becomes difficult to use a coating agent such as ultraviolet curing performed through a film for use in a transfer foil or the like. Preferably the haze of the polyester film is less than 5%, more preferably less than 2%. The haze decreases as the film thickness decreases. However, it is difficult to make the haze 0.2% or less at a thickness of 25 μm. Therefore, the lower limit of haze of the polyester film seems to be about 0.2%.

  For example, when the polyester film of the present invention is used for a transfer foil application, each layer such as a release layer / top coat layer / printing layer / adhesive layer is provided on the film as the transfer foil. Since the surface shape of the film surface on which the release layer is provided is transferred to the transfer target, at least one surface of the polyester film of the present invention preferably has a surface roughness Ra in the range of 20 to 100 nm. When the surface roughness Ra is 20 to 100 nm, the outermost surface of the polyester film of the present invention is the other layer (a layer that is neither a polyester (A) layer nor a polyester (B) layer) and a polyester (A) layer. The polyester (A) layer is preferred. When the polyester film of the present invention has a polyester (A) layer on both sides, or when the polyester film of the present invention consists only of a polyester (A) layer, the surface roughness Ra of at least one side is in the range of 20 to 100 nm. Preferably there is. When the surface roughness Ra exceeds 100 nm, it is not preferable because coating spots and the like of each layer are likely to occur. On the other hand, if the surface roughness Ra is less than 20 nm, blocking or the like occurs and handling properties deteriorate, which is not preferable.

  For example, when the polyester film of the present invention is used for a transfer foil, the thickness unevenness is preferably in the range of less than ± 10% from the viewpoint of coatability. If the thickness unevenness exceeds ± 10%, it is not preferable because the coating unevenness of each layer is likely to occur. The polyester non-stretched film of the present invention is more difficult to control the thickness variation than the biaxially stretched film, and the thickness variation is about ± 3%.

  The polyester film of the present invention preferably has a 5% deformation temperature in the range of 80 to 120 ° C. when the temperature is raised by applying a load of 1.2 MPa. For example, when the polyester film of the present invention is used for transfer foil applications, each layer such as a release layer, a topcoat layer, a printing layer, and an adhesive layer is provided on the film. These coating materials contain various organic solvents, and the organic solvent is dried by being heated near the boiling point of the organic solvent or above the boiling point. At that time, tension is applied so that the film has a uniform surface. The tension is about 4.0 to 1.2 MPa. As the tension is higher, the film is more likely to be deformed, such as wrinkled, elongated, or shrunk. When the transfer foil made of the polyester film of the present invention is transferred to a molded product, the printed product is deformed and easily causes molding defects. The maximum tension at which this deformation is likely to occur was taken as the measured tension, and a 5% deformation temperature was determined from a thermomechanical analyzer (TMA) curve when the temperature was increased by applying a load of stress 1.2 MPa. The lower limit of the 5% deformation temperature is, for example, ethyl acetate (boiling point: 77 ° C.), methyl ethyl ketone (boiling point: 80 ° C.), acetone (boiling point: 56 ° C.) as an organic solvent often used in various coating materials. If the boiling point is the lower limit, it is considered to be 80 ° C. The upper limit of the 5% deformation temperature is preferably as the deformation temperature is higher from the viewpoint of heat resistance. However, if it is too high, the moldability tends to be inferior. If the 5% deformation temperature is less than 80 ° C., it is not preferable from the viewpoint of coater suitability. Conversely, if the 5% deformation temperature exceeds 120 ° C., the coater suitability is excellent, but the molding stress becomes large and the moldability tends to deteriorate, such being undesirable.

  In the polyester film of the present invention, it is important that the stress at 400% elongation is in the range of 2 to 20 MPa in an atmosphere of 120 ° C. Recently, UV curable coatings and the like are used, and UV curable coatings cause decomposition such as separation and foaming at high temperatures, so lowering the molding temperature is being studied. . The upper limit temperature at which decomposition of the coating starts is said to be about 120 ° C., and moldability at 120 ° C. is required. The moldability is required to have the characteristics of high elongation at low stress at the molding temperature, and in order to stretch the film uniformly, it is required that there is no yield point in the stress-strain curve. Thus, as a result of intensive studies, in the case of deep drawing, the elongation at break at 120 ° C. is 400% or more and the stress at 400% elongation is preferably as low as possible. It was found that the elongation at break of% or more could not be obtained.

  Moreover, it is difficult for a normal biaxially stretched polyester film to have a breaking elongation of 400% or more under an atmosphere of 120 ° C. When the surface magnification (longitudinal draw ratio × lateral draw ratio) is about 6 times or less, a biaxially stretched polyester film having a breaking elongation of 400% or more may be obtained. -Since the yield point in a distortion curve appears or the stress at 400% elongation exceeds 20 MPa, it is not preferable from the viewpoint of formability.

  From the above points, the stress at 400% elongation under an atmosphere of 120 ° C. is preferably in the range of 2 to 20 MPa. The stress at 400% elongation under an atmosphere of 120 ° C. is more preferably in the range of 5 to 20 MPa, further preferably in the range of 5 to 15 MPa.

  In the polyester film of the present invention, a plasticizer other than the extender, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and a whitening agent are provided as long as the effects of the present invention are not impaired. You may add compounds, such as an agent, a coloring agent, a electrically conductive agent, inorganic particle | grains, organic particle | grains, another kind polymer, etc.

  The polyester film of the present invention can be improved in coatability, printability and the like as necessary by performing a surface treatment such as a corona discharge treatment. Various coatings may be applied, and the type, coating method, and thickness of the coating compound are not particularly limited as long as the effects of the present invention are not impaired. Furthermore, it can be used after being subjected to molding processing such as embossing, printing, or the like, if necessary.

  The thickness of the film can be freely determined according to the application to be used. The thickness is usually in the range of 20 to 500 μm, preferably 30 to 200 μm, more preferably 50 to 200 μm from the viewpoint of film formation stability.

  The polyester film of the present invention can be obtained by a melt extrusion method such as a T-die method or an inflation method. For example, when a film is obtained by the T-die method, it is an important condition that the extruded film is rapidly cooled and solidified by cooling.

  Next, although the manufacturing method of the polyester film of this invention is demonstrated, this invention is not limited to this.

  The polyester film of the present invention is, for example, after drying a resin mainly containing polyester (A) in the polyester (A) layer and a resin mainly containing polyester (B) in the polyester (B) layer as necessary. To a known melt extruder. The extruder may be a single-screw melt extruder or a twin-screw melt extruder provided with a vent port. The supplied resin is melted at a temperature of the melting point of each polyester + 20-30 ° C. and then passed through a leaf disk filter having a filtration accuracy of 20-40 μm.

  Next, it passes through 3 layers of A layer / B layer / A layer or a 2-layer pinole tube of A layer / B layer, is led to a slit-shaped T die die, and is extruded into a sheet shape. Adhering to a casting drum adjusted to a surface temperature of 40 to 80 ° C. by electrostatic application method using a needle-like edge pinning device, air nozzle, air chamber method, suction chamber method, etc. at both ends of the extruded sheet And a polyester film can be obtained by cooling and solidifying from a molten state. The casting drum may be a mirror drum or a satin drum, but a satin drum is preferred from the viewpoint of adhesion of the film to the drum and adhesiveness. The surface roughness of the satin drum is preferably in the range of 100 to 1000 nm in terms of the centerline surface roughness Ra from the viewpoint of achieving both adhesion and adhesiveness. More preferably, it is the range of 200-500 nm. When a satin drum is used, the adhesion to the drum tends to be insufficient, and a film with poor transparency may be obtained. Therefore, it is preferable to use another adhesion method in combination.

The obtained film is a non-oriented non-stretched film having a plane orientation coefficient fn of 0.00 to 0.04. In order to make the full width at half maximum of the spectrum band in the laser Raman method on the surface of the A layer 23 cm ⁻¹ or less, the casting drum temperature is preferably 40 to 80 ° C. When the temperature exceeds 80 ° C., the full width at half maximum of the spectrum band in the laser Raman method of layer A is 23 cm ⁻¹ or less, but the film tends to stick to the casting drum and the productivity is poor. On the other hand, if the upper limit is exceeded, the film will be whitened, which may be inferior in transparency or inferior in moldability. Conversely, if it is less than 40 ° C., the full width at half maximum of the spectrum band in the laser Raman method of layer A exceeds 23 cm ⁻¹ , and the solvent resistance and heat resistance are inferior.

  The polyester film of the present invention is excellent in solvent resistance and heat resistance. In particular, in terms of moldability, it can be molded into a deep drawing or molded into a complicated shape, and has a complicated surface shape, such as an automotive interior / exterior component or a building material. It can be preferably used as a film for transfer foils such as decorative sheets, bathroom panels, home appliance parts, OA product parts, and packaging containers.

EXAMPLES Hereinafter, although this invention is demonstrated along an Example, this invention is not restrict | limited by these Examples. Various characteristics were measured and evaluated by the following methods.
(1) Glass transition temperature (Tg), crystallization temperature (Tc) and melting point (Tm)
Using a differential scanning calorimeter DSCII type manufactured by Seiko Instrument Co., Ltd., a glass transition temperature (Tg) and a crystallization temperature (Tg) were obtained from a DSC curve when a sample 5 mg was heated at a heating rate of 10 ° C./min. Tc) and melting point (Tm) were determined. The peak temperature of the endothermic melting curve was defined as the melting point (Tm).
(2) Thickness, lamination thickness of polyester (A) layer and ratio of polyester (A) layer When measuring the thickness of the entire film, using a dial gauge, 5 arbitrary locations on each sample cut out from the film The thickness was measured and averaged.

  When measuring the layer thickness of the laminated film, using a metal microscope Leica DMLM manufactured by Leica Microsystems Co., Ltd., photograph the transmitted light at a magnification of 100 times, and measure the layer thickness of each layer of the laminated film. It was measured.

The ratio with respect to the thickness of the whole film was calculated | required from each thickness of the measured polyester (A) layer.
(3) Intrinsic viscosity The value calculated by the following formula from the solution viscosity measured in orthochlorophenol at 25 degreeC is used. That is,
ηsp / C = [η] + K [η] ² × C
Here, ηsp = (solution viscosity / solvent viscosity) −1, C is the dissolved polymer mass per 100 ml of solvent (g / 100 ml), and K is the Huggins constant (assuming 0.343). The solution viscosity and solvent viscosity were measured using an Ostwald viscometer.
(4) Plane orientation coefficient (fn)
Using the Abbe refractometer with sodium D-line (wavelength 589 nm) as the light source, the longitudinal refractive index (Nx), the width refractive index (Ny), and the thickness direction refractive index (Nz) of the film surface are measured. The plane orientation coefficient (fn) was calculated from the equation.
-Planar orientation coefficient fn = {(Nx + Ny) / 2} -Nz
(5) Full width at half maximum of spectrum band at 1730 cm ⁻¹ in laser Raman method After embedding a polyester film with an epoxy resin, a cross-section is prepared by a microtome, a measurement point of 1 μm from the film (A) layer surface, and a polyester (A) layer and polyester the measurement points 1μm from the interface of the (B) layer to the polyester layer (B), the Raman spectrum was measured by the following apparatus and measurement conditions were measured full width at half maximum of the Raman band near 1730cm ^{-1 (cm -1).} The number of measurements n = 5 was measured at different locations, the average value was obtained, and the full width at half maximum of the spectrum band was obtained.
Device: Ramnor T-64000 (Horiba Jobin Yvon)
Micro-Raman (Raman microprobe) function is combined. Microprobe Beam Splitter: Right objective lens: × 100
Beam diameter: 1μm
Cross slit: 200 μm
Light source Ar + Laser: NEC GLG3460 5145A
Laser power: 40mW
-Spectrometer configuration: 640mm Triple Monochromator
Diffraction grating: PAC Holographic 76 × 76mm
Spectrograph 1800gr / mm
Dispersion: Single, 7A / mm
Slit: 100 μm
Detector CCD: Jobin Yvon 1024 × 256
(6) Surface roughness Ra of satin drum
Using a 80 μm thick triacetylcellulose film (Bioden RFA triacetylcellulose / solvent: methyl acetate), applying a linear pressure of 9.8 N / cm to the matte drum surface with a pressure roller on the matte drum surface, the surface shape of the satin drum The replica sample was used as a measurement sample after drying the solvent at room temperature.

The surface side to which the drum surface shape of the measurement sample was transferred was measured using a high precision thin film level difference meter ET-10 manufactured by Kosaka Laboratory. Measurement was carried out under the conditions of a stylus tip radius of 0.5 μm, a needle pressure of 5 mg, a measurement length of 1 mm, and a cut-off of 0.08 mm to determine the centerline surface roughness Ra. The definition of each parameter is shown in, for example, Nara Jiro surface roughness evaluation method (General Technology Center, 1983).
(7) Heat resistance (5% deformation temperature)
Seiko Instruments Co., Ltd .: TMA thermal analysis system EXSTAR6000 makes temperature rise rate 10 ° C./min, measurement temperature range 25-200 ° C., sample test length 20 mm, sample width 4 mm, with a stress of 1.2 MPa. Measured. The number of tests n = 5 is measured in the longitudinal direction and the width direction of the film, the temperature when the test length is elongated by 5% is determined from the elongation curve, the average value in the longitudinal direction and the width direction is taken as the 5% deformation temperature, The heat resistance was evaluated according to the evaluation criteria. ○ and △ are acceptable levels.
○: 5% deformation temperature exceeds 80 ° C.
Δ: 5% deformation temperature is in the range of 75-80 ° C.
X: 5% deformation temperature is less than 75 ° C.
(8) Stress at 400% elongation and elongation at break at 120 ° C. From a polyester film, a sample having a length of 200 mm and a width of 10 mm was cut in two directions, the machine direction and the width direction, and ASTM-D-882- In accordance with 81 (Method A), measurement was performed at a tensile rate of 200 mm / min in an atmosphere of 120 ° C. with a test number n = 5 in each of the machine direction and the width direction, and an average value of all measurement results of stress at 400% elongation was calculated. It was determined as the stress at 400% elongation. The breaking elongation of the sample was also measured under the same measurement conditions.
(9) Solvent resistance Three types of ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, and methyl isobutyl ketone were dropped on the surface of the film for 3 hours, and then the solvent was wiped clean. According to the evaluation criteria, it was visually observed and judged. ○ and △ are acceptable levels.
○: For all solvents, no whitening, shrinkage, deformation, or trace of solvent is observed.
Δ: A relatively light whitening, shrinkage, or deformation is observed in any solvent.
X: Whitening, shrinkage, or deformation is observed with any solvent.
(10) Formability Formability was evaluated under a temperature condition of 120 ° C using a cup-type vacuum forming machine. Molding was performed using a cup shape with a diameter of 50 mm under the condition of a drawing ratio of 1.0, and the state when molded under the best temperature condition was determined based on the following criteria. ○ and △ are acceptable levels.
○: Corners were also sharply shaped and the thickness after molding was uniform.
Δ: Slightly rounded corners and slightly non-uniform thickness after molding.
X: The thickness after molding was uneven, and wrinkles and tearing occurred.
(11) Comprehensive evaluation Based on the evaluation results of heat resistance, solvent resistance, and moldability, it was determined according to the following criteria. ○ and △ are acceptable levels.
(Circle): About all evaluation of heat resistance, solvent resistance, and moldability, all are evaluation of (circle), and it can use preferably as a film for transfer foil.
(Triangle | delta): Although it was evaluation of (triangle | delta) about one item or two items about heat resistance, solvent resistance, and a moldability, it is evaluation of (circle) other than that, and it can fully endure the practical use as a film for transfer foils.
X: About heat resistance, solvent resistance, and moldability, at least one item is evaluation of x, cannot be practically used as a film for transfer foil, or is difficult to use as a film for transfer foil.

The following polyesters and particle masters were used in Examples and Comparative Examples.
[Polyethylene terephthalate (PET)]
To a mixture of 95.3 parts by mass of dimethyl terephthalate and 54.7 parts by mass of ethylene glycol, 0.09 parts by mass of magnesium acetate and 0.03 parts by mass of diantimony trioxide are added, and the temperature is raised by heating in a conventional manner. A transesterification reaction was performed.

Subsequently, 0.026 part by mass of trimethyl phosphate was added to the transesterification reaction product, and then transferred to a polycondensation reaction tank. Next, the reaction system was gradually depressurized while being heated and heated, and polymerization was performed at 290 ° C. under a reduced pressure of 1.33 × 10 ² Pa or less to produce a polyester having an intrinsic viscosity of 0.65 dl / g.

The obtained polymer had a glass transition temperature of 80 ° C. and a melting point of 257 ° C.
[Isophthalic acid copolymerized polyethylene terephthalate (PET-I)]
Except for using a mixture of 75.5 parts by weight of dimethyl terephthalate, 16.0 parts by weight of dimethyl isophthalate, and 58.5 parts by weight of ethylene glycol, the same method as in the above PET, melting point 223 ° C., intrinsic viscosity 0.70 dl / g An isophthalic acid copolymerized polyethylene terephthalate (PET-I) was obtained.
[Polybutylene terephthalate (PBT)]
To a mixture of 69.7 parts by weight of dimethyl terephthalate and 80.3 parts by weight of 1,4-butanediol, 0.05 parts by weight of tetrabutyl titanate and 0.02 parts by weight of IRGANOX 1010 (Ciba Specialty Chemicals) were added. Finally, the temperature was raised to 210 ° C. to conduct a transesterification reaction.

After the transesterification reaction, 0.01 parts by mass of trimethyl phosphate, 0.07 parts by mass of tetrabutyl titanate, and 0.03 parts by mass of IRGANOX 1010 were added. The temperature was gradually raised and the pressure was reduced, and finally a polycondensation reaction was performed at 245 ° C. and 1.33 × 10 ² Pa or less to produce a polyester having an intrinsic viscosity of 0.85 dl / g.

The obtained polymer had a glass transition temperature of 30 ° C. and a melting point of 224 ° C.
[Polypropylene terephthalate (PPT)]
0.06 parts by mass of tetrabutyl titanate is added to a mixture of 80.5 parts by mass of dimethyl terephthalate and 69.5 parts by mass of 1,3-propanediol, and the temperature is finally raised to 220 ° C. went.

After transesterification, 0.05 part by mass of trimethyl phosphate and 0.04 part by mass of tetrabutyl titanate were added. The temperature was gradually raised and reduced, and finally a polycondensation reaction was carried out at 260 ° C. and 1.33 × 10 ² Pa or less to produce a polyester having an intrinsic viscosity of 0.70 dl / g.

The obtained polymer had a glass transition temperature of 50 ° C. and a melting point of 223 ° C.
[Polyethylene naphthalate (PEN)]
0.06 parts by mass of tetrabutyl titanate is added to a mixture of 99.4 parts by mass of dimethyl 2,6-naphthalenedicarboxylate and 50.6 parts by mass of ethylene glycol, and finally the temperature is raised to 220 ° C. for transesterification. Went.

After transesterification, 0.05 part by mass of trimethyl phosphate and 0.04 part by mass of tetrabutyl titanate were added. The temperature was gradually raised and reduced, and finally a polycondensation reaction was carried out at 290 ° C. and 1.33 × 10 ² Pa or less to produce a polyester having an intrinsic viscosity of 0.69 dl / g.

The obtained polymer had a glass transition temperature of 124 ° C. and a melting point of 270 ° C.
[Particle Master 1 (MS-1)]
A mixture of 90 parts by weight of the PET obtained above and 10 parts by weight of silicon dioxide (“Silysia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter: 2.5 μm) was added to a 30 mmφ vented different direction double extruder (L / D = 35) and kneaded at 260 ° C. to prepare a silicon dioxide master (MS-1) containing 10% by mass of silicon dioxide.
[Particle Master 2 (MS-2)]
A mixture of 90 parts by mass of PBT obtained above and 10 parts by mass of silicon dioxide (“Silysia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle size: 2.5 μm) was converted into a 30 mmφ vented opposite-direction double extruder (L / D = 35) and kneaded at 260 ° C. to prepare a silicon dioxide master (MS-2) containing 10% by mass of silicon dioxide.
[Particle Master 3 (MS-3)]
A mixture of 90 parts by mass of PPT obtained above and 10 parts by mass of silicon dioxide (“Silicia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle size: 2.5 μm) was converted into a 30 mmφ vented opposite-direction double extruder (L / D = 35) was kneaded at 260 ° C. to prepare a silicon dioxide master (MS-3) containing 10% by mass of silicon dioxide.
[Particle Master 4 (MS-4)]
A mixture of 90 parts by mass of PEN and 10 parts by mass of silicon dioxide (“Silicia 445” manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter of 2.5 μm) obtained above was added to a 30 mmφ vented opposite-direction double extruder (L / D = 35) and kneaded at 300 ° C. to prepare a silicon dioxide master (MS-4) containing 10% by mass of silicon dioxide.
[Elongation agent-1]
Ethylene bislauric acid amide (EBLA)
[Elongation agent-2]
Ethylene bis-stearic acid amide (EBSA)
[Elongation agent-3]
Bis (p-methylbenzylidene) sorbitol (BMBS)
[Elongation agent-4]
[Extender 1] (30 g) and [Extender 3] (30 g) were added to 200 ml of dimethyl sulfoxide (DMSO), and the system was heated to 100 ° C. and stirred until the solution became transparent. Then, DMSO was distilled off under reduced pressure, and further dried with a vacuum dryer at 100 ° C. for 12 hours to obtain a solution mixture [extender 4].

When the ¹ H-NMR spectrum (DMSO solvent) of [extender 4] was confirmed, the proton peak of the amide in [extender 1] observed in the vicinity of 3.4 ppm was about 0.0. The proton peak of the hydroxyl group in [Elongation agent-3] observed in the vicinity of 4.5 ppm was shifted by a high magnetic field of about 0.05 ppm compared with the single substance. From this, it was found that a hydrogen bond was formed between ethylenebislauric acid amide and bis (p-methylbenzylidene) sorbitol in [Elongation agent-4].
[Elongation agent-5]
[Extender 1] (30 g) and [Extender 3] (30 g) were melt-mixed at 300 ° C. for 5 minutes in a nitrogen atmosphere to obtain a melt mixture [Extender 5].

In addition, when the ¹ H-NMR spectrum (DMSO solvent) of [extender 5] was confirmed, the proton peak of the amide in [extender 1] observed in the vicinity of 3.4 ppm was about 0.0. The proton peak of the hydroxyl group in [Elongation agent-3] observed in the vicinity of 4.5 ppm was shifted by a high magnetic field of about 0.05 ppm compared with the single substance. From this, it was found that a hydrogen bond was formed between ethylenebislauric acid amide and bis (p-methylbenzylidene) sorbitol in [extender 5].
[Release Agent-1]
In a reaction kettle, 600 parts by mass of water was added, to a mixture of 70 parts by mass of behenyl methacrylate and 30 parts by mass of methacrylic acid, 1 part by mass of azobisisobutyronitrile, and 0.6 parts by mass of carboxymethyl solosolve as a dispersant. Then, 0.5 part by mass of sodium polyacrylate was added and reacted at 85 ° C. for 5 hours while stirring. The polymer content was washed with water to obtain a solid. The solid was analyzed using FT-IR (manufactured by Shimadzu Corporation, FTIR-8100M) and ¹³ C-NMR (manufactured by JEOL Ltd., JNM-EX400). It was a long-chain alkyl acrylate copolymer resin having 69.8% by mass of behenyl methacrylate units and 30.2% by mass of methacrylic acid units, and had a copolymer composition almost identical to the charged monomer composition ratio.
Example 1
As a polyester of the polyester (A) layer, a mixture of PBT pellets (97% by mass), particle master MS-2 pellets (2% by mass), and [extender 1] 1% by mass was used. As the polyester of the polyester (B) layer, PET pellets (94% by mass) and PBT pellets (5% by mass) were set in the vent type different direction twin screw extruder A (2 vent ports, L / D = 70). ), And a mixture of extender-1 (1% by mass), respectively, were administered to a vent type different direction twin screw extruder B set at an extrusion temperature of 280 ° C. (2 vent ports, L / D = 70), and A 3 layer pinole of layer / B layer / A layer is passed through a T die die with a slit gap of 0.8 mm set at 280 ° C., extruded into a film shape, and needle-shaped edge pinning equipment is used at both ends of the extruded sheet Electrostatic mark In combination with a method and an air chamber method, it is brought into close contact with a satin casting drum (center line surface roughness Ra = 200 to 350 nm) having a surface temperature of 60 ° C. to cool and solidify, and a thickness of 100 μm (A layer / B layer / A layer thickness = A polyester film of 10 μm / 80 μm / 10 μm) was produced. The plane orientation coefficient (fn) of the film was 0.00. The polyester film could be formed stably, did not cause curling, and was excellent in handleability.

  Next, a release layer, a topcoat layer, a printing layer, and an adhesive layer were formed in this order on the polyester (A) layer surface of the obtained polyester film to prepare a transfer foil. The release agent-1 was used as the release layer, and the solid content after drying was 0.2 μm thick. As the top coat layer, an ultraviolet curable acrylic resin {"LAROMER" LR8983 manufactured by BASF Japan Ltd.} With a thickness of 60 μm and a polyurethane resin gravure ink (“Hiramic” manufactured by Dainichi Seika Kogyo Co., Ltd., main solvent: toluene / methyl ethyl ketone / isopropyl alcohol, ink: 723B yellow / 701R white) as a printing layer with a thickness of 70 μm Furthermore, an acrylonitrile / butadiene / styrene (ABS) copolymer resin film (ABS film “Hiflex” manufactured by Okamoto Co., Ltd., thickness 100 μm) was used as the adhesive layer. In order to cure the printed layer, aging was performed at a temperature of 40 ° C. for 72 hours.

  Next, an acrylonitrile / butadiene / styrene (ABS) copolymer resin (manufactured by Toray Industries, Inc., ABS resin “Toyolac” 930) is used as a molding resin with a draw ratio of 1.0 and a diameter of 50 mm cup concave mold. Then, an ABS copolymer resin cup-shaped molded product was produced by injection molding.

  Further, the transfer foil was heated to a temperature of 80 ° C., and an ABS copolymer resin cup-shaped molded product was arranged on the adhesive layer surface side of the transfer foil, and transfer molded at a temperature of 85 ° C. using a pressure forming machine. After releasing the pressure, with the transfer foil attached, the top coat layer is cured with ultraviolet rays using a wavelength of 365 nm, and then the bonded film layer on the outer surface is peeled off, and the ABS resin cup is visible from the outer surface. A molded product was produced.

The obtained molded article made of ABS copolymer resin was a molded article having excellent design and deep shape with embossed printing on the surface. Moreover, when it was set as the transfer foil film, it was excellent in transparency, heat resistance, solvent resistance, and moldability, and was an excellent film as a film for transfer foil.
(Example 2)
As a polyester of the polyester (A) layer, a mixture of PBT pellets (96% by mass), particle master pellets MS-2 (2% by mass), and extender 2 (2% by mass) was used. A thickness of 75 μm (A) was obtained in the same manner as in Example 1 except that a mixture of PET pellets (90% by mass), PBT pellets (8% by mass), and extender 2 (2% by mass) was used as the polyester. Layer / B layer thickness = 22.6 μm / 42.4 μm). Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Example 3)
As a polyester of the polyester (A) layer, a mixture of PPT (97 mass%), pellets of particle master MS-3 (2 mass%) and extender 3 (1 mass%) is used as a polyester of the polyester (B) layer. 50 μm in thickness (A layer / B layer) in the same manner as in Example 1 except that a mixture of PET pellets (89 mass%), PPT (10 mass%), and extender 3 (1 mass%) was used. / A layer thickness = 10 μm / 30 μm / 10 μm). Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
Example 4
As a polyester of the polyester (A) layer, a mixture of PEN pellets (97% by mass), particle master MS-4 (2% by mass), and extender 4 (1% by mass) was used. ) Example 1 except that a mixture of PET pellets (89% by mass), PEN pellets (10% by mass) and extender 4 (1% by mass) was used as the polyester of the layer and the extrusion temperature was 285 ° C. A polyester film having a thickness of 60 μm (A layer / B layer / A layer thickness = 3 μm / 54 μm / 3 μm) was produced in the same manner. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Example 5)
PBT pellets (98% by mass) and particle master MS-2 (2% by mass) were used as the polyester in the polyester (A) layer, and PET pellets (79% by mass) and PBT were used as the polyester in the polyester (B) layer. 30 μm in thickness (A layer / B layer / A layer thickness = 7.5 μm / min) in the same manner as in Example 1 except that a mixture of 20% by mass of pellets and a mixture of extender 5 (1% by mass) was used. A polyester film of 15 μm / 7.5 μm) was produced. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Example 6)
As a polyester of the polyester (A) layer, a mixture of PBT pellets (97.5% by mass), particle master MS-2 pellets (2% by mass), and extender 1 (0.5% by mass) is used. B) 90 μm thickness (A layer / B layer / A layer thickness = 15 μm / 60 μm / 15 μm) in the same manner as in Example 1 except that PET-I (100 mass%) was used as the polyester of the layer. A polyester film was prepared. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Example 7)
As the polyester of the polyester (A) layer, a mixture of PBT pellets (97% by mass), particle master MS-2 pellets (2% by mass), and extender 1 (1% by mass) was used. A single-layer polyester film having a thickness of 100 μm was produced in the same manner as in the Examples except that polyester was not used. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Comparative Example 1)
As a polyester of the polyester (A) layer, a mixture of PET pellets (97% by mass), particle master MS-1 (2% by mass), and extender 1 (1% by mass) is used, and the extrusion temperature is 280 ° C. (B) A single-layer polyester film having a thickness of 100 μm was prepared in the same manner as in Example 1 except that a mixture of PET pellets (99% by mass) and extender 1 (1% by mass) was used as the polyester of the layer. Produced. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Comparative Example 2)
As a polyester of the polyester (A) layer, a mixture of PBT pellets (98% by mass) and particle master MS-2 (2% by mass) was used, and as a polyester of the polyester (B) layer, PET pellets (92% by mass) The thickness was 50 μm (A layer / B layer / A layer thickness = 0.8 μm / 48.4 μm / 0.00 mm) in the same manner as in Example 1 except that a mixture of PBT master pellets (8% by mass) was used. 8 μm) polyester film was prepared. Further, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Comparative Example 3)
A polyester film having a thickness of 100 μm (A layer / B layer / A layer thickness = 10 μm / 80 μm / 10 μm) was produced in the same manner as in Example 1 except that the temperature of the satin cast drum was 25 ° C. Further, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.
(Comparative Example 4)
As polyester of the polyester (A) layer, a mixture of PBT pellets (98.8% by mass), particle master MS-2 (0.2% by mass), and extender 1 (1% by mass) (150 ° C. × 4 hours reduced pressure) A mixture of PET pellets (99% by mass) and extender 1 (1% by mass) as a polyester in the polyester (B) layer (150 ° C. × 4 hours drying under reduced pressure), each was administered to a single screw extruder B set at an extrusion temperature of 280 ° C., passed through a 3-layer pinole of A layer / B layer / A layer, and a slit gap of 0.8 mm set at 280 ° C. The film was guided to a T die die, extruded into a film shape, and wound around a mirror surface metal drum maintained at 25 ° C. while being electrostatically applied to be cooled and solidified to obtain an unstretched film.

  Next, this unstretched film was stretched 3.2 times at 90 ° C. in the longitudinal direction, stretched 3.2 times at 115 ° C. in the width direction, heat-treated at 220 ° C., and a thickness of 30 μm (A layer / B Layer / A layer thickness = 3 μm / 24 μm / 3 μm) was produced. Also, a transfer foil and a cup-shaped molded product were produced in the same manner as in Example 1.

  Tables 1 and 2 collectively show the composition of the polyester used in the above Examples and Comparative Examples, and the evaluation results of the film properties.

In Table 1 and Table 2, the abbreviations used are shown.
PET: Polyethylene terephthalate PET-I: Isophthalic acid copolymerized polyethylene terephthalate PBT: Polybutylene terephthalate PPT: Polypropylene terephthalate PEN: Polyethylene naphthalate When the films obtained in Examples 1-2 and 5 were used as transfer foils, It was excellent in transparency, heat resistance, solvent resistance and moldability, and was an excellent film as a film for transfer foil.

  The film obtained in Example 3 was a film having excellent transparency and moldability, although heat resistance and solvent resistance were slightly inferior. There was no practical problem in heat resistance and solvent resistance.

  The films obtained in Example 4 and Example 7 were excellent in transparency, heat resistance and solvent resistance and slightly inferior in moldability, but there was no practical problem.

  On the other hand, the films obtained in Comparative Examples 1 to 4 were not films satisfying all of transparency, heat resistance, solvent resistance, and moldability.

  The polyester film of this invention can obtain the polyester film excellent in transparency, solvent resistance (printability), heat resistance, and moldability.

  More specifically, since the solvent resistance (printability) is excellent in solvent resistance to the solvent contained in the printing ink, particularly ethyl acetate, methyl ethyl ketone, toluene, acetone, etc., various printing inks may be used. it can. Moreover, it is excellent in especially a moldability by containing an extending | stretching agent in a polyester (A) layer and / or a polyester (B) layer.

  Since the polyester film of the present invention is excellent in moldability such as deep drawing, complex shape molding, etc., in-mold transfer foil used by printing and molding, automotive interior / exterior parts, bathroom panels, home appliance parts, It is suitably used as a transfer foil for performing printing transfer processing on packaging containers and the like.

Claims (6)

Having at least a polyester (A) layer spectral band full width at half maximum of 1730 cm ^-1 is less than 23cm ^-1 in the laser Raman method,
The polyester (A) layer contains an extender,
Under an atmosphere of 120 ° C., the stress at 400% elongation is in the range of 2 to 20 MPa,
A polyester film having a haze of 10% or less. Polyester (A) layer spectral band full width at half maximum of 1730 cm ^-1 in the laser Raman method is less than 23cm ^-1, polyester (B) layer spectral band full width at half maximum of 1730 cm ^-1 is 23cm ^-1 or more in the laser Raman Having at least
The polyester (A) layer and / or polyester (B) layer contains an extender,
Under an atmosphere of 120 ° C., the stress at 400% elongation is in the range of 2 to 20 MPa,
A polyester film having a haze of 10% or less. The extender is at least one selected from the group consisting of an aliphatic carboxylic acid amide and an N-substituted urea;
The layer containing the extender further contains at least one selected from the group consisting of aliphatic alcohols, sorbitol compounds, amino acids, and polypeptides, according to claim 1 or 2. Polyester film.   The polyester (A) which is the main component of the polyester (A) layer is a polyester comprising at least one selected from the group consisting of polypropylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and copolymers thereof. The polyester film according to any one of claims 1 to 3, wherein the polyester film is characterized.   The polyester film according to any one of claims 2 to 4, wherein the polyester (B) which is a main component of the polyester (B) layer is a polyester made of polyethylene terephthalate or a copolymer of polyethylene terephthalate. .   The polyester film according to claim 2, wherein the polyester film has a polyester (A) layer on both sides of the polyester (B) layer.