Laminated film

Abstract

To provide a laminated film which is flexible and has excellent transparency, and furthermore has high frame retardancy, and is composed of a polyester block copolymer.SOLUTION: There is provided a laminated film in which a coating layer (II layer) is applied to one surface or double surfaces of a layer (I layer) composed of a polyester block copolymer resin composition, wherein the I layer is a layer composed of a polyester block copolymer resin composition which contains 0.01-3 pts.mass of an aliphatic carboxylic acid alkali metal salt (B) having 10 or more and 20 or less carbon atoms or 0.2-20 pts.mass of an ethylene copolymer (C) having a carboxylic acid metal base on its side chain, with respect to 100 pts.mass of a polyester block copolymer (A) containing 10-50 mass% of a high melting point crystalline polymer segment (a) composed of a crystalline aromatic polyester unit and 90-50 mass% of a low melting point polymer segment (b) composed of an aliphatic polyester unit and / or an aliphatic polyester unit as main components, and the II layer is a coating layer containing flame retardant particles (H) having a refractive index of 1.40-1.60.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a laminated film. [Background technology]

[0002] In automotive interior parts and buildings (such as shops, hotels, and private homes), for example, the use of synthetic leather has increased from genuine leather to seat materials. Various synthetic resins are used as synthetic leather materials, including polyvinyl chloride and urethane resin. Leather materials require a good tactile feel and aesthetic appeal because they are touched by people, thus requiring flexible materials.

[0003] In recent years, decorative panels and display devices have been used in automotive interiors and buildings. For example, an automobile's instrument panel is equipped with a wide variety of display devices and controls, including speedometers and other instruments, the display and control units for car navigation systems, external monitors, and lighting. The materials used for the exteriors of such display devices in car interiors and buildings require high transparency to enhance visibility, as well as a pleasant tactile feel and aesthetic appeal, given that they are visible to the public. Furthermore, for safety reasons, flame retardancy is required, meaning that the material is difficult to burn even when exposed to flames, and that even if a portion burns, it does not easily spread. As an example of the use of transparent resin display devices, Patent Document 1 shows an example in which polycarbonate resin is used for the exterior of the instrument panel in the driver's seat of an automobile.

[0004] Furthermore, one possible method to improve the flame retardancy of translucent resins is to incorporate a flame retardant into the resin. Patent Document 2 shows a flame-retardant resin composition containing at least 50% by weight of polycarbonate resin, a specific phosphorus compound, and a thermoplastic resin. Patent Document 3 shows an optical fiber that exhibits a certain degree of transparency and flame retardancy by incorporating a metal phosphinate salt into a transparent elastomer resin such as polyester elastomer, polyamide elastomer, or polyurethane elastomer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent No. 5301847 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2004 - 18767 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2017 - 167358 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] However, since the polycarbonate resin as shown in Patent Document 1 is generally hard, it is useful as a structural part, but as a film that requires flexibility, it has poor touch and limited designability.

[0007] In Patent Document 2, although it contains a thermoplastic resin that is more flexible than the polycarbonate resin, since it contains 50% by weight of the polycarbonate resin, as a film that requires flexibility, it has poor touch and limited designability.

[0008] In Patent Document 3, since it contains a metal phosphinate such as aluminum hypophosphite as a flame retardant in the base resin, although some transparency is obtained, high transparency cannot be obtained, and it cannot be used for members or films that require visibility. Also, since it contains a large amount of flame retardants in the base resin, there is a concern about appearance defects such as bleed - out.

[0009] The present inventors focused on the refractive indices of the polyester block copolymer and the flame retardant, and considered that a film obtained by laminating a layer (I) composed of a specific polyester block copolymer resin composition and a layer (II) containing specific flame - retardant particles might be preferably used for a film having both flame retardancy and transparency, and thus made intensive efforts.

[0010] The object of the present invention is to provide a laminated film made of a polyester block copolymer resin composition that is flexible, maintains excellent transparency, and has high flame retardancy. Furthermore, the object of the present invention is to provide a film suitable for interior display devices by using the said film. [Means for solving the problem]

[0011] (1) A laminated film characterized in that a coating layer (II layer) is applied to one or both sides of a layer (I layer) made of a polyester block copolymer resin composition, wherein the I layer is made of a polyester block copolymer resin composition containing 10 to 50% by mass of a high-melting-point crystalline polymer segment (a) made of crystalline aromatic polyester units and 90 to 50% by mass of a low-melting-point polymer segment (b) made of aliphatic polyether units and / or aliphatic polyester units as the main components, and 0.01 to 3 parts by mass of an alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms or 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal base in the side chain, and the II layer is a coating layer containing flame-retardant particles (H) having a refractive index of 1.40 to 1.60. (2) The laminated film according to (1), characterized in that the flame-retardant particles (H) contain a sulfur compound or a phosphorus compound and have an average particle diameter of 10 nm or more and 2500 nm or less. (3) The laminated film according to (1) or (2), characterized in that the thickness of the coating layer (Layer II) is 1 μm or more and 20 μm or less. (4) The coating layer (Layer II) contains fine particles of a hydrotalcite-like compound containing a sulfur compound or a phosphorus compound, wherein the hydrotalcite-like compound containing the sulfur compound or phosphorus compound has a general formula [M 2+ 1-x M 3+ x (OH)2][A n- x / n It is represented as [·mH2O] and the host element is M 2+ and M 3+are Mg and Al, or Zn and Al respectively, and A which is an interlayer anion n- x / n is SO3NH2 - , S2O8 2- , SO3CF3 - , and P2O7 4- The laminated film according to any one of (1) to (3), characterized in that it is one or more selected from (5) The laminated film according to any one of (1) to (4), characterized in that the coating layer (II layer) contains a binder (G). (6) The laminated film according to any one of (1) to (5), characterized in that the total light transmittance of the laminated film is 60% or more. (7) The laminated film according to any one of (1) to (6), characterized in that the laminated film is an exterior film for an interior display device. [Advantages of the Invention]

[0012] It is possible to provide a laminated film made of a polyester block copolymer resin composition that is flexible, maintains excellent transparency, and has high flame retardancy. Furthermore, by using the film, it is intended to provide a film preferable for an interior display device of an automobile. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, embodiments of the present invention will be described in detail. The laminated film of the present invention is a laminated film in which a coating layer (II layer) containing specific flame retardant particles is applied to one or both sides of a layer (I layer) made of a specific polyester block copolymer resin composition.

[0014] The layer (I layer) made of the polyester block copolymer resin composition of the present invention is composed of a polyester block copolymer resin composition comprising a specific polyester block copolymer (A) and an alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms or an ethylene copolymer (C) having a carboxylic acid metal base in its side chain.

[0015] The polyester block copolymer resin composition preferably has a total light transmittance of 60% or more as measured in accordance with ASTM D1003 for a 2 mm thick sheet. Furthermore, it is preferable that the surface hardness conforming to JIS K7215 is 20 to 50D.

[0016] A layer made of a polyester block copolymer resin composition with a total light transmittance of 60% or more is transparent or translucent to the naked eye, ranging from those that are translucent to the naked eye but transmit light, allowing text to be easily read when placed on printed material, to those that are transparent to the naked eye and allow text to be very clearly visible when placed on printed material. A layer made of a polyester block copolymer resin composition with a total light transmittance of less than 60% is opaque to the naked eye, and text cannot be easily read when placed on printed material.

[0017] A layer made of a polyester block copolymer resin composition with a surface hardness of 20-50D, measured on a 2mm thick sheet according to JIS K7215, includes layers that deform significantly when pressed with a finger, as well as layers that deform only slightly. If the surface hardness is less than 20D, the strength is insufficient, and if the surface hardness is greater than 50D, a flexible feel cannot be obtained.

[0018] The refractive index of the polyester block copolymer resin composition is preferably 1.40 to 1.60. More preferably 1.42 to 1.58, and most preferably 1.45 to 1.55. The refractive index can be achieved by the weight ratio of a high-melting-point crystalline polymer segment (a) consisting of crystalline aromatic polyester units constituting the polyester block copolymer (A) and a low-melting-point polymer segment (b) consisting of aliphatic polyether units and / or aliphatic polyester units, or by including an alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms or an ethylene copolymer (C) having a carboxylic acid metal base in its side chain, within the scope of the present invention. Here, refractive index refers to the refractive index in the D line (light ray with a wavelength of 589 nm).

[0019] The layer (Layer I) made of the polyester block copolymer resin composition in the present invention contains 100 parts by mass of polyester block copolymer (A), which mainly consists of 10 to 50% by mass of a high-melting-point crystalline polymer segment (a) made of crystalline aromatic polyester units and 90 to 50% by mass of a low-melting-point polymer segment (b) made of aliphatic polyether units and / or aliphatic polyester units, and 0.01 to 3 parts by mass of alkali metal salt (B) of an aliphatic carboxylic acid having 10 to 20 carbon atoms, or 0.2 to 20 parts by mass of ethylene copolymer (C) having a carboxylic acid metal base in the side chain.

[0020] The polyester block copolymer (A) in the present invention mainly comprises a high-melting-point crystalline polymer segment (a) consisting of crystalline aromatic polyester units and a low-melting-point polymer segment (b) consisting of aliphatic polyether units and / or aliphatic polyester units.

[0021] The high-melting-point crystalline polymer segment (a) of the polyester block copolymer (A) in the present invention is a polyester formed from an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol, preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. In addition, it may be a dicarboxylic acid component such as isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or ester-forming derivatives thereof, and a diol with a molecular weight of 300 or less, for example, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol. Polyesters derived from aliphatic diols such as ethylene glycol, neopentyl glycol, and decamethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and tricyclodecanedimethylol; xylylene glycol; bis(p-hydroxy)diphenyl; bis(p-hydroxyphenyl)propane; 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane; bis[4-(2-hydroxy)phenyl]sulfone; 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane; 4,4'-dihydroxy-p-terphenyl; 4,4'-dihydroxy-p-quarterphenyl; and other aromatic diols; or copolymerized polyesters using two or more of these dicarboxylic acid and diol components in combination. It is also possible to copolymerize polyfunctional carboxylic acid components with three or more functions, polyfunctional oxyacid components, and polyfunctional hydroxyl components in amounts of 5 mol% or less.

[0022] The low-melting-point polymer segment (b) of the polyester block copolymer (A) in the present invention is an aliphatic polyether and / or aliphatic polyester. Examples of aliphatic polyethers include poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of poly(propylene oxide) glycol, and copolymers of ethylene oxide and tetrahydrofuran.

[0023] Examples of aliphatic polyesters include poly(ε-caprolactone), polyenanthractone, polycapryloractone, polybutylene adipate, and polyethylene adipate. From the elastic properties of the polyester block copolymers obtained among these aliphatic polyethers and / or aliphatic polyesters, poly(tetramethylene oxide) glycol, ethylene oxide adducts of poly(propylene oxide) glycol, poly(ε-caprolactone), polybutylene adipate, and polyethylene adipate are preferred. Furthermore, the number-average molecular weight of these low-melting-point polymer segments is preferably around 300 to 6000 in the copolymerized state.

[0024] In the present invention, the copolymerization amount of the high-melting-point crystalline polymer segment (a) in the polyester block copolymer (A) is 10 to 50% by mass, and the copolymerization amount of the low-melting-point polymer segment (b) is 90 to 50% by mass. Preferably, the copolymerization amount of the high-melting-point crystalline polymer segment (a) in the polyester block copolymer (A) is 10 to 40% by mass, and the copolymerization amount of the low-melting-point polymer segment (b) is 90 to 60% by mass. If the copolymerization amount of the high-melting-point crystalline polymer segment (a) is less than 10% by mass, the crystallinity becomes insufficient, resulting in poor moldability and heat resistance. On the other hand, if the copolymerization amount of the high-melting-point crystalline polymer segment (a) exceeds 50% by mass, the transparency desired by the present invention will not be sufficiently achieved.

[0025] The polyester block copolymer (A) in the present invention can be produced by known methods. For example, by transesterifying a lower alcohol diester of a dicarboxylic acid, an excess amount of low molecular weight glycol, and a low melting point polymer segment component in the presence of a catalyst, and then polycondensing the resulting reaction product. Alternatively, by esterifying a dicarboxylic acid, an excess amount of glycol, and a low melting point polymer segment component in the presence of a catalyst, and then polycondensing the resulting reaction product. Another method involves preparing a high melting point crystalline segment in advance, adding a low melting point segment component to it, and then randomizing it by transesterification. A third method involves linking the high melting point crystalline segment and the low melting point polymer segment with a chain linker. Furthermore, when poly(ε-caprolactone) is used as the low melting point polymer segment, any of the following methods may be used, such as adding the ε-caprolactone monomer to the high melting point crystalline segment.

[0026] The layer (Layer I) made of the polyester block copolymer resin composition in the present invention contains 0.01 to 3 parts by mass of an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B) or 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal base in its side chain, per 100 parts by mass of polyester block copolymer (A).

[0027] When the product contains 0.01 to 3 parts by mass of an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B) per 100 parts by mass of polyester block copolymer (A), it is preferably blended in the following proportions: preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 1 part by mass.

[0028] Aliphatic carboxylic acids are compounds in which a carboxyl group is attached to a linear or branched aliphatic group, and may have other substituents such as unsaturated groups, alicyclic groups, aromatic groups, hydroxyl groups, or phosphate ester groups in part of the bond. The number of carbon atoms in an aliphatic carboxylic acid is preferably 10 to 18, and more preferably 10 to 15. Examples of aliphatic carboxylic acids include capric acid (10 carbon atoms), undecylic acid (11 carbon atoms), lauric acid (12 carbon atoms), tridecylic acid (13 carbon atoms), myristic acid (14 carbon atoms), pentadecylic acid (15 carbon atoms), palmitic acid (16 carbon atoms), margaric acid (17 carbon atoms), stearic acid (18 carbon atoms), tuberculinostearic acid (19 carbon atoms), and arachidic acid (20 carbon atoms). Among these, capric acid, lauric acid, myristic acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid are preferred. Among alkali metal salts, sodium salts are preferred in terms of solubility in polyester elastomers and good crystal nucleation properties. In addition, one or more alkali metal salts (B) of aliphatic carboxylic acids having 10 to 20 carbon atoms may be used in combination.

[0029] Alkali metal salts of aliphatic carboxylic acids having 10 to 20 carbon atoms (B) are preferred from the viewpoints of solubility, compatibility with polyether ester block copolymers, and bleed-out. Alkali metal salts of aliphatic carboxylic acids having 9 or fewer carbon atoms are preferred because they can improve transparency with small amounts, but their short carbon chains cause bleed-out. Also, there is a risk of reduced adhesion to the coating layer. On the other hand, alkali metal salts of aliphatic carboxylic acids having more than 20 carbon atoms are preferred because their long carbon chains suppress bleed-out and inhibit the crystallinity of the polyether ester block copolymer, thereby improving transparency. However, large amounts are required to obtain sufficient transparency, and large amounts of addition cause bleed-out.

[0030] As described above, the layer (Layer I) made of the polyester block copolymer resin composition in the present invention contains 0.01 to 3 parts by mass of an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B) or 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal base in its side chain, per 100 parts by mass of polyester block copolymer (A).

[0031] When a polyester block copolymer (A) contains 100 parts by mass of ethylene copolymer (C) having a carboxylic acid metal base in its side chain, the amount of C added is preferably 0.5 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass. If the amount of ethylene copolymer (C) having a carboxylic acid metal base in its side chain is less than 0.2 parts by mass, the light transmittance and transparency are insufficient, and if it is 20 parts by mass or more, phase separation occurs, and it is thought that the mechanical properties and light transmittance and transparency decrease.

[0032] Ethylene copolymers (C) having a carboxylic acid metal base in the side chain are obtained by neutralizing copolymers of ethylene and ethylene-based unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid with alkali metal ions, alkaline earth metal ions, or zinc ions. These are commercially available, for example, as "Sarlin" from DuPont or "Hymiran" from Mitsui Dow Polychemicals. Among these, those neutralized with alkali metal ions such as sodium, potassium, and lithium are preferred.

[0033] The combined use of an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B) and an ethylene copolymer having a carboxylic acid metal base in its side chain (C) results in a synergistic effect, further improving transparency.

[0034] In the polyester block copolymer resin composition of the present invention, if heat resistance is required in the layer (Layer I), it is preferable to contain a hindered phenol-based radical scavenger (D) and a peroxide decomposer (E). If thermal discoloration is required, it is preferable that the hindered phenol-based radical scavenger (D) has a structure consisting of carbon and oxygen.

[0035] The amount of hindered phenol radical scavenger (D) is preferably 0.05 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of polyester block copolymer (A). More preferably 0.05 to 2.5 parts by mass, even more preferably 0.05 to 1.0 part by mass, and most preferably 0.05 to 0.5 parts by mass.

[0036] The amount of peroxide decomposing agent (E) is preferably 0.05 to 5.0 parts by mass per 100 parts by mass of polyester block copolymer (A). More preferably 0.05 to 2.5 parts by mass, more preferably 0.05 to 0.1 parts by mass, and most preferably 0.05 to 0.5 parts by mass.

[0037] The amount of hindered phenol radical scavenger (D) and peroxide decomposer (E) is important. If the amount of hindered phenol radical scavenger (D) and peroxide decomposer (E), which consist of carbon and oxygen, is less than 0.05 parts by mass, the effect of preventing thermal degradation is poor. If the amount of hindered phenol radical scavenger (D) and peroxide decomposer (E) exceeds 2.5 parts by mass, problems occur with bleed-out, discoloration due to heat, initial color tone, and appearance.

[0038] The hindered phenol radical scavenger (D) is preferably added during polymerization, but may also be added to the polyester block copolymer after polymerization.

[0039] Examples of hindered phenol radical scavengers (D) include tetrakis[methylene-3(3',5'-di-t-4'-hydroxyphenol)propionate]methane, 2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)mesitylene, 1,1,3-tri(4-hydroxy-2-methyl-5-t-butylphenyl)butane, 1,1-bis(3-t-butyl-6-methyl-4-hydroxyphenyl)butane, 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, pentaerythritol tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, and 3-(4-hydroxy-3 Examples include octyl 2,4-dimethyl-6(-1-methylpentadecyl)phenol ,5-diisopropylphenyl)propionate, bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene), 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4',4''-(1-methylpropanyl-3-inden)tris(6-t-butyl-m-cresol), 6,6'-di-t-butyl-4,4'-butylidene di-m-cresol, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0040] As the peroxide decomposing agent (E), phosphorus-based peroxide decomposing agents and sulfur-based peroxide decomposing agents are preferred. Since some phosphorus-based peroxide decomposing agents are hygroscopic, sulfur-based antioxidants are more preferred from a handling standpoint.

[0041] Phosphorus-based peroxide decomposing agents (E) include 3,9-bis(p-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tri(mononylphenyl)phosphite, triphenoxyphosphine, isodecylphosphite, and bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester. Phosphate, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl Mono(tridecyl) phosphite, trilauryl trithiophosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12~C15 alkyl)-4,4'-isopropylidene Diphenyl phosphite, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, trioctadecyl phosphite, tetraphenyltetratridecyl pentaerythritol tetraphosphite, diethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid, phenyl diisodecyl phosphite, diphenyldecyl phosphite, diphenylisodecyl phosphite, diphenyl(tridecyl) phosphite, tris(cyclohexylphenyl) phosphite, tris(4-phenylphenol) phosphite, diphenylnonylphenyl phosphite, di(nonylphenyl)dinonylphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl 4,4'-biphenylenediphosphonite), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, diisodecylpentaerythritol phosphite Examples include phytes, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrairubi(2,4-di-t-butylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphite, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(nonylphenyl) phosphite, cyclic neopentanetetrairubi(2,4-di-t-butyl-4-methylphenyl) phosphite, and cyclic neopentanetetrairbis(octadecyl) phosphite.

[0042] As sulfur-based peroxide decomposing agents (E), dilaurylthiopropionate, distearyltheodipropionate, laurylsteaaryltheodipropionate, dimyristylthiodipropionate, dioctadecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, dilauryl-3,3-thiodipropionate, dimyristyl-3,3'-thiodipropionate, dilaurylthiodipropionate, ditridecylthiodipropionate Examples include dimycythyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, distearyl-β,β'-thiodibutyrate, 3,3'-thiodipropionic acid, pentaerythritol tetra(β-lauryl thiopropionate ester), bis[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid] glycol ester, and thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0043] The polyester elastomer resin composition in the present invention may contain an ultraviolet absorber (F) and a hindered amine compound (G). The ultraviolet absorber (F) is a substance that absorbs in the ultraviolet region and is used to prevent the degradation of the polymer chain itself by absorbing ultraviolet light before it acts on the polymer chain and converting it into harmless substances such as heat. The hindered amine compound (G) is used to capture radicals generated by ultraviolet light. Preferably, the amine in the hindered amine compound (G) is of the third class. If the amine is of the first or second class, weather resistance is improved, but discoloration due to heat may occur.

[0044] Because UV absorbers (F) and hindered amine compounds (G) have different mechanisms for suppressing discoloration caused by light, combining them produces a synergistic effect.

[0045] For example, UV absorbers (F) that can be incorporated into the polyester elastomer resin composition of the present invention include 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)- Examples include 5-chloroben azotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2,5-bis-[5'-t-butylbenzoxazolyl-(2)]-thiophene, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and phenyl salicylate.

[0046] The ultraviolet absorber (F) is preferably one or more compounds selected from the group consisting of benzotriazole compounds, triazine compounds, and cyanoacrylate compounds. In particular, to improve appearance, an ultraviolet absorber with low absorbance in the wavelength range of 360 mm or more, which is the visible light range, is preferred.

[0047] As hindered amine compounds (G), polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, mono(1,2,2,6,6-pentamethyl) sebacate Examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butylpropanediate bis(1,2,2,6,6-pentamethyl-4-piperidyl)(-3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(2-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanediate bis[1,2,2,6,6-pentamethyl-4-piperidinyl]).

[0048] Among hindered amine compounds (G), it is preferable that the amine is of the tertiary class. Most preferably, the structure is one in which all atoms bonded to the nitrogen atom are carbon atoms.

[0049] The amounts of the ultraviolet absorber (F) and the hindered amine compound (G) are preferably 0.1 to 5.0 parts by mass, each per 100 parts by mass of the polyester block copolymer (A). More preferably, the amount is 0.1 to 2.5 parts by mass, and particularly preferably 0.1 to 1.0 part by mass.

[0050] The polyester block copolymer resin composition in the present invention may contain light stabilizers other than the ultraviolet absorber (F) and the hindered amine compound (G), but it is preferable that it contains only the ultraviolet absorber (F) and the hindered amine compound (G).

[0051] The polyester elastomer resin composition of the present invention may contain various other additives. In addition to the polyether ester block copolymer (A), the aliphatic carboxylic acid alkali metal salt (B) having 10 to 20 carbon atoms, and the ethylene copolymer (C) having a carboxylic acid metal base in its side chain, other additives widely used in polyester block copolymer resin compositions may be added, including flame retardants, inorganic fillers, stabilizers, and antioxidants.

[0052] In addition, other additives such as coloring pigments, inorganic and organic fillers, coupling agents, tack enhancers, quenchers, stabilizers such as metal deactivators, and polyfunctional glycidyl group-containing styrene polymers may be added. Alternatively, inorganic pigments such as carbon black and titanium dioxide, organic pigments, dyes, inks, heat stabilizers, light stabilizers, crosslinking agents, dispersants, lubricants, anti-slip agents, nucleating agents, foaming agents, antibacterial agents, deodorants, adsorbents, conductive agents, and flame retardants may also be included.

[0053] The polyester block copolymer resin composition in the present invention preferably comprises a total of 80% by mass or more of a polyether ester block copolymer (A), an aliphatic carboxylic acid alkali metal salt (B) having 10 to 20 carbon atoms, and / or an ethylene copolymer (C) having a carboxylic acid metal base in its side chain. More preferably, the total of (A), (B), (C), (D), (E) or (A), (B), (C), (D), (E), (F), (G) is 90% by mass or more, and even more preferably 95% by mass or more.

[0054] The method for producing the polyester block copolymer resin composition of the present invention is not particularly limited, but can be appropriately employed, for example, by supplying a raw material mixture of a polyester block copolymer, an alkali metal aliphatic carboxylic acid salt having 10 to 20 carbon atoms and / or an ethylene copolymer having a metal carboxylic acid base in its side chain, and other additives to a screw-type extruder and melt-kneading it, or by first supplying the polyester block copolymer to the screw-type extruder and melting it, and then supplying the ethylene copolymer having an alkali metal aliphatic carboxylic acid salt having 10 to 20 carbon atoms and / or a metal carboxylic acid base in its side chain, and other additives through another supply port and kneading them.

[0055] The coating layer (Layer II) containing specific flame-retardant particles contains flame-retardant particles (H) with a refractive index of 1.40 to 1.60. Examples of flame-retardant particles (H) with a refractive index of 1.40 to 1.60 include metal hydroxides, inorganic metal acid salts, metal oxides, metals, ceramics, silica, silicon dioxide, hydrotalcite, hydrotalcite-like compounds, glass beads, glass fibers, and organic polymers. It is preferable that the refractive index of the flame-retardant particles (H) is small compared to that of the layer (Layer I) made of polyester block copolymer resin composition.

[0056] The flame-retardant particles (H) preferably contain a sulfur compound or a phosphorus compound. The phosphorus-based and sulfur-based compounds may also contain ionic compounds, such as sulfate derivative ions, sulfonic acid derivative ions, and phosphate derivative ions.

[0057] The average particle diameter of the flame-retardant particles (H) is preferably between 10 nm and 2500 nm. More preferably it is 1000 nm or less, and even more preferably 800 nm or less. If the average particle diameter of the flame-retardant particles (H) is 2500 nm or more, it is possible that light transmission will be reduced.

[0058] The thickness of the coating layer (Layer II) is preferably 1 μm to 20 μm. More preferably, it is 1 μm to 10 μm. If the thickness of the coating layer (Layer II) is 20 μm or more, transparency will decrease and the inherent flexibility of the polyester block copolymer resin composition may be impaired. On the other hand, if it is less than 1 μm, sufficient flame retardancy may not be imparted. The thickness can be determined by measurement with an electron microscope or by converting the coating amount to thickness.

[0059] The coating layer (Layer II) preferably contains fine particles of a hydrotalcite-like compound containing a sulfur compound or a phosphorus compound. The hydrotalcite-like compound containing a sulfur compound or a phosphorus compound has a multilayer structure and has a general formula [M 2+ 1-x M 3+ x (OH)2][A n- x / n It is represented as [mH2O]. In this case, M 2+ and M 3+ is the host element, A n- x / n This is a guest ion, an interlayer anion. A known method can be used to micronize a multilayer structure such as hydrotalcite; for example, the method described in Japanese Patent Application Publication No. 2013-209488 may be used. Here, micron refers to particles with an average particle size of 2500 nm or less.

[0060] As a sulfate derivative ion, sulfamate ion (SO3NH2) - ), peroxodisulfate ion (S2O8 2- Examples include sulfate ions, persulfate ions, disulfate ions, sulfite ions, disulfite ions, thiosulfate ions, dithionite ions, hydrogen sulfate ions, fluorosulfonic acid ions, etc. Furthermore, examples of sulfonic acid derivative ions include aliphatic sulfonic acids such as trifluoromethanesulfonate ions and methylsulfonate ions; and aromatic sulfonic acid ions such as p-toluenesulfonate ions, p-phenolsulfonate ions, sulfophthalate ions, and polystyrenesulfonate ions. Among these, sulfamate ions (SO3NH2) are particularly noteworthy.- ), peroxodisulfate ion (S2O8 2- ), trifluoromethanesulfonate ion (SO3CF3 - ) is preferable.

[0061] Examples of phosphate derivative ions include phosphate ions, diphosphate ions, acidic phosphate ester ions, phosphate amide ions, polyphosphate ions, phosphite ions, hypophosphate ions, superphosphate ions, triphosphate ions, phosphonate ions, phosphinate ions, peroxomonophosphate ions, hexafluorophosphate ions, thiophosphate ions, thiophosphate ester ions, etc. Among these, diphosphate ions (P2O7) are particularly noteworthy. 4- ) is preferable.

[0062] The host element is M 2+ Ca 2+ Mg 2+ Fe 2+ Co 2+ ,Ni 2+ ,Cu 2+ Zn 2+ These are some examples. Also, M 3+ As for Al 3+ , Ti 3~4+ ,Cr 3+ Fe 3+ Co 3+ ,(Mo 5~6+ Examples include: M 2+ and M 3+ Preferred combinations include Mg and Al, and Zn and Al.

[0063] The coating layer (Layer II) preferably contains a binder (G). The binder (G) is not particularly limited, and various organic and inorganic compounds can be used as long as the adhesion between the layer (Layer I), which is made of a polyester block copolymer resin composition, and the coating layer (Layer II) is good. From the viewpoint of adhesion and moldability, organic compounds are preferred. Examples of organic compounds include polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives, polyacrylamide, polyamine, polyalkylene oxide, polypropylene glycol, urea resin, phenol resin, furan resin, acrylic acid polymer, melamine resin, starch, sugars, polyethyleneimine, polyamidine, oxazoline group-containing water-soluble polymer, acrylic resin, polyester resin, polyurethane, polyisocyanate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl chloride, epoxy resin, polycarbonate, amide resin, imide resin, polyphenylene ether, silicone, and the like. Among these, amide-based, imide-based, alcohol-based, polyester-based, acrylic-based, epoxy resins, ABS, PC, PBT, PET, and AS resins are preferred. The binder (G) is preferably added to the coating agent, which can significantly improve the flame retardancy of the laminated film. Furthermore, the binder content in the coating layer (layer II) is preferably 20% to 80% by mass, and more preferably 35% to 65% by mass, relative to the total solid content.

[0064] The coating layer (Layer II) may optionally contain metal hydroxides, inorganic powders, phosphoric acid compounds, sulfuric acid compounds, salts of alkyl sulfonic acids and phosphonic acids, and other dispersions, as well as additives (dispersants, organic solvents) that improve the workability, stability, water resistance, etc., of the flame retardant layer, within limits that do not impede the present invention.

[0065] For example, examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and hydrotalcite. Examples of inorganic powders include calcium carbonate powder, titanium dioxide powder, zinc oxide powder, molybdenum oxide powder, and zinc borate powder. Examples of phosphoric acid compounds include phosphates such as guazinidine phosphate, ammonium phosphate, melamine phosphate, ethylenediamine phosphate, piperazine phosphate, phosphate amides, and acidic phosphate esters, as well as their dimers, trimers, oligomers, and polymers. Examples of sulfuric acid compounds include sulfamic acid, peroxodisulfate, sulfuric acid, persulfate, ammonium salts of disulfate, and salts of amines such as melamine and ethylenediamine.

[0066] The coating layer (Layer II) can be formed by applying a coating solution containing flame-retardant particles (H) or flame-retardant particles (H) and a binder (G) to a layer (Layer I) made of a polyester block copolymer resin composition, drying it, and removing water and alcohol to form a thin flame-retardant film on the surface of the layer (Layer I) made of a polyester block copolymer resin composition.

[0067] The solvent for the coating solution may be either an aqueous or non-aqueous solvent, and can be arbitrarily selected and used within the range that achieves the effects of the present invention. Water is usually preferred, but other examples include alcohols such as methanol, ethanol, and isopropyl alcohol; glycols such as ethylene glycol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; glycol ethers such as methyl cellosolve and butyl cellosolve; nitrogen-containing compounds such as dimethylformamide and N-methylpyrrolidone; and carbonaceous compounds such as cyclohexane, n-hexane, isooctane, toluene, and xylene.

[0068] The coating solution contains 0.1% by mass or more, preferably 1% by mass, and more preferably 5% by mass or more, of the hydrotalcite-like compound. It also contains 50% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less, of the hydrotalcite-like compound.

[0069] For example, when a coating solution containing fine particles of a hydrotalcite-like compound containing a sulfur compound or a phosphorus compound is applied and heated, for example, it dehydrates and carbonizes [M 2+ 1-x M 3+ x O (2+x) / 2 It is believed that this layered structure remains, maintaining a dense layered structure. This layered structure can block oxygen, and because its refractive index is close to that of the layer (Layer I) made of polyester block copolymer resin composition, it can prevent combustion while maintaining transparency.

[0070] Furthermore, the coating layer (Layer II) containing fine particles of hydrotalcite-like compounds that contain sulfur compounds or phosphorus compounds forms a dense hydrotalcite-like compound layer, resulting in extremely low solubility in water and providing high water resistance to the layer (Layer I) made of polyester block copolymer resin composition. In addition, the dispersion itself is neutral to weakly alkaline and does not decompose, so it does not become acidic over time. As a result, the layer (Layer I) made of polyester block copolymer resin composition is not subjected to acid degradation.

[0071] The layer (Layer I) made of the polyester block copolymer resin composition preferably has good adhesion to the coating layer (Layer II), and it is particularly preferable that this adhesion is maintained even when heat is applied. As a result, the adhesion between the layer (Layer I) made of the polyester block copolymer resin composition and the coating layer (Layer II) is maintained even when heat is applied, so that the coating layer (Layer II) can act as a barrier to prevent the burning of the layer (Layer I) made of the polyester block copolymer resin composition. For this reason, the layer (Layer I) made of the polyester block copolymer resin composition preferably contains an ethylene copolymer (C) having a carboxylate metal base in its side chain, and it is preferable that it contains an ethylene copolymer (C) having a carboxylate metal base in its side chain and an aliphatic carboxylate alkali metal salt (B) having 10 to 20 carbon atoms. Furthermore, as mentioned above, it is preferable that the coating layer (Layer II) contains a binder (G).

[0072] It is preferable to further laminate a surface protection layer (Layer III) on top of the coating layer (Layer II) to improve abrasion resistance and scratch resistance, as well as to adjust the feel and gloss, and to enhance sterilization, deodorization, and conductivity, without impairing flexibility. By laminating the surface protection layer (Layer III), the coating layer (Layer II) becomes less likely to peel off from the layer (I) made of polyester block copolymer. Furthermore, by laminating the surface protection layer (Layer III), the smoothness of the flame-retardant particles contained in the coating layer (Layer II) can be improved, thereby improving transparency and cloudiness.

[0073] For the surface protective layer (Layer III), it is preferable to use a known resin such as an acrylic resin, polyester resin, or polyurethane resin. While there are no particular limitations on the thickness, a range of several micrometers to several tens of micrometers is preferred, as long as flexibility is not compromised.

[0074] As for other layers, a primer layer may be provided between the layer (I) made of the polyester block copolymer resin composition and the coating layer (II) to improve the adhesion between them, and a primer layer may also be provided between the surface protection layer (III) and the coating layer (II) to improve the adhesion between them.

[0075] To improve the adhesion between the polyester block copolymer layer (Layer I) and the coating layer (Layer II), the polyester block copolymer resin composition layer (Layer I) may be pre-treated. The pre-treatment method can be any known method, such as corona discharge treatment, ultraviolet treatment, plasma treatment, flame treatment, or primer treatment. Corona discharge treatment is particularly preferred.

[0076] The method for producing the layer (Layer I) made of the polyester block copolymer resin composition of the present invention is not particularly limited, but may be any known method such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, or in-mold molding. Examples of extrusion molding methods include molten casting, T-die method, and inflation method.

[0077] The method for laminating the coating layer (Layer II) is not particularly limited, but examples include spin coating, dipping, spraying, bar coating, gravure coating, roll coating, and die coating. In particular, bar coating, gravure coating, spraying, and die coating are preferred.

[0078] The laminated film of the present invention preferably has a total light transmittance of 60% or more, as measured according to ASTM D1003. Laminated films with a total light transmittance of 60% or more are transparent or translucent to the naked eye, and include those that are translucent to the naked eye but transmit light, allowing text to be easily read when this layer is placed on top of printed material, and those that are transparent to the naked eye and allow text to be extremely clearly seen when this layer is placed on top of printed material. Laminated films with a total light transmittance of less than 60% are opaque to the naked eye, and text cannot be easily read when this layer is placed on top of printed material.

[0079] The laminated film of the present invention is made of a polyester block copolymer resin composition and has excellent flexibility, transparency, and flame retardancy, making it suitable, for example, as an exterior film for interior display devices. Interior use refers to environments where the device is not directly exposed to sunlight or wind and rain, but is expected to be exposed to strong ultraviolet rays through glass. Specifically, this includes environments such as inside buildings (stores, hotels, and private homes, etc.) and inside automobiles.

[0080] For example, when used in a display device, the present invention comprises a display element including a light source and a laminated film of the present invention arranged to overlap the display element. The light source used in the display element is not particularly limited, but may be a conventionally known configuration including a liquid crystal element with a backlight, an electroluminescent element, or an LED.

[0081] The aforementioned exterior film refers to a film that decorates and protects the parts of the display element that are visible from the outside, and is a film that people may touch.

[0082] The interior display device using the laminated film of the present invention is preferably for use in the interior of an automobile, and is preferably used mainly around the windshield and side windows. For example, it is used in instrument panels and upholstery, and is preferably used in instrument panels. Examples of instrument panel parts include meter panels such as speedometers and tachometers, navigation panels such as car navigation systems, and control panels such as overhead control panels. Examples of upholstery parts include door trims, front panels, glove box panels, and shifter panels.

[0083] The laminated film of the present invention preferably has a thickness of 50 μm to 2 mm, and more preferably 100 μm to 1 mm, in order to impart flexibility. The surface condition can be smooth or uneven (in the case of an uneven surface, it may take the form of a geometric shape or a leather-like shape. Among these, a particularly preferred surface is a textured surface in which fine irregularities of 1 μm to 10 μm are formed within larger irregularities of 200 μm to 500 μm). The method for creating the uneven surface is not particularly limited, but any known method such as imprint transfer or resin coating may be used.

[0084] Furthermore, the laminated film of the present invention achieves excellent durability. Specifically, because it is a film made of a polyester block copolymer resin composition, it has excellent heat resistance, light resistance, chemical resistance, oil resistance, and flexural fatigue resistance. Due to its excellent heat resistance and weather resistance, it is less restricted by the atmosphere in which it can be used and can be used indoors or in vehicle interiors at high temperatures. Because it also has excellent chemical resistance and oil resistance, it does not deteriorate easily even when operated with hands that have oil on them or when used in environments where machine oil is present, so it can be used for touch panels, translucent surfaces, etc. In addition, because it has excellent flexural fatigue resistance, it can be used in next-generation flexible display devices and flexible modules.

[0085] The film of the present invention may have a multilayer structure, and the substrate that is laminated with and supports the film, which is made of a polyester block copolymer or the like, may be a piezoelectric film, a mirror film, a conductive film, a metal vapor-deposited film, a film having a circuit pattern, a touch panel, etc. The appearance of the film is not limited to the leather-like appearance described above, but may also be wood grain, wallpaper-like, metallic, stone-like, tile-like, etc.

[0086] Furthermore, the laminated film of the present invention has the added advantage of excellent moldability and heat sealability. For example, since the laminated film of the present invention is a polyester block copolymer, it has excellent adhesion to glass or resin glass placed on its surface, and is particularly excellent in heat adhesion and conformability to curved surfaces. In other words, since the laminated film of the present invention adheres firmly and without gaps to any display element, it is easy to form a display device of a desired shape. In addition, although it has excellent heat sealability, an adhesive may be used to further improve adhesion. [Examples]

[0087] The effects of the present invention will be explained below with reference to examples. Note that Example 7 shall be interpreted as Reference Example 1. In the examples, percentages and parts all refer to mass unless otherwise specified. Furthermore, the physical properties shown in the examples were measured as follows.

[0088] <Polyester block copolymer (Layer I)> • Melting point A differential scanning calorimeter (TA Instruments DSC Q1000) was used to measure the peak temperature of the melting point when heated at a heating rate of 10°C / min under a nitrogen gas atmosphere.

[0089] • Total light transmittance and haze value Using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industrial Co., Ltd., test specimens measuring 125 mm × 75 mm with a thickness of 2 mm were prepared at 220°C (mold temperature: 40°C). The surface roughness of the test specimens was measured using a VK-9700 manufactured by KEYENCE and was found to be 0.46 μm. Using these test specimens, the total light transmittance and haze value were measured according to ASTM D1003 using a DIRECT READING HAZEMETER manufactured by Toyo Seiki Seisakusho Co., Ltd.

[0090] • Surface hardness (Shore D scale) The aforementioned test specimens were measured in accordance with JIS K-7215.

[0091] ·exterior The printed material was placed beneath the aforementioned test specimen and evaluated according to the following criteria. ×: I am completely unable to read the text in printed materials. ○; Can read printed text. ◎; Able to clearly read the text in printed materials.

[0092] <Regarding laminated films> • Total light transmittance and haze value Using the laminated film described later, the total light transmittance and haze value were measured according to ASTM D1003 using a DIRECT READING HAZEMETER manufactured by Toyo Seiki Seisakusho Co., Ltd.

[0093] Flame retardant Using the laminated film described later, the combustion rate B (mm / min) was calculated in accordance with JIS-D1201-1998. The combustion rate was calculated as 60 × combustion distance (mm) / combustion time (sec), and the combustion rate was evaluated as follows. ×: Greater than 150 (mm / min) 〇: 100~150 (mm / min) ◎: Less than 100 (mm / min).

[0094] ·exterior The printed material was placed under the laminated film described later and evaluated according to the following criteria. ×: I am completely unable to read the text in printed materials. ○; Can read printed text. ◎; Able to clearly read the text in printed materials.

[0095] ·Flexibility ×: Cannot be stretched by hand. ○: Can be stretched by hand.

[0096] Reference example Production of polyester block copolymer (A-1) 278 parts terephthalic acid, 686 parts poly(tetramethylene oxide) glycol with a number average molecular weight of approximately 1400, 316 parts 1,4-butanediol, and 0.1 parts titanium tetrabutoxide were charged together in a reaction vessel equipped with a helical ribbon-type stirring blade, and the esterification reaction was carried out by heating at 190-225°C for 3 hours while distilling off the reaction water from the system. After adding 0.1 parts by mass of "IRGANOX" 1330 (a hindered phenol-based radical scavenger manufactured by BASF) to 100 parts by mass of the polyester block copolymer component, the temperature was raised to 245°C, and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 2 hours and 45 minutes. The obtained polymer was discharged in strand form into water and cut to form pellets.

[0097] Production of polyester block copolymer (A-2) 234 parts terephthalic acid, 754 parts poly(tetramethylene oxide) glycol with a number average molecular weight of approximately 2000, 228 parts 1,4-butanediol, and 0.2 parts titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon-type stirring blade, and the esterification reaction was carried out by heating at 190-225°C for 3 hours while distilling off the reaction water from the system. After adding 0.5 parts by mass of "IRGANOX" 1330 (a hindered phenol-based radical scavenger manufactured by BASF) to 100 parts by mass of the polyester block copolymer component, the temperature was raised to 245°C, and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 3 hours and 30 minutes. The obtained polymer was discharged in strand form into water and cut to form pellets.

[0098] Production of polyester block copolymer (A-3) 374 parts terephthalic acid, 610 parts poly(tetramethylene oxide) glycol with a number average molecular weight of approximately 1400, 335 parts 1,4-butanediol, and 0.2 parts titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon-type stirring blade, and the esterification reaction was carried out by heating at 190-225°C for 3 hours while distilling off the reaction water from the system. After adding 0.05 parts by mass of "IRGANOX" 1098 (a hindered phenol-based radical scavenger manufactured by BASF) to 100 parts by mass of the polyester block copolymer component, the temperature was raised to 245°C, and then the pressure in the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 2 hours and 45 minutes. The obtained polymer was discharged in strand form into water and cut to form pellets.

[0099] Table 1 shows the composition and physical properties of polyester block copolymers (A-1), (A-2), and (A-3).

[0100] [Table 1]

[0101] Preparation of layers (I-1 to I-5) made of polyester copolymer Polyester block copolymers (A-1), (A-2), and (A-3) obtained in the reference example were dry-blended with alkali metal salts of aliphatic carboxylic acids having 10 to 20 carbon atoms (NS-3A (sodium laurate) manufactured by Nitto Chemical Industries, Ltd.) (B-1), (sodium stearate manufactured by Nitto Chemical Industries, Ltd.) (B-2), and ethylene copolymers having a sodium carboxylate base in the side chain ("Sarlin" AD8610 manufactured by DuPont) (C-1) or ("Hymiran" 1707 manufactured by Mitsui Dow Polychemical Co., Ltd.) (C-2) in the proportions shown in Table 2. The mixture was then melt-kneaded and pelletized using a twin-screw extruder with a cylinder diameter of 45 mmφ.

[0102] After drying these pellets at 80°C for 3 hours, test specimens measuring 125 mm × 75 mm and 2 mm thick were prepared using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industrial Co., Ltd. at 220°C (mold temperature: 40°C). The total light transmittance (%), haze value (%), and surface hardness (D scale) were measured using the obtained 2 mm thick sheets, and their appearance was evaluated. The results are shown in Table 2. The refractive index measured using the 2 mm thick sheets according to JIS K7142 was 1.50 for the polyester copolymer layer (I-3) and 1.51 for the polyester copolymer layer (I-5).

[0103] Preparation of a layer (I-6) made of polyester copolymer After drying the polyester block copolymer (A-1) pellets obtained in the reference example at 80°C for 3 hours, test specimens measuring 125 mm × 75 mm and 2 mm thick were prepared using an electric injection molding machine (NEX-1000) manufactured by Nissei Plastic Industrial Co., Ltd. at 220°C (mold temperature: 40°C). The resulting 2 mm thick sheets were used to measure total light transmittance (%), haze value (%), and surface hardness (D scale), and their appearance was also evaluated. The results are shown in Table 2.

[0104] [Table 2]

[0105] As shown in Table 2, the layers (I-1 to I-5) made of the polyester block copolymer of the present invention are transparent. On the other hand, the layer (I-6) made of the polyester block copolymer that does not contain 0.01 to 3 parts by mass of an alkali metal salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms (B) or 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal base in the side chain, per 100 parts by mass of polyester block copolymer (A), was opaque.

[0106] <Coating layer (Layer II)> Manufacturing of the coating layer (H-1) Flame retardant particles with a refractive index of 1.40 to 1.60, general formula: Mg3Al(OH)8(CO3 2- ) 0.5 A commercially available carbonate-type LDH (Layered Double Hydroxide) represented as 2H2O, hydrotalcite (product name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: approximately 1 μm, refractive index: 1.51), was calcined at 700°C for 2 hours to obtain a calcined product of a specific inorganic layered compound. 34.4 parts by mass of the obtained calcined product were added to a mixture of 25.1 parts by mass of ammonium sulfamate (NH4SO3NH2) and 1500 parts by mass of decarboxylated deionized water, and stirred at 60°C for 2 hours to generate flame-retardant particles containing a guest compound, a sulfur compound. The precipitate of the sulfur compound-containing flame-retardant particles generated in solution was centrifuged and then washed with water. Water was added to the obtained precipitate of flame-retardant particles, and the mixture was highly dispersed to prevent precipitation, thereby obtaining a dispersion containing sulfur compound-containing flame-retardant particles. The average particle size of the sulfur compound-containing flame-retardant particles in the dispersion was measured using a dynamic light scattering analyzer (manufactured by Malvern Co., Ltd.) and found to be 210 nm. Furthermore, the refractive index measured using an Abbe refractometer in accordance with JIS K0062 was 1.50. In addition, a coating agent was prepared by adding a binder (amino-based resin, 20% solids, 25 parts by mass) to the obtained dispersion.

[0107] Manufacturing of the coating layer (H-2) As flame-retardant particles with a refractive index not between 1.40 and 1.60, alumina monohydrate (trade name: Boehmite C20, manufactured by Daimei Chemical Industry Co., Ltd., average particle size: approximately 2.3 μm, refractive index: 1.65), represented by the general formula AlOOH, was used, and a dispersion was obtained by adding water to achieve a solid content of 5% (by mass). A coating agent was then prepared by adding a binder (amino-based resin, solid content 20%, 25 parts by mass) to the obtained dispersion.

[0108] Example 1~ 7 Pellets prepared according to the mixing ratios shown in Table 2 were dried at 80°C for 3 hours, and then nipped by T-die extrusion with both sides sandwiched between PET films acting as separators to produce layers (I-1) to (I-5) consisting of film-like polyester block copolymers with widths of 1050 mm and thicknesses of 300 μm and 600 μm.

[0109] Coating solution (H-1) was dropped along one side of layers (I-1) to (I-5) made of polyester block copolymer to achieve the thickness shown in Table 3 after drying. The coating was applied by sliding a bar coater, and the layers were dried at room temperature for 5 minutes. Subsequently, the layers were dried in a forced-retention dryer at 120°C for 5 minutes and left at room temperature overnight or longer to produce laminated films. The total light transmittance (%) and haze (%) of the obtained laminated films were measured, and their appearance, flame retardancy, and flexibility were evaluated. The results are shown in Table 3.

[0110] Comparative Examples 1-2 Pellets prepared according to the mixing ratios shown in Table 2 were dried at 80°C for 3 hours, and then nipped by T-die extrusion with both sides sandwiched between PET films acting as separators to produce a layer (I-3) consisting of a film-like polyester block copolymer with a width of 1050 mm and a thickness of 300 μm.

[0111] In Comparative Example 1, no coating layer (Layer II) was provided. In Comparative Example 2, coating liquid (H-2) was dropped along one side of a layer (I-3) made of polyester block copolymer to achieve the thickness shown in Table 3 after drying, and the coating was applied by sliding a bar coater, and dried at room temperature for 5 minutes. After that, it was dried at 120°C for 5 minutes using a forced-retention dryer and left at room temperature overnight or longer to produce a laminated film. The total light transmittance (%) and haze (%) of the obtained laminated film were measured, and its appearance, flame retardancy, and flexibility were evaluated. Comparative Example 1 The results are shown in Table 3.

[0112] [Table 3]

[0113] As is clear from Examples 1 to 6 in Table 3, a laminated film comprising a polyester block copolymer (Layer I) containing 100 parts by mass of polyester block copolymer (A) whose main components are 10 to 50% by mass of high-melting-point crystalline polymer segments (a) consisting of crystalline aromatic polyester units and 90 to 50% by mass of low-melting-point polymer segments (b) consisting of aliphatic polyether units and / or aliphatic polyester units, and 0.01 to 3 parts by mass of alkali metal salt of an aliphatic carboxylic acid (B) having 10 to 20 carbon atoms or 0.2 to 20 parts by mass of ethylene copolymer (C) having a carboxylic acid metal base in the side chain, and a coating layer containing flame-retardant particles (H) with a refractive index of 1.40 to 1.60, exhibited high flame retardancy while maintaining flexibility and excellent transparency.

[0114] On the other hand, as shown in Comparative Example 1, the material that did not contain a coating layer (Layer II) containing flame-retardant particles (H) with a refractive index of 1.40 to 1.60 exhibited excellent flexibility and transparency, but poor flame retardancy. Also, Comparative Example 2 So Furthermore, coatings (Layer II) containing flame-retardant particles (H-2) with a refractive index of 1.65 (not 1.40-1.60) exhibited poor transparency and flame retardancy. [Industrial applicability]

[0115] The laminated film of the present invention is a laminated film having a layer made of a polyester block copolymer resin composition that is flexible, maintains excellent transparency, and has high flame retardancy. Therefore, it is used in interior applications where high design quality is required, particularly in automotive interior applications.

Claims

1. The laminated film is characterized in that a coating layer (Layer II) is applied to one or both sides of a layer (Layer I) made of a polyester block copolymer resin composition, wherein Layer I consists of 100 parts by mass of polyester block copolymer (A) whose main components are 10 to 50% by mass of a high-melting-point crystalline polymer segment (a) made of crystalline aromatic polyester units and 90 to 50% by mass of a low-melting-point polymer segment (b) made of aliphatic polyether units and / or aliphatic polyester units, and an aliphatic carboxylic acid alkali having 10 to 20 carbon atoms. A laminated film characterized by a layer made of a polyester block copolymer resin composition containing 0.01 to 3 parts by mass of a metal salt (B) or 0.2 to 20 parts by mass of an ethylene copolymer (C) having a carboxylic acid metal base in its side chain, wherein the II layer is a coating layer containing flame-retardant particles (H) having a refractive index of 1.40 to 1.60, the flame-retardant particles (H) containing a sulfur compound or a phosphorus compound, having an average particle diameter of 10 nm to 2500 nm, the thickness of the coating layer (II layer) being 1 μm to 20 μm, and a total light transmittance of 60% or more.

2. The coating layer (II layer) contains fine particles of a hydrotalcite-like compound containing a sulfur compound or a phosphorus compound, and the hydrotalcite-like compound containing the sulfur compound or the phosphorus compound has the general formula [M ２＋ １－ｘ M ３＋ ｘ (OH) ２ [A ｎ－ ｘ／ｎ ·mH ２ O], where the host elements M ２＋ and M ３＋ are Mg and Al, or Zn and Al, respectively, and the interlayer anion A ｎ－ ｘ／ｎ is SO ３ NH ２ － , S ２ O ８ ２－ , SO ３ CF ３ － , and P ２ O ７ ４－ The laminated film according to claim 1, characterized in that it is one or more selected from the above.

3. The laminated film according to claim 1 or 2, characterized in that the coating layer (layer II) contains a binder (G).

4. The laminated film according to claim 1 or 2, characterized in that the laminated film is an exterior film for an interior display device.

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